Dissertations / Theses: 'Photoelectrocatalytic'

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Kosa, Samia Abdulhamied. "Photoelectrocatalytic disinfection of E. coli by TiOâ‚‚." Thesis, University of Newcastle Upon Tyne, 2004. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.407580.

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Zaballa, Vicente. "Photoelectrocatalytic degradation of organic pollutants with TiOâ‚‚ electrodes." Thesis, University of Strathclyde, 2001. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.248657.

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Purnama, Herry. "Photocatalytic and photoelectrocatalytic Decolourization of Dyes by Titanium dioxide." Thesis, University of Newcastle Upon Tyne, 2009. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.506503.

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Li, Guiying. "A Tio2 Photoelectrocatalytic System for Wastewater Detoxification and Disinfection." Thesis, Griffith University, 2010. http://hdl.handle.net/10072/367000.

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This work systematically investigate the nanoparticulate TiO2 photocatalysis and photoelectrocatalysis based methods for decomposition, detoxification and disinfection of a series of biological contaminants ranged from small biological compounds such as amino acids and nucleotide bases, to large biological compounds including protein, lipid and DNA, to living microorganisms such as bacteria and virus. The small biological compounds (e.g., amino acids and nucleotide bases) are the basic building blocks of the large biological compounds (e.g., proteins and DNA), and the large biological compounds are the building blocks of the living microorganisms (e.g., bacteria and viruses). Due to the complicity involved, in order to understand the full spectrum of the decomposition, detoxification and disinfection mechanisms of living microorganisms, a bottom-up strategy was employed in this study. The photocatalytic and photoelectrocatalytic degradation of small biological compounds were firstly investigated to gain the necessary information for a better understanding of degradation mechanisms of large biological compounds. The photocatalytic and photoelectrocatalytic degradation of large biological compounds were then investigated to gain the necessary information for a better understanding of decomposition/disinfection mechanisms of living microorganisms. This was followed by the investigation of photocatalytic and photoelectrocatalytic decomposition/detoxification/disinfection of living microorganisms. Chapter 1 of the thesis provides comprehensive literature reviews of the present status of research developments relevant to this work and the justification for the research topic. Nanoparticulate TiO2 photoanode is a key element of the proposed research. Chapter 2 describes the fabrication and characterisation of the nanoparticulate TiO2 photoanode. The nanoparticulate TiO2 photoanode was successfully fabricated using a sol-gel method. The photoelectrocatalytic properties of the resultant TiO2 photoanodes were systematically evaluated using water, as well as organic model compounds in both bulk and thin-layer photoelectrochemical cells. The results indicated that the resultant photoanodes possess high photocatalytic activity. The measured net charge under the exhaustive conditions in a thin-layer photoelectrochemical cell is essentially the same as the theoretically required charge, demonstrating a superior oxidation power and 100% electron collection efficiency. Photocatalytic (PC) and photoelectrocatalytic (PEC) degradation of small biological compounds such as amino acids and nucleotide bases were carried out in Chapters 3 and 4. These small biological compounds were found to be photocatalytically and photoelectrocatalytically degradable. The degradation efficiency of PEC method was found to be higher than that of PC method for all compounds investigated. The organic nitrogens in the original compounds can be oxidised to either NH3/NH4 + or NO3- or both, depending the chemical structures of the original compounds and the degradation methods used. Both experimental results and the theoretically calculated frontier electron densities values of (2FEDHOMO)2 and (FEDHOMO)2+(FEDLUMO)2 demonstrated that the reaction mechanisms/pathways of PEC processes differed remarkably from that of PC processes. As a part of the proposed “bottom-up” strategy, PC and PEC degradation of large biological compounds such as bovine serum albumin (BSA), lecithin and bacteria genomic DNA were performed in Chapter 5. A new method for estimating the theoretical charge required to mineralise these large biological compounds with unknown chemical formula was firstly developed and experimentally validated. The degradation efficiency of PEC method was found to be higher than that of PC method for all large biological compounds investigated. In Chapter 6, a bactericidal technique (PEC-Br) utilising in situ photoelectrocatalytically generated photohole (h+), Br2•- and active oxygen species (AOS) for instant inactivation and rapid decomposition of Gram-negative bacteria such as E. coli was proposed and experimentally validated. The method is capable of inactivating 99.90% and 100% of 9×106 CFU/mL E. coli within 0.40 s and 1.57 s, respectively. To achieve the same inactivation effect, the PEC-Br method is 358 and 199 times faster than that of the PEC method, and 2250 and 764 times faster than that of the PC method. The Chapter 7 demonstrated the bactericidal technique developed in Chapter 6 can also be applied as a virucidal technique for rapid inactivation of viruses such as replication-deficient recombinant adenovirus (RDRADS). The PEC-Br method is capable of deactivating 99.77% and 100% of RDRADS within 14.32 s and 31.65 s, respectively. The final chapter of the thesis (Chapter 8) summarises the outcomes of this study and future work.
Thesis (PhD Doctorate)
Doctor of Philosophy (PhD)
Griffith School of Environment
Science, Environment, Engineering and Technology
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Cibrev, Dejan. "Photoelectrocatalytic and photoelectrochromic properties of composite nanostructured metal oxide films." Doctoral thesis, Universidad de Alicante, 2019. http://hdl.handle.net/10045/99689.

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Los materiales llamados semiconductores (muchos de ellos óxidos metálicos) son capaces de generar portadores de carga (huecos y electrones) cuando se iluminan con luz suficientemente energética. Estos portadores son capaces de sostener reacciones redox. Los electrones de la banda de conducción (BC) y los huecos de la banda de valencia (BV) pueden reducir y oxidar, respectivamente, especies que estén en contacto directo con el semiconductor. Además, los electrones y huecos fotogenerados pueden eliminarse en el proceso que se conoce como recombinación. El grado en que se producen estas reacciones redox depende de la eficiencia en la separación de las cargas fotogeneradas. Una separación de los portadores efectiva da lugar a aplicaciones. En esta tesis se abordan detalladamente los procesos de foto(electro)cromismo y foto(electro)catálisis. La separación de los portadores de carga en un material puede verse favorecida por: - La creación de heterouniones entre dos semiconductores (óxidos) distintos. - El diseño adecuado de la nanoestructura de los óxidos: estructuras ordenadas y/o estructuras con mucha superficie interfacial. - La modificación de la superficie o del seno de los óxidos semiconductores (dopado). En las aplicaciones prácticas se pretende que haya una transferencia de carga capaz de impulsar el proceso de interés. Por lo tanto, el control de los procesos de transferencia de carga del semiconductor a través de sus interfases es fundamental en el diseño de materiales para una determinada aplicación. Teniendo todo esto en cuenta, los objetivos establecidos para esta tesis han sido: I. Preparar estructuras ordenadas de nanobarras de α-Fe2O3 (hematita) sobre vidrio conductor e investigar sus propiedades catalíticas para fotooxidar agua. Optimizar el proceso de fotooxidación del agua sobre electrodos de hematita aplicando un pretratamiento electroquímico. Estudiar el efecto del pretratamiento sobre la composición, morfología y estructura electrónica de la hematita. II. Modificar los electrodos de hematita con Ti de dos maneras distintas, una que afecte principalmente a todo el material y otra que afecte a la superficie de la hematita, con el fin de mejorar sus propiedades catalíticas para fotooxidar agua. Aplicar y estudiar el pretratamiento reductivo para los electrodos de hematita tras ser modificados con Ti. III. Modificar la superficie de las nanobarras de hematita con trimetilaluminio (TMA) mediante depósito de capa atómica (Atomic layer deposition - ALD) desde fase gas o por adsorción en fase líquida, con el fin de mejorar sus propiedades fotoelectroquímicas para oxidar agua. Investigar los cambios en las propiedades electrónicas y electroquímicas de los electrodos de hematita tras ser modificados. IV. Preparar electrodos nanoporosos de Ni(OH)2 sobre vidrio conductor (SnO2:F - FTO) e investigar sus propiedades catalíticas para oxidar agua en medio alcalino en función de la cantidad depositada y de la morfología del hidróxido. V. Preparar electrodos nanoporosos basados en capas mixtas TiO2/Ni(OH)2 sobre vidrio conductor e investigar la separación de carga en los mismos con el fin de estudiar su posible utilización en dispositivos fotoelectrocrómicos. Estudiar las cinéticas de los procesos de la coloración y decoloración a través de medidas (foto)(espectro)electroquímicas. Las siguientes cinco conclusiones generales resumen los resultados más importantes en relación con los cinco objetivos previamente mencionados. I. En este estudio se ha conseguido sintetizar barras de hematita nanoestructuradas y con orientación (110) depositadas sobre vidrio conductor a través de un método de baño químico. Estas capas se han utilizado para estudiar el proceso de fotoxidación del agua. Para mejorar las propiedades fotocatalíticas de estas capas se ha empleado un pretratamiento electroquímico simple y altamente controlable que consiste en la aplicación de potenciales negativos por un tiempo muy corto (en el rango de segundos). Este pretratamiento da lugar a una mejora de la fotocorriente de hasta ocho veces asociada a la oxidación del agua, junto con un desplazamiento negativo de 20 mV del potencial de inicio de la fotocorriente. Este pretratamiento también induce cambios en la morfología de los electrodos, capacidad electrocatalítica y en su estructura electrónica. Por lo tanto, el dopado electroquímico no puede considerarse simplemente como un dopado tipo-n capaz de aumentar la fotoactividad de las capas debido a una mejora en el transporte de electrones. En realidad, los resultados obtenidos muestran claramente que se producen cambios mucho más profundos en la estructura electrónica y la composición de las capas que mejoran significativamente las propiedades tanto electro- como foto-electrocatalíticas. De hecho, ambas propiedades siguen una tendencia general similar con el potencial del pretratamiento empleado. Dentro de un marco más general, el pretratamiento reductivo puede ser utilizado también para la mejora de estructuras de hematita previamente modificadas o dopadas. Desde una perspectiva práctica, el dopaje electroquímico tiene la limitación de no ser permanente, lo que significa que debe aplicarse periódicamente. Esto no es un inconveniente serio en un dispositivo práctico, siempre y cuando la mejora inducida por el pretratamiento compense claramente esta limitación. II. Se han diseñado dos estrategias de modificación de hematita económicas utilizando una disolución con un mismo precursor de Ti. En un procedimiento el Ti se introduce en la estructura de hematita, mientras que en la otra, se forma una capa de TiO2 ultra-delgada que cubre por completo la superficie de hematita. Ambas modificaciones inducen un aumento significativo en la fotocorriente para la oxidación de agua (4 - 6 veces). La razón principal de la mejora en las capas modificadas con Ti es la disminución significativa del proceso de recombinación. El freno de la recombinación en las muestras modificadas con una sobre-capa de TiO2 se atribuye principalmente al bloqueo de estados superficiales, mientras que en el caso de las muestras modificadas con Ti intercalado en la estructura se relaciona principalmente con el aumento del área interfacial junto con un aumento de la conductividad electrónica. III. Se han preparado electrodos basados en nanobarras de hematita modificadas con TMA empleando una estrategia simple de impregnación a partir de una disolución de hexano. Los resultados se han comparado con los obtenidos modificando los electrodos de hematita con TMA por ALD. Los electrodos modificados muestran una importante mejora, aumentando tres veces la fotocorriente de oxidación de agua. Por un lado, el TMA bloquea los estados superficiales de hematita y por otro, induce un enriquecimiento electrónico. Tal conclusión fue confirmada cualitativamente en el caso de muestras modificadas con TMA utilizando la técnica de ALD. A pesar de que la modificación en fase líquida ha dado una foto-actividad menor en términos de la magnitud de la fotocorriente que la de ALD, representa una alternativa mucho más económica. Además, el método de impregnación a partir de una disolución es industrialmente escalable. Dentro de un marco más general, la modificación con TMA es potencialmente aplicable a otros semiconductores tipo n. Por lo tanto, podría constituir una estrategia relevante para mejorar la eficiencia de la fotooxidación de agua utilizando otros materiales tales como TiO2, BiVO4, WO3, entre otros. IV. Este estudio muestra que, a través de un procedimiento simple y potencialmente escalable como el baño químico, se pueden producir capas nanoestructuradas ultra-finas de Ni(OH)2 sobre FTO. Estas películas se caracterizan por una gran actividad electrocatalítica. Son capaces de oxidar el agua desarrollando corrientes iguales o superiores a las de películas mucho más gruesas. Esto último está relacionado con el hecho de que la reacción de generación de oxígeno depende de la formación de níquel (IV) que puede verse limitada por la baja conductividad eléctrica de Ni(OH)2. Por tanto, el proceso se favorece en capas finas donde la distancia al substrato conductor es menor. Esta noción es muy importante de cara a su aplicación. No solo se minimiza la cantidad de Ni(OH)2 necesaria sino se producen también ánodos altamente eficientes transparentes y prácticamente incoloros. V. Este trabajo ha mostrado que una capa nanoporosa mixta y delgada de TiO2/Ni(OH)2 depositada sobre vidrio conductor y sometida a un potencial catódico constante puede colorearse al ser iluminada con luz ultravioleta, mientras que se decolora completamente cuando se interrumpe la iluminación. Este fenómeno se ha denominado “fotoelectrocromismo reversible potenciostatico”. El valor del potencial empleado permite seleccionar tanto el contraste en la coloración como la cinética de la decoloración. Este fenómeno es posible debido a la existencia de un área interfacial extendida de contacto TiO2/Ni(OH)2 debido a la estructura nanoporosa que permite un contacto íntimo entre ambos componentes. Desde un punto de vista práctico, estos resultados podrían facilitar el desarrollo de ventanas inteligentes con una nueva funcionalidad porque, además del convencional efecto electrocrómico, trabajarían en un segundo modo, en el que, la coloración respondería a la intensidad de la luz incidente (a un potencial constante).

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Yu, Jie. "IN SITU INFRARED STUDIES OF CARBON DIOXIDE CAPTURE AND PHOTOELECTROCATALYTIC REDUCTION." University of Akron / OhioLINK, 2017. http://rave.ohiolink.edu/etdc/view?acc_num=akron1502103664018951.

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Sohn, Yon S. "Photoelectrocatalytic degradation of organic dye molecules on titanium dioxide nanotubular array." abstract and full text PDF (UNR users only), 2008. http://0-gateway.proquest.com.innopac.library.unr.edu/openurl?url_ver=Z39.88-2004&rft_val_fmt=info:ofi/fmt:kev:mtx:dissertation&res_dat=xri:pqdiss&rft_dat=xri:pqdiss:1455707.

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Osugi, Marly Eiko. "Avaliação de processos de degradação de corantes dispersos por técnicas eletroquímica e fotoeletroquímica usando eletrodos de Pt, filmes finos e nanotubos de 'TI'/'TI"O IND. 2' e bicomponentes 'W'/'W"O IND. 3'/'TI"O IND. 2' /." Araraquara : [s.n.], 2008. http://hdl.handle.net/11449/105732.

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Orientador: Maria Valnice Boldrin Zanoni
Banca: Paulo Roberto Bueno
Banca: Arthur de Jesus Motheo
Banca: Romeu Cardozo Rocha Filho
Bana: Rodnei Bertazolli
Resumo: O comportamento eletroquímico de três corantes dispersos, Vermelho Disperso 1, Laranja Disperso 1 e Vermelho Disperso 13 foi investigado em N,N-dimetilformamida usando tetrafluorborato de tetrabutilamônio como eletrólito de suporte. O grupo nitro dos corantes é reduzido em potenciais de -0,85 V, -0,79 V e -0,69 V, respectivamente, para os corantes Vermelho Disperso 1, Laranja Disperso 1 e Vermelho Disperso 13. A oxidação do grupo amino, também presente nos corantes investigados, ocorre, respectivamente, em potencial de 0,95 V, 0,90 V e 1,0 V e promove a clivagem do grupo azo. Devido à toxicidade e mutagenicidade destes corantes, analisada pelos testes de citotoxicidade em células humanas embrionárias HEK293 e de Ames, respectivamente, investigou-se no presente trabalho novos métodos de degradação dos mesmos em meio aquoso usando o agente dispersante comercial "Emulsogen" por meio de tratamento com cloro ativo (cloração convencional) e fotoeletroquimicamente pela geração de radicais cloro "in situ" sobre eletrodos nanoparticulados de Ti/TiO2, preparados pelo método sol-gel, em NaCl 0,1 mol L-1. A oxidação fotoeletrocatalítica, sobre eletrodos nanoparticulados de Ti/TiO2 em NaCl, mostrou-se mais eficiente quando comparada à cloração convencional, tanto na descoloração que promoveu 100% de remoção de cor, quanto na mineralização dos mesmos (até 60% de remoção de COT). A mutagenicidade dos corantes estudados foi drasticamente reduzida após tratamento fotoeletroquímico. No entanto, a cloração convencional não foi eficiente para total remoção da atividade mutagênica dos corantes, observando-se, ainda, um aumento para o corante Vermelho Disperso 13. A degradação também foi investigada sobre eletrodos de nanotubos de Ti/TiO2, preparados pelo método de anodização eletroquímica... (Resumo completo, clicar acesso eletrônico abaixo)
Abstract: The electrochemical behavior of three disperse dyes, Disperse Red 1, Disperse Orange 1 and Disperse Red 13, was investigated using N,N-dimethylformamide using in tetrabutylammonium tetrafluoroborate as supporting electrolyte. The nitro group of the dyes is reduced in potential of -0.85 V, 0.79 V and -0.69 V, respectively, for Disperse Red 1, Disperse Orange 1 and Disperse Red 13. The oxidation of amine group, also presents in the dyes molecules, occurs, respectively, at 0.95 V, 0.90 V and 1.0 V and promotes cleavage of azo group. Because of these dyes toxicity and mutagenicity, analyzed by citotoxicity in embryonic human cells HEK293 and mutagenicity detected by Ames test, respectively, new methods of degradation of these dyes in aqueous medium using the commercial dispersant agent "Emulsogen" was investigated by active chlorine treatment (conventional chlorination) and photoelectrochemically by "in situ" chlorine radicals generation using Ti/TiO2 nanoparticulates electrodes, prepared by solgel method, in 0.1 mol L-1 NaCl. The photoelectrocatalytic oxidation, using Ti/TiO2 nanoparticulates electrodes in NaCl presented higher efficiency when compared to conventional chlorination, leading to 100% of color removal and also 60% of mineralization of dyes measured as TOC removal. The mutagenicity of all investigated dyes was dramatically reduced after photoelectrochemical treatment. However, the conventional chlorination was not efficient for mutagenic activity removal of dyes and promoted an increase for Disperse Red 13. The degradation was also investigated using Ti/TiO2 nanotubes electrodes, prepared by electrochemical anodization in fluoride medium and characterized by SEM and photocurrent curves. These electrodes presented 100% of discoloration of all investigated dyes and total organic carbon removal around 70% after 3 hours of photoelectrocatalytic degradation... (Complete abstract click electronic access below)
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Zhang, Lin. "Photoelectrocatalytic CO2 conversion in ionic liquid/aqueous mixture solution studied by scanning electrochemical microscopy." Thesis, Sorbonne université, 2020. https://accesdistant.sorbonne-universite.fr/login?url=http://theses-intra.upmc.fr/modules/resources/download/theses/2020SORUS122.pdf.

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Cette thèse concerne l’étude de la réaction photoélectrochimique de réduction du CO2 (PEC CO2RR) sur le semi-conducteur de type p CuCo2O4 en abordant le rôle cocatalytique des RTIL à base d'imidazolium par microscopie photoélectrochimique à balayage (SPECM). Le CuCo2O4 a été étudié dans différents électrolytes supports, notamment une solution aqueuse, une solution de mélange binaire (25 vol.% [C2mim][BF4]/H2O et 25 vol.% [C4mim][BF4]/H2O) et des liquides ioniques pur pour explorer par SPECM le rôle des RTIL dans les performances des PEC. Un courant de photoréduction significativement amélioré sous l'éclairage UV-vis et visible est obtenu dans une solution à 25 vol.% [C2mim][BF4]/H2O. Seul le CO généré par la PEC CO2RR a été détecté sur une fibre optique à double sonde - ultra-microélectrode (OF-UME) développée au laboratoire et sur une électrolyse en volume sous illumination. La formation de CO à des potentiels plus positifs que la valeur thermodynamique est rapportée ici et il est clairement indiqué que la réduction directe du CO2 à la surface de l'électrode n'est pas le mécanisme. Un schéma de réaction possible pour la PEC CO2RR par l'intermédiaire de [C2mim]+ est proposé. Ainsi, nos résultats ont démontré pour la première fois le rôle cocatalytique de [C2mim]+ pour le PEC CO2RR. En outre, la CO2RR électrochimique a également été étudiée sur divers catalyseurs de métaux de transition, d'azote et de carbone (M–N–Cs). 25%Fe25%Co–N–C a montré la meilleure performance parmi les M–N–Cs étudiés. La présence de sites Co a fourni un effet synergique pour la génération de microcubes distribués riches en Fe, qui agissent comme des sites actifs dans la CO2RR électrochimique
This thesis studies photoelectrochemical CO2 reduction reaction (PEC CO2RR) on p-type semiconductor CuCo2O4 addressing the cocatalytic role of imidazolium based RTILs by scanning photoelectrochemical microscopy (SPECM). CuCo2O4 was studied in different solvent supporting electrolyte systems including: aqueous solution (0.1 M KHCO3 and 0.1 M Na2SO4), binary mixture solution (25 vol.% [C2mim][BF4]/H2O and 25 vol.% [C4mim][BF4]/H2O) and pure RTILs ([C2mim][BF4], [C4mim][BF4]) to explore by SPECM the role of RTILs in CuCo2O4 semiconductor PEC performance. Significantly enhanced photoreduction current under both UV-vis and visible light illumination is reported in 25 vol.% [C2mim][BF4]/H2O solution. Only CO generated from PEC CO2RR was detected using an in-situ detection method based on a home-made dual tip optical fiber-ultramicroelectrode (OF-UME) and from bulk electrolysis under illumination. The formation of CO at potentials more positive than the thermodynamic value clearly points out that direct CO2 reduction on the electrode surface is not the mechanism. A possible reaction scheme for the PEC CO2RR mediated by [C2mim]+ is proposed. Thus, our results have demonstrated for the first time the cocatalytic role of [C2mim]+ for the PEC CO2RR. In addition, electrochemical CO2RR has also been studied on various synthesized transition metal–nitrogen–carbon catalysts (M–N–Cs) by rotating disk electrode. 25%Fe25%Co–N–C exhibited the best performance among the studied M–N–Cs in this thesis. The presence of Co sites in that catalyst provided synergic effect for the generation of distributed Fe-rich microcubes, which act as active sites in electrochemical CO2RR

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Todd, Malcolm John. "Development and characterisation of a WO3-based photoanode for application in a photoelectrocatalytic fuel cell." Thesis, Available from the University of Aberdeen Library and Historic Collections Digital Resources, 2009. http://digitool.abdn.ac.uk:80/webclient/DeliveryManager?application=DIGITOOL-3&owner=resourcediscovery&custom_att_2=simple_viewer&pid=33583.

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Gutkowski, Ramona [Verfasser], Wolfgang [Gutachter] Schuhmann, and Martin [Gutachter] Muhler. "Photoelectrocatalytic energy conversion using metal oxide composite photoanodes / Ramona Gutkowski. Gutachter: Wolfgang Schuhmann ; Martin Muhler." Bochum : Ruhr-Universität Bochum, 2016. http://d-nb.info/1112326790/34.

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Osugi, Marly Eiko [UNESP]. "Avaliação de processos de degradação de corantes dispersos por técnicas eletroquímica e fotoeletroquímica usando eletrodos de Pt, filmes finos e nanotubos de 'TI'/'TIO IND. 2' e bicomponentes 'W'/'WO IND. 3'/'TIO IND. 2'." Universidade Estadual Paulista (UNESP), 2008. http://hdl.handle.net/11449/105732.

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Made available in DSpace on 2014-06-11T19:35:07Z (GMT). No. of bitstreams: 0 Previous issue date: 2008-06-26Bitstream added on 2014-06-13T18:46:17Z : No. of bitstreams: 1 osugi_me_dr_araiq.pdf: 5124429 bytes, checksum: 14021678a48aab65aa631f6d8a8b3003 (MD5)
Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
O comportamento eletroquímico de três corantes dispersos, Vermelho Disperso 1, Laranja Disperso 1 e Vermelho Disperso 13 foi investigado em N,N-dimetilformamida usando tetrafluorborato de tetrabutilamônio como eletrólito de suporte. O grupo nitro dos corantes é reduzido em potenciais de -0,85 V, -0,79 V e -0,69 V, respectivamente, para os corantes Vermelho Disperso 1, Laranja Disperso 1 e Vermelho Disperso 13. A oxidação do grupo amino, também presente nos corantes investigados, ocorre, respectivamente, em potencial de 0,95 V, 0,90 V e 1,0 V e promove a clivagem do grupo azo. Devido à toxicidade e mutagenicidade destes corantes, analisada pelos testes de citotoxicidade em células humanas embrionárias HEK293 e de Ames, respectivamente, investigou-se no presente trabalho novos métodos de degradação dos mesmos em meio aquoso usando o agente dispersante comercial “Emulsogen” por meio de tratamento com cloro ativo (cloração convencional) e fotoeletroquimicamente pela geração de radicais cloro “in situ” sobre eletrodos nanoparticulados de Ti/TiO2, preparados pelo método sol-gel, em NaCl 0,1 mol L-1. A oxidação fotoeletrocatalítica, sobre eletrodos nanoparticulados de Ti/TiO2 em NaCl, mostrou-se mais eficiente quando comparada à cloração convencional, tanto na descoloração que promoveu 100% de remoção de cor, quanto na mineralização dos mesmos (até 60% de remoção de COT). A mutagenicidade dos corantes estudados foi drasticamente reduzida após tratamento fotoeletroquímico. No entanto, a cloração convencional não foi eficiente para total remoção da atividade mutagênica dos corantes, observando-se, ainda, um aumento para o corante Vermelho Disperso 13. A degradação também foi investigada sobre eletrodos de nanotubos de Ti/TiO2, preparados pelo método de anodização eletroquímica...
The electrochemical behavior of three disperse dyes, Disperse Red 1, Disperse Orange 1 and Disperse Red 13, was investigated using N,N-dimethylformamide using in tetrabutylammonium tetrafluoroborate as supporting electrolyte. The nitro group of the dyes is reduced in potential of –0.85 V, 0.79 V and –0.69 V, respectively, for Disperse Red 1, Disperse Orange 1 and Disperse Red 13. The oxidation of amine group, also presents in the dyes molecules, occurs, respectively, at 0.95 V, 0.90 V and 1.0 V and promotes cleavage of azo group. Because of these dyes toxicity and mutagenicity, analyzed by citotoxicity in embryonic human cells HEK293 and mutagenicity detected by Ames test, respectively, new methods of degradation of these dyes in aqueous medium using the commercial dispersant agent “Emulsogen” was investigated by active chlorine treatment (conventional chlorination) and photoelectrochemically by “in situ” chlorine radicals generation using Ti/TiO2 nanoparticulates electrodes, prepared by solgel method, in 0.1 mol L-1 NaCl. The photoelectrocatalytic oxidation, using Ti/TiO2 nanoparticulates electrodes in NaCl presented higher efficiency when compared to conventional chlorination, leading to 100% of color removal and also 60% of mineralization of dyes measured as TOC removal. The mutagenicity of all investigated dyes was dramatically reduced after photoelectrochemical treatment. However, the conventional chlorination was not efficient for mutagenic activity removal of dyes and promoted an increase for Disperse Red 13. The degradation was also investigated using Ti/TiO2 nanotubes electrodes, prepared by electrochemical anodization in fluoride medium and characterized by SEM and photocurrent curves. These electrodes presented 100% of discoloration of all investigated dyes and total organic carbon removal around 70% after 3 hours of photoelectrocatalytic degradation... (Complete abstract click electronic access below)

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13

Tian, Fang. "Studies of LPCVD and anodised TiOâ†2 thin films and their photoelectrocatalytic photochemical properties for destruction of organic effluents." Thesis, University of Strathclyde, 2001. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.366874.

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14

Tinlin, James Robert. "Photoelectrocatalysis by TIOâ‚‚ electrodes." Thesis, University of Newcastle Upon Tyne, 2002. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.270802.

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15

Li, Wei. "Understanding and Controlling Photoelectrode Surface for Solar Fuel Production and Beyond." Thesis, Boston College, 2018. http://hdl.handle.net/2345/bc-ir:108121.

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Thesis advisor: Udayan Mohanty
Among the existing strategies to direct solar energy harvesting and storage, solar fuel production by photoelectrocatalysis promises a comparatively simple, low-cost route. The science behind this process is straightforward: stable semiconductors absorb sunlight and use the energy to excite charges, which then drive redox reactions at the surface. Careful studies of the photoelectrode surface provide important considerations in building a high-performance photoelectrode. Specifically, I focused on controlling the surface band alignment of Cu2O photocathode|water for hydrogen evolution reaction. A ZnS buried heterojunction is formed to improve the photovoltage. Then I focused on understanding the influence of chemical species on surface kinetics and energetics for water oxidation reaction. Two hematite photoanodes with preferably exposed {001} and {012} facets were examined. Further, I systematically studied three different types of surfaces, bare hematite, hematite with a heterogenized Ir water oxidation catalyst (WOC), and a heterogeneous IrOx WOC. While both WOCs improve the performance of hematite by a large margin, their working mechanisms are found to be fundamentally different. I also focused on utilizing surface photoexcited species to control product selectivity. Selective CO production by photoelectrochemical methane oxidation is successfully demonstrated. Detailed experimental investigations revealed that a synergistic effect by adjacent Ti3+ sites is the key to CO formation
Thesis (PhD) — Boston College, 2018
Submitted to: Boston College. Graduate School of Arts and Sciences
Discipline: Chemistry

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16

Nissen, Silke. "Remediation of water-borne pollutants and pathogens by photoelectrocatalysis." Thesis, Available from the University of Aberdeen Library and Historic Collections Digital Resources, 2009. http://digitool.abdn.ac.uk:80/webclient/DeliveryManager?application=DIGITOOL-3&owner=resourcediscovery&custom_att_2=simple_viewer&pid=25471.

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17

Li, Lihong. "Nanostructured Titanium Dioxide Photoelectrocatalysis Based Analytical Systems for Determination of Organic Compounds." Thesis, Griffith University, 2011. http://hdl.handle.net/10072/365630.

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Chemical oxygen demand (COD) is an important water quality parameter for estimating organic pollution. Conventional COD method has several drawbacks including lengthy assay time, complex procedure and requiring the use of highly toxic and expensive chemicals. Considerable efforts have been devoted to improve conventional COD methods. In this regard, the PeCODTM method has been the most noticeable technique. This method utilizes the superior oxidation power of UV illuminated nanostructured titanium dioxide (TiO2) to achieve organic degradation while simultaneously enabling quantification of the COD value by directly measuring the photocatalytic oxidation current/charge that originated from photocatalytic degradation of organics. The method is an absolute method that requires no calibration. It is an environmentally friendly method that requires/generates no toxic reagent. It is a simple and rapid method for sensitive and accurate COD determination. However, PeCODTM method needs to be improved in few aspects for more broad applications, especially for the field-based applications. These include the portability and high degradation efficiency for those oraganic compounds with difficulty to be oxidized. This study is therefore focused on improving the portability and applicability of PeCODTM method.
Thesis (PhD Doctorate)
Doctor of Philosophy (PhD)
Griffith School of Environment
Science, Environment, Engineering and Technology
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18

Zu, Meng. "TiO2-based Photoelectrocatalysis Technology for Degradation and Detection of Organics in Wastewater." Thesis, Griffith University, 2021. http://hdl.handle.net/10072/406505.

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With industrialization rapidly progressing in recent decades, great amounts of refractory organic pollutants are found in water bodies, which severely jeopardizes ecosystem health. Monitoring the organic compounds in water bodies and removing organic pollutants from wastewater is essential for ameliorating threats to aquatic life and human health. Photocatalytic (PC) and photoelectrocatalytic (PEC) degradation and detection of organic pollutants in wastewater are promising strategies for fulfilling these goals sustainably, since PC and PEC technologies can take advantage of solar energy, which is one of the most abundant energy sources on earth. Titanium dioxide (TiO2) is a commonly used photocatalyst due to its appropriate band position, high chemical stability, low cost, and nontoxicity. However, pristine TiO2 photocatalysts can only be stimulated by UV irradiation because the band gap of pristine TiO2 is higher than 3.0 eV, which seriously impedes its development with low-cost and environmentally friendly solar energy. There are several efficient strategies to overcome these disadvantages of pristine TiO2, such as morphology modification, bandgap engineering, and applying co-catalysts with the host photocatalysts. Herein, this thesis aims to utilize different strategies to enhance the photocatalytic performance of TiO2-based photocatalysts under visible light irradiation and apply those modified photocatalysts to degradation and detection of organics in wastewater. In the first study, a photoelectrochemical Chemical Oxygen Demand (COD) sensor based on a linear photocurrent-concentration analytical principle was designed for the on-site determination of COD. A high-performance anatase-branch@hydrogenated rutile-nanorod TiO2 (AB@H-RTNR) photoelectrode was fabricated. The as-prepared photoanodes successfully achieved sensitive determination of COD with a detection limit of 0.2 ppm (S/N = 3), an RSD% of 1.5 %, a wide linear detection range of 1.25−576 ppm, and an average recovery rate fluctuating between 100% ± 4% for artificial wastewater sample analyses. The satisfying results of this work suggest that AB@H-RTNR can serve as a promising photocatalyst for fast and accurate detection of organic compounds in water bodies. In addition to detecting COD in water bodies, the degradation of refractory organic compounds in water is also crucial for healthy ecosystems. Highly efficient, low-cost, and portable wastewater treatment and purification solutions are urgently needed for aqueous pollution removal. Herein, in the second study, we coupled a TiO2-based PC system with a persulphate (PS) oxidation system into a portable advanced oxidation device for rapid and deep degradation of organic contaminants in wastewater. Using hydrogenation, we fabricated hydrogenated anatase branched-rutile TiO2 nanorod (H-AB@RTNR) photocatalysts that enable PC degradation to occur under visible light to improve the utilization of solar energy. A degradation rate of 100% and a reaction rate constant of 0.0221 min−1 for degrading 1 L Rhodamine B (20 mg L-1) was achieved in 120 min in a specially designed thin-layer cell under visible light irradiation. These encouraging results suggest that the H-AB@RTNR photocatalysts/PS synergistic degradation system could be an alternative approach for the efficient degradation of organic pollutants in wastewater. Motivated by the result of the PC/PS synergistic degradation system, we further employed a PC/chlorination system for synergistic degradation of antibiotics. In the third study, we demonstrated the use of visible light (>420 nm) to produce •HO and •ClO through the assistance of photocatalysts (TiO2/WO3 nanofibers) and free chlorine (HOCl/ClO−). The introduction of visible-light-driven photocatalysts can significantly boost the yield of active radicals, which favors the degradation of antibiotics in water bodies. The synergistic PC/chlorination degradation system obtained a pseudo-first-order degradation rate constant of a model antibiotic, tetracycline hydrochloride, of 21.438 min-1, which is 3.66 and 86.57 times higher than that in the pure TiO2/WO3 photocatalysis and traditional chlorination processes, respectively. The stability test exhibits that the performance decline is negligible after multiple use cycles. The results of this study suggest that PC/chlorine degradation is a feasible, lowcost, and environmental-friendly strategy for antibiotics removal under visible irradiation. Another approach to improve the degradation efficiency of TiO2-based photocatalysts is using co-catalysts to assist the host photocatalysts. In the fourth study, we fabricated noble-metal free co-catalysts, i.e., N-doped carbon wrapped FeNi nanoparticles (FeNi@NGC), via a pyrolysis method. Hydrogenated TiO2 (H-TiO2) was synthesized as the host photocatalysts and coupled with as-prepared FeNi@NGC to obtain superior PC activity in the degradation of tetracycline hydrochloride (TC-HCl), a model antibiotic. The FeNi@NGC/H-TiO2 system achieved a degradation rate of 100% within 120 min on degrading 100 mL 20 mg L-1 TC-HCl under visible light irradiation (λ>420 nm). The degradation rate constant of the FeNi@NGC/H-TiO2 system reached 23.18 min-1, which was 33.99, 26.98, and 2.23 times compared to that of TiO2, FeNi@NGC/TiO2, and H-TiO2 system. The favorable performance of the FeNi@NGC/H-TiO2 system can be ascribed to two reasons: the secondary electron transfer in the FeNi intermetallic compounds that facilitates the photo-induced charge separation in photocatalysts; and the enhanced visible light absorption ability resulted from the N-doped graphitized carbon shell. Moreover, the oxygen vacancies brought by the hydrogenation process also improves the visible light absorbance of the photocatalysts, which favors the degradation performance. This study suggests that coupling FeNi@NGC cocatalyst with H-TiO2 is a promising strategy for improving the photocatalytic degradation performance on antibiotics. In summary, the strategies presented in this thesis show that the morphology and electronic properties of TiO2 can be manipulated to resolve the problems of poor visible light absorption and the large recombination rate of photogenerated charge carriers. Moreover, the degradation performances of organic compounds show that applying a synergistic system with TiO2-based materials is promising in the removal of refractory organics in the wastewater. The strategies utilized in the thesis (i.e., morphology manipulation, bandgap engineering, and applying co-catalysts) can be utilized in other members of the semiconductors family (such as SnO2, BiVO4, SrTiO3) for developing more sustainable and low-cost approaches and techniques to improve human and aquatic ecosystem health.
Thesis (PhD Doctorate)
Doctor of Philosophy (PhD)
School of Environment and Sc
Science, Environment, Engineering and Technology
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Gan, Wee Yong Chemical Sciences &amp Engineering Faculty of Engineering UNSW. "Synthesis and characterization of titanium dioxide thin films." Publisher:University of New South Wales. Chemical Sciences & Engineering, 2009. http://handle.unsw.edu.au/1959.4/43310.

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In this thesis, titanium dioxide (TiO2)-based thin film photocatalysts of different morphologies were synthesized and studied for their photoelectrocatalytic and photocatalytic properties. The superhydrophilicity of selected TiO2 films were also assessed. The work started with the synthesis of nanocrystalline TiO2 thin films with minimal porosity. A photoelectrocatalytic study was performed to evaluate the films?? photocurrent response in the presence of various organic compounds. At low concentrations, the amount of photocurrent generated was found to be influenced by the molecular structure of the organic compounds. As the concentration increased, the photocurrent response became dependent on the level of interaction of the organic compounds and their partially degraded intermediates with the TiO2 surface. Highly dispersed platinum (Pt) were added onto TiO2 films by a photo-deposition method, and their photocatalytic and photoelectrocatalytic activities were assessed using a novel thin-layer photo(electrochemical)-catalytic system. The system allowed the photocurrent data that originated from the photoelectrocatalysis process to be collected in the reaction cell, and the amount of organic compound being oxidized to be quantified. The Pt deposits were found to enhance photocatalysis by increasing the photogenerated charge-carriers separation, but conversely they retarded the photoelectrocatalysis process. The next part of the work covered the development of mesoporous TiO2 films via the evaporative-induced self-assembly procedure. The structural characteristics of the films were altered by controlling the relative humidity and temperature during the coating and thermal treatment processes. The effect of key structural parameters, such as film porosity, surface area and crystallinity, on the photoelectrocatalytic activity was investigated. These parameters were found to affect the photoelectrocatalysis because the performance of a catalyst in the photoelectrocatalysis application relies strongly on attributes such as the photocatalyst particles?? interconnectivity and the contact to the conducting substrate. The last part of this thesis demonstrated the effort undertaken to improve the UV-induced superhydrophilic effect of a TiO2 film. A multilayer structure of TiO2 nanoparticles was assembled to create a novel TiO2 film that required no UV-activation to induce a uniform water sheeting across its surface. The novel TiO2 thin film exhibited stable superhydrophilic wetting and anti-fogging behaviors after repetitive cycles of heat and wetting treatment, and this performance was affected by the porosity and surface hydroxyl (-OH) contents.

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20

Gomes, Francisco Edvan Rodrigues. "Análise do propilparabeno e do butilparabeno em amostras de água da Bacia do Rio Pardo e estudos da sua degradação por fotólise e fotoeletrocatálise e avaliação da toxicidade e atividade estrogênica." Universidade de São Paulo, 2016. http://www.teses.usp.br/teses/disponiveis/75/75135/tde-20042016-160953/.

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Baseado na técnica de Microextração Liquido-Líquido Dispersiva (DLLME) desenvolveu-se uma metodologia de extração para analisar, por Cromatografia Líquida de Alta Eficiência com detector ultravioleta (HPLC-UV), a presença do propilparabeno (PrP) e do butilparabeno (BuP) nas águas da Bacia do Rio Pardo. O método proposto apresentou um limite de detecção e de quantificação de 62,60 e 187,60 µg/L para o Prp e de 58,40 e 175,20 µg/L para o BuP. Análise das amostras coletadas (18 amostras) apresentou um teor de 2,2 a 6,8 µg/L para o PrP e de 1,9 a 4,9 µg/L para o Bup. Além de analisar a presença dos parabenos nas águas do Rio Pardo, estudou-se também a degradação do PrP, do BuP e da mistura PrP mais BuP ( PrP + BuP) pelas técnicas de fotólise e fotoeletrocatálise em solução de água deionizada e em água de rio (Rio Pardo) em diferentes concentrações (5, 10, 20 e 30 mg/L) e pH (4, 7 e 10). A remoção dos parabenos em ambas as técnicas foi superior a 99%. Na fotólise, o tempo de degradação da menor para a maior concentração variou de 25 a 85 minutos enquanto na fotoeletrocatálise ele foi de 12 a 55 minutos, sendo as melhores condições em água deionizada e em meio ácido e neutro (pH 4 e 7). Análise do Carbono Orgânico Total (TOC) das soluções fotolisadas em água deionizada e em diferentes pH\'s (4, 7 e 10) revelou, para o PrP, uma remoção de 16,3 a 25,25 %. Para o BuP, na mesma sequência de pH, a remoção foi de 15 a 23,55%. Na fotoeletrocatálise a remoção de TOC para o PrP nos pH 4, 7 e 10 variou de 33,3 a 36,5 % enquanto para o BuP ela foi de 35,2 a 38,3 %. Teste de citotoxicidade mostrou que o PrP, o BuP e a mistura PrP-BuP são atóxico para as células de fibroblastos Balb/c 3T3 clone A31 antes e após as degradações, todavia são estrogênicos para as células de adenocarcinoma mamário MCF-7. Para o PrP, após ambos os processos de degradação, a estrogenicidde foi completamente abolida, enquanto que para o BuP e para mistura (PrP+BuP) ela foi reduzida, porém não totalmente eliminada.
Based on the dispersive Liquid-Liquid Microextraction technique (DLLME) developed an extraction methodology to analyze by High Performance Liquid Chromatography with Ultraviolet detection (HPLC-UV), the presence of propylparaben (PrP) and butylparaben (BuP) in the waters of the Pardo River Basin. The proposed method has a limit of detection and quantification of 62,60 and 187,60 µg /L of PrP and 58.40 and 175.20 µg /L for BuP. Analysis of the samples (18 samples) showed a content of 2.2 to 6.8 µg / L for the PrP and 1.9 to 4.9 µg / L for the Bup. In addition to analyzing the presence of parabens in the waters of the Pardo River, studied also the degradation of PrP, BuP and mixture PrP more BuP (PrP + BuP) for photolysis and photoelectrocatalysis techniques in deionized water solution and river water (Pardo River) at different concentrations (5, 10, 20 and 30 mg / L) and pH (4, 7 and 10). Removal of parabens in both techniques was greater than 98%. The degradation time in the photolysis ranged from 25 to 85 minutes while in photoelectrocatalysis was of 12 to 55 minutes, being the best conditions in deionized water and in acidic and neutral medium (pH 4 and 7). Analysis of Total Organic Carbon (TOC) of the solution photolysed in deionized water at different pHs (4, 7 and 10) showed to PrP, a removal of 16.3 25.25%. For BuP in the same sequence pH, the removal was 15 to 23.55%. In photoelectrocatalysis TOC removal for PrP in pH 4, 7 and 10 ranged from 33.3 to 36.5% whereas for BuP it was 35.2 to 38.3%.Cytotoxicity test showed that PrP, BUP and PrP-BuP mixture is nontoxic to the cells fibroblasts Balb / c 3T3 clone A31 before and after degradation, however are estrogenic for breast adenocarcinoma cells MCF-7. For the PrP, after photolysis and photoelectrocatalysis, it was completely abolished whereas for BuP and mixture (PrP + BuP), it was reduced but not completely eliminated.

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Štefancová, Eva. "Kinetika elektrofotokatalytické dezinfekce vody." Master's thesis, Vysoké učení technické v Brně. Fakulta chemická, 2019. http://www.nusl.cz/ntk/nusl-401840.

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In this work, electrophotocatalytic disinfection on selected microorganisms was verified. The electrophotocatalytic system allows the application of electrical bias to the photoanode coated with a titanium dioxide layer. The disinfecting effect was observed on E.coli and C.glabrata in aqueous solution. The effect of radiation intensity on electrophotocatalysis and selected optimal conditions for further experiments was observed in the E. coli organism. Photocatalytic disinfection was carried out under suitable conditions on C.glabrata yeast and the effect of sodium sulfate electrolyte on electrophotocatalytic disinfection was observed in this case.

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22

Roloff, Glauco Aurelio. "Degradação do hormônio estradiol por eletrólise, fotólise e fotoeletrocatálise." Universidade de São Paulo, 2007. http://www.teses.usp.br/teses/disponiveis/75/75131/tde-14042008-161820/.

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Neste projeto investigou-se o uso de três técnicas: (i) eletrólise, (ii) fotoeletrocatálise e (iii) fotólise, na degradação do hormônio estradiol, comumente encontrado nos esgotos domésticos, e que geram sérias preocupações com a ação nefasta que podem provocar na vida selvagem e humana. Os ensaios eletroquímicos foram realizados sobre eletrodos de platina e carbono vítreo. A técnica de fotoeletrocatálise foi aplicada empregando-se placas de titânio recobertas com nanocamadas de TiO2. Como fonte de radiação ultravioleta utilizou-se uma lâmpada de vapor de mercúrio de 125 W tanto na fotoeletrocatálise como na fotólise. Através dos estudos da oxidação do estradiol por voltametria cíclica, sobre os eletrodos acima mencionados, foi possível definir o seu potencial de oxidação em soluções de KCl e tampão fosfato (pH 7), sobre platina e carbono vítreo. Estes parâmetros serviram de base para a realização das eletrólises sob condições controladas. A fotoeletrocatálise do estradiol foi realizada sobre Ti/TiO2 preparado por técnica sol-gel e se mostrou muito mais efetiva que a eletrólise eletrolítica. Finalmente, a fotólise também foi testada empregando-se apenas a lâmpada de vapor de mercúrio. Neste último caso a degradação do estradiol foi ligeiramente inferior que aquela observada por fotoeletrocatálise. Identificou-se que em soluções de KCl há a formação de hipoclorito, o que auxilia o processo oxidativo do estradiol. Espectroscopia de UV-vís e cromatografia líquida (HPLC) foram empregadas para acompanhar os processos de degradação. Apesar de ter sido observado o surgimento de bandas e picos cromatográficos devidos aos produtos formados, não foi possível identifica-los.
In this project the use of three techniques was investigated: (i) electrolysis, (ii) photoelectrocatalysis and (iii) photolysis, in the degradation of the hormone estradiol, commonly found in the domestic sewers. This hormone can generate serious concerns with a disastrous action that can provoke in the wild and human life. The electrochemistry studies were accomplished on platinum and glassy carbon electrodes. The photoelectrocatalysis technique was applied using titanium plate covered with nanolayers of TiO2. As a source of ultra-violet radiation was used a lamp bulb of mercury vapor of 125 W for the photoelectrocatalysis as also in the photolysis. Through the studies of the oxidation of the estradiol by cyclic voltammetry, on the electrodes above mentioned, it was possible to define the oxidation potential of the organic specie in both solutions, KCl and phosphate buffers (pH 7), for platinum and glassy carbon. These parameters served as base for the realization of the electrolysis under controlled conditions. The photoelectrocatalysis of the estradiol was accomplished on Ti/TiO2 prepared by sol-gel technique and it was shown much more effective than the electrolyitc electrolysis. Finally, the photolysis was also tested being just used the mercury vapor lamp. In this last case the degradation of the estradiol was lightly inferior to that observed by photoelectrocatalysis It was identified that in solutions of KCl there is the hypochlorite formation, what aids the oxidation of the estradiol. Spectroscopy of UV-vis and high performance liquid chromatography (HPLC) were used to accompany the degradation processes. In spite of the appearance of bands and chromatographyc peaks owed to the formed products having been observed, however, it were not possible identify them.

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23

Faber, Marcelo [UNESP]. "Tratamento fotocatalítico de corante ácido usando filmes finos de vidro/Ti 'O IND. 2' e degradação fotoeletrocatalítica de corante vat sobre eletrodos de filmes finos de Ti/Ti 'O IND. 2'." Universidade Estadual Paulista (UNESP), 2010. http://hdl.handle.net/11449/105716.

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
Os estudos de degradação do corante VAT idantreno verde oliva foram realizados empregando-se solução 5x10-5 mol L-1 do corante em meio de NaCl 0,1 mol L-1 , pH=2,0 por meio do processo fotoeletrocatalítico sobre eletrodos de filmes finos de Ti/TiO2. Após 210 min de tratamento foi obtido 100% de descoloração e 86 % de mineralização. A aplicação do método fotocatalítico nas mesmas condições experimentais leva a apenas 60% de remoção do corante, indicando que o método fotoeletrocatalítico apresenta maior eficiência que a técnica de fotocatálise. A degradação do corante ácido vermelho 8 foi investigada através de processo fotoquímico empregando irradiação UV com lâmpada germicida de 4 W e lâmpada de mercúrio de 80 W. Foi observado significativa remoção da cor, porém análises de carbono orgânico total mostraram que o processo não apresenta nenhuma mineralização da matéria orgânica. Utilizando-se lâmpada de 80 W a degradação do corante ocorre segundo reação de pseudo primeira ordem com constante de velocidade de 0,0122 min-1 . A degradação do corante vermelho 8 é mais eficiente pelo processo fotocatalítico. A oxidação fotocatalítica de solução 5x10-5 mol L-1 do corante em meio de Na2SO4 0,1 mol L-1 , pH=6,0, sobre vidro/TiO2 promoveu 100 % de remoção da cor e aproximadamente 43 % de mineralização do corante. A eficiência fotocatalítica de filmes de TiO2 suportados em substrato de vidro obtidos pelo método dip-coating foi investigada testando-se a degradação do corante ácido vermelho em filmes obtidos variando-se os parâmetros: número de etapas de recobrimento, velocidade de deposição e temperatura de calcinação. O filme que mostrou maior eficiência fotocatalítica na degradação do corante ácido vermelho 8, foi construído com 1 depósito de TiO2, velocidade de recobrimento de 50 mm/min e temperatura...
Studies of degradation of the dye VAT Indanthrene olive green were performed using solution was 5x10-5 mol L-1 dye in NaCl 0.1 mol L-1 , pH = 2.0 through the process photoelectrocatalytic thin-film electrodes Ti/TiO2. After 210min of treatment was obtained 100% discoloration and 86% of mineralization. The application of the photocatalytic the same experimental condition leads to 60% removal of dye, indicating that the method photoelectrocatalytic is more efficient than the technique of photocatalysis. The degradation of acid red dye 8 was investigated by photochemical process using irradiation with UV germicidal lamp 4W and mercury lamp of 80W. Have been observed significant removal of color, but the analysis of carbon organic total no shows mineralization of organic matter. Using 80W lamp degradation of the dye is second reaction under pseudo first order rate constant of 0.0122 min-1 . The degradation of the red dye 8 is more efficient for the photocatalytic process. The photocatalytic oxidation of solution 5x10-5 mol L-1 dye in the midst of Na2SO4 0.1 mol L-1 , pH= 6.0 on glass/TiO2 promoted 100% removal of color and approximately 43% mineralization of the dye. The efficiency of photocatalytic TiO2 films supported on glass substrate obtained by dip-coating method was investigated by testing the degradation of acid red dye in films obtained by varying the parameters: number of steps of coating, deposition rate and temperature calcination. The film showed better photocatalytic degradation of dye Acid Red 8, was built with 1 deposit TiO2, coating speed of 50 mm/min and calcination temperature of 350°C film. Under these conditions the degradation of the dye second reaction is pseudo first-order rate constant of degradation of k = 0.121 min-1 . Therefore, it is concluded that the technique of photolysis and photocatalysis can be an excellent alternative to decolorize... (Complete abstract click electronic access below)

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Bonancêa, Carlos Eduardo. "Estudo espectroscópico de processos de degradação fotoquímica e fotoeletroquímica de corantes." Universidade de São Paulo, 2010. http://www.teses.usp.br/teses/disponiveis/46/46132/tde-01032011-112239/.

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Este trabalho visa o estudo de processos de degradação fotocatalítica e fotoeletrocatalítica de corantes sobre dióxido de titânio. O enfoque está voltado ao uso de técnicas espectroscópicas, com especial destaque para o desenvolvimento de metodologias de espectroscopia vibracional Raman intensificada. Nesse sentido, tem-se em vista a investigação dos mecanismos envolvidos nos processos de fotodegradação e fotoeletrodegradação de corantes, através da identificação de intermediários e produtos de processos de degradação por técnicas de espectroscopia eletrônica e Raman. Os estudos de fotocatálise são também expandidos para ambientes eletroquímicos. Nos chamados processos fotoeletrocatalíticos, a combinação de processos eletroquímicos e fotoquímicos mostra-se bastante promissora para a degradação de poluentes orgânicos. O primeiro desafio no desenvolvimento desse trabalho foi construir o fotorreator adequado que permitisse a obtenção de amostras para serem analisadas por espectroscopia Raman, e apresentasse boa eficiência nos processos de fotocatálise e também fotoeletrocatálise. Encontrado o fotorreator adequado, investigamos o comportamento cinético dos processos foto(eletro)degradação de corantes, buscando verificar a dependência com o potencial eletroquímico aplicado, o efeito do eletrólito suporte, e a identificação de intermediários formados durante o processo de degradação. Analisamos também aspectos relacionados aos mecanismos de adsorção de corantes sobre a superfície do dióxido de titânio. Tais aspectos podem ser de significativa relevância no desenvolvimento de técnicas eficazes para o tratamento de poluentes orgânicos. Nossos estudos estiveram principalmente centrados em dois corantes: o azocorante verde de Janus e o corante antraquinônico alizarina vermelha S. Os resultados obtidos nos estudos da cinética dos processos fotoeletrocatalíticos sugerem que o efeito do potencial aplicado depende de maneira significativa da natureza química do corante. Observou-se uma tendência dos processos fotoeletrocatalíticos serem mais eficientes na remoção da coloração da solução corante do verde de Janus quando comparados aos fotocatalíticos. Tal tendência não foi observada para o corante alizarina vermelha S. Essa diferença de comportamento pôde ser relacionada à natureza das interações específicas de entre cada corante e a superfície do catalisador. Nossos estudos a respeito dos mecanismos envolvidos nos processos de degradação do verde de Janus revelaram que as primeiras etapas dos processos de fotodegradação e fotoeletrodegradação seguem mecanismos diferentes. Os resultados obtidos mostram que a degradação do verde de Janus em suspensão de TiO2 envolve entre suas etapas modificações na ligação azo desse corante (N=N), resultando na formação de um composto intermediário derivado da fenossafranina. No processo fotoeletrocatalítico, por outro lado, observa-se um mecanismo diferenciado o qual não envolve em suas etapas iniciais a quebra da ligação azo do corante
This work focuses on the study of photocatalytic and photoelectrocatalytic degradation processes of dyes over titanium dioxide. The main approach is based on the use of spectroscopic techniques, with special emphasis to methodologies based on surface-enhanced Raman spectroscopy. Within this context, the mechanisms involved in the photodegradation and photoelectrodegradation of dyes are investigated by the identification of degradation intermediates through vibrational and electronic spectroscopies. In the so-called photoelectrocatalytic processes, the combination of electrochemical and photochemical processes is an interesting and promising approach for the degradation of a wide variety of organic pollutants. The first step in the development of the present work was to build a photo reactor that allowed the analysis of samples through Raman spectroscopy and presented a good efficiency for both photocatalytic and photoelectrocatalytic processes. We then investigated the kinetic behavior of the photo(electro)degradation of dyes in order to verify the dependence upon the electrochemical applied potential, the effect of the supporting electrolyte, and the identification of intermediate products formed during the degradation process. We also analyzed aspects related to the adsorption mechanisms of the dyes on the titanium dioxide surface. Such aspects can be relevant to the understanding and to the development of efficient techniques for the remediation of organic pollutants. Our studies focused mainly on two dyes: the azo dye Janus green and the anthraquinonic dye alizarin red S. The results obtained in the kinetic study of the photoelectrocatalytic processes suggest that the effect of the applied electrochemical potential strongly depends on the chemical nature of the investigated dye. We have observed that the decolorization of Janus green is favored for photoelectrocatalytic process as compared to the photocatalytic degradation. Such behavior was not observed for the anthraquinonic dye alizarin red S. This difference was related to the nature of the specific interactions between each dye and the catalyst surface. Our studies regarding the mechanisms of degradation revealed that the first steps of the photocatalytic and photoelectrocatalytic processes of Janus green followed different routes. The obtained results indicate that the degradation of Janus green in aqueous TiO2 suspension involves changes in the azo bond (N=N), resulting in the formation of an intermediate compound a derived from the phenosafranine structure, whereas for the photoelectrocatalytic process there are evidences of a different mechanism that does not involve the cleavage of the azo bond.

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Faber, Marcelo. "Tratamento fotocatalítico de corante ácido usando filmes finos de vidro/Ti 'O IND. 2' e degradação fotoeletrocatalítica de corante vat sobre eletrodos de filmes finos de Ti/Ti 'O IND. 2'. /." Araraquara : [s.n.], 2010. http://hdl.handle.net/11449/105716.

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Orientador: Maria Valnice Boldrin
Banca: Hideko Yamanaka
Banca: Mercedes de Moraes
Banca: Jeosadaque José de Sene
Banca: Denise Alves Fungaro
Resumo: Os estudos de degradação do corante VAT idantreno verde oliva foram realizados empregando-se solução 5x10-5 mol L-1 do corante em meio de NaCl 0,1 mol L-1 , pH=2,0 por meio do processo fotoeletrocatalítico sobre eletrodos de filmes finos de Ti/TiO2. Após 210 min de tratamento foi obtido 100% de descoloração e 86 % de mineralização. A aplicação do método fotocatalítico nas mesmas condições experimentais leva a apenas 60% de remoção do corante, indicando que o método fotoeletrocatalítico apresenta maior eficiência que a técnica de fotocatálise. A degradação do corante ácido vermelho 8 foi investigada através de processo fotoquímico empregando irradiação UV com lâmpada germicida de 4 W e lâmpada de mercúrio de 80 W. Foi observado significativa remoção da cor, porém análises de carbono orgânico total mostraram que o processo não apresenta nenhuma mineralização da matéria orgânica. Utilizando-se lâmpada de 80 W a degradação do corante ocorre segundo reação de pseudo primeira ordem com constante de velocidade de 0,0122 min-1 . A degradação do corante vermelho 8 é mais eficiente pelo processo fotocatalítico. A oxidação fotocatalítica de solução 5x10-5 mol L-1 do corante em meio de Na2SO4 0,1 mol L-1 , pH=6,0, sobre vidro/TiO2 promoveu 100 % de remoção da cor e aproximadamente 43 % de mineralização do corante. A eficiência fotocatalítica de filmes de TiO2 suportados em substrato de vidro obtidos pelo método dip-coating foi investigada testando-se a degradação do corante ácido vermelho em filmes obtidos variando-se os parâmetros: número de etapas de recobrimento, velocidade de deposição e temperatura de calcinação. O filme que mostrou maior eficiência fotocatalítica na degradação do corante ácido vermelho 8, foi construído com 1 depósito de TiO2, velocidade de recobrimento de 50 mm/min e temperatura... (resumo completo, clicar acesso eletrônico abaixo)
Abstract: Studies of degradation of the dye VAT Indanthrene olive green were performed using solution was 5x10-5 mol L-1 dye in NaCl 0.1 mol L-1 , pH = 2.0 through the process photoelectrocatalytic thin-film electrodes Ti/TiO2. After 210min of treatment was obtained 100% discoloration and 86% of mineralization. The application of the photocatalytic the same experimental condition leads to 60% removal of dye, indicating that the method photoelectrocatalytic is more efficient than the technique of photocatalysis. The degradation of acid red dye 8 was investigated by photochemical process using irradiation with UV germicidal lamp 4W and mercury lamp of 80W. Have been observed significant removal of color, but the analysis of carbon organic total no shows mineralization of organic matter. Using 80W lamp degradation of the dye is second reaction under pseudo first order rate constant of 0.0122 min-1 . The degradation of the red dye 8 is more efficient for the photocatalytic process. The photocatalytic oxidation of solution 5x10-5 mol L-1 dye in the midst of Na2SO4 0.1 mol L-1 , pH= 6.0 on glass/TiO2 promoted 100% removal of color and approximately 43% mineralization of the dye. The efficiency of photocatalytic TiO2 films supported on glass substrate obtained by dip-coating method was investigated by testing the degradation of acid red dye in films obtained by varying the parameters: number of steps of coating, deposition rate and temperature calcination. The film showed better photocatalytic degradation of dye Acid Red 8, was built with 1 deposit TiO2, coating speed of 50 mm/min and calcination temperature of 350°C film. Under these conditions the degradation of the dye second reaction is pseudo first-order rate constant of degradation of k = 0.121 min-1 . Therefore, it is concluded that the technique of photolysis and photocatalysis can be an excellent alternative to decolorize... (Complete abstract click electronic access below)
Doutor

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Marien, Cédric. "Synthèse, caractérisation et réactivité de matériaux nanostructurés en TiO2 pour la dégradation photo(électro)catalytique du Paraquat." Thesis, Strasbourg, 2017. http://www.theses.fr/2017STRAF045/document.

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Le développement de traitements photo(électro)catalytiques pour l’élimination de polluants organiques requiert la préparation de nano-TiO2 immobilisé sur des supports pour simplifier leur séparation du liquide traité. Deux procédés ont été développés dans le cadre de cette thèse. Le premier consiste à préparer des mousses en TiO2/SiC puis à les intégrer dans un réacteur annulaire entouré de lampes UV-C. Plusieurs paramètres ont été étudiés : le nombre de lampes, la température, la concentration en polluant (paraquat, herbicide) et la stabilité mécanique des mousses. Ensuite, les sous-produits de dégradation ont été identifiés. L’autre procédé développé vise à améliorer la séparation des paires électrons-trous en appliquant une différence de potentiel. Le photocatalyseur doit alors être immobilisé sur une surface conductrice. Dans cette optique, la synthèse par anodisation électrochimique de nanotubes de TiO2/Ti en milieu fluoré est une technique très prometteuse. Plusieurs paramètres ont été étudiés afin de réaliser des électrodes de grande surface et favoriser le passage de l’échelle laboratoire à l’échelle pilote. Les propriétés photoélectrochimiques des nanotubes ont ensuite été optimisées notamment via la détermination de leur longueur optimale. Par la suite, la dégradation photoélectrocatalytique du paraquat a mis en évidence qu’une faible différence de potentiel (0,5 à 1 volt) suffit pour maximiser la séparation des paires électron-trou. La conductivité de l’électrolyte doit également être suffisamment élevée pour maximiser les performances du procédé photoélectrocatalytique
The development of photo(electro)catalytic methods for the removal of organic pollutants requires the elaboration of supported TiO2 nanomaterials in order to simplify the recovery of the photocatalyst from treated effluents. Two different approaches were developed during this PhD thesis. The first approach consists in producing a thin film of TiO2 onto alveolar SiC foams. The TiO2/SiC assembly was then integrated into a tubular reactor surrounded by UV-C lamps. Many parameters were studied: number of lamps, the temperature, pollutant’s concentration (paraquat, weed killer) and the mechanical stability of TiO2/SiC foams. Then, paraquat’s by-products of degradation were identified. Another approach was then developed in order to improve the electron-hole pair of the photocatalytic process by applying a small electrical bias. For this purpose, the photocatalyst must be coated on a conductive surface. In this field, TiO2 nanotubes grown on titanium substrate by electrochemical synthesis in a fluoride media are very promising. Many parameters were studied in order to produce large electrodes and favor the upscaling. Photoelectrochemical properties of TiO2 nanotubes were studied and optimized especially concerning nanotube’s length. Besides, photoelectrocatalytic degradation of paraquat evidences that a small applied bias (0,5 to 1 volt) is enough to ensure optimal electron-hole separation. It was also demonstrated that the effluent conductivity also has a large influence on the photoelectrochemical performances

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Kaeffer, Nicolas. "Construction de cathodes et photocathodes moléculaires pour la production d'hydrogène." Thesis, Université Grenoble Alpes (ComUE), 2016. http://www.theses.fr/2016GREAV024/document.

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Générer des carburants solaires, comme l’hydrogène via la photoélectrolyse de l’eau, est une stratégie à explorer pour notre futur énergétique. Pour éviter l’emploi du platine en tant que catalyseur de production d’hydrogène, des métaux abondants peuvent être utilisés. Au laboratoire, le complexe diimine-dioxime de cobalt, catalyseur moléculaire de réduction des protons, a pu être immobilisé pour créer une cathode produisant de manière stable de l’hydrogène en milieu aqueux. Dans ces travaux, nous avons étudié l’introduction du catalyseur dans des dispositifs photoélectrocatalytiques. Différentes conditions opératoires dans l’eau, solvant de choix, ont été examinées. Le complexe se dégrade s’il est en solution mais son activité est maintenue, même en présence d’oxygène, s’il est supporté sur électrode. Cette électrode a ainsi pu être intégrée en cellule tandem. De nouveaux dérivés du complexe ont aussi été développés pour l’attachement sur oxydes transparents conducteurs. Un dérivé a été co-immobilisé avec des photosensibilisateurs sur une surface de NiO, oxyde de type p. Les photocathodes co-greffées obtenues ont été caractérisées par un ensemble de techniques analytiques et ont démontré la production d’hydrogène en conditions photoélectrocatalytiques. Des entités colorant-catalyseur pouvant s’ancrer sur surface ont également été synthétisées et ouvrent de nouvelles voies pour élaborer des photocathodes moléculaires
Solar fuels generated from the light-induced splitting of water into H2 and O2 is an appealing strategy for securing future energy. The use of platinum for catalyzing hydrogen evolution may be bypassed with earth-abundant catalysts. In a previous study, our lab realized the immobilization of a proton reduction catalyst, the cobalt diimine-dioxime molecular complex, within a cathode material steadily evolving H2 from fully aqueous media. In this work, we report on the implementation of this catalyst into light-driven devices. Operating conditions in the solvent of interest, water, were screened. The molecular catalyst degrades when free in solution, but retains activity when supported on an electrode, even in the presence of O2, and could thus be integrated into a tandem cell. Further on, new derivatives of the catalyst were developed for the attachment onto transparent conducting oxides. Co-grafted photocathodes were constructed by anchoring a functionalized catalyst along with photosensitizers onto p-type NiO. These architectures were checked by a whole set of analytical techniques and light-driven catalytic hydrogen evolution was achieved by photocathodes assessed under device-related photoelectrochemical conditions. Immobilizable dye-catalyst dyads were also successfully synthetized as alternative derivatives and open up new possibilities to develop molecular photocathodes

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Hilliard, Samantha. "Photocatalyse de décomposition de l'eau : conception et construction d'une cellule photoelectrocatalyique pour la photodissociation de l'eau." Thesis, Paris 6, 2016. http://www.theses.fr/2016PA066034/document.

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La photoelectrocatalyse de l'eau par rayonnement solaire est une solution communément proposée pour la production propre d'hydrogène. En termes de rendement solaire-à-hydrogène, un tandem dual photosystème est accepté comme la configuration plus efficace concernant les cellules photoelectrocatalytique pour la dissociation de l'eau. Ce travail s'intéresse au trioxyde de tungstène (WO3) et au bismuth vanadate (BiVO4) sous la forme de photoanodes type n en couches minces pour la complétion d'oxydation de l'eau dans la demi-réaction pour la dissociation complète de l'eau dans une cellule tandem dual photosystème photoelectrocatalytique. Ces couches minces sont fabriquées par des méthodes robustes, économiques, et extensibles de sol-gel dip coating, et caractérisées par différentes techniques pour vérifier leurs caractéristiques physiques et leur performance photoelectrochimique. WO3 et BiVO4 sont optimises par nanostructuration, modification des couches interfaciales, et addition des co-catalyseurs de surface pour améliorer les performances et la stabilité, respectivement dans des conditions acides et neutres. Ces matériaux sont couples avec une photocathode de type p en oxyde de cuivre (II) pour compléter la réaction de dissociation de l'eau. La cellule photoelectrocatalytique ainsi construite est inspirée par la littérature concernant les systèmes innovateurs de tandem dual photosystèmes. Ce travail aboutit à l'une des seules cellules de dissociation de l'eau par photoelectrocatalyse à base des oxydes de métaux, fabriquée via des techniques faciles et économiques. L'efficacité de la production solaire-à-hydrogène est de 0.01%, et applied-bias-to-photon efficacité de 0.06%
Solar water splitting by photoelectrocatalysis is a proposed long term solution for the production of renewable hydrogen. A wired dual photosystem photoelectrocatalytic cell is thermodynamically considered to possess the highest attainable solar-to-hydrogen efficiency. To realize a photoelectrocatalytic water splitting cell for practical application, facile fabrication methods and abundant low cost materials are essential. This research investigates tungsten trioxide (WO3) and bismuth vanadate (BiVO4) as thin film n-photoanodes to complete the oxygen evolution half reaction for water splitting application in a tandem dual photosystem photoeletrocatalyic water splitting cell. These thin films are fabricated by low cost, robust, scalable, sol-gel dip coating methods and characterized by several techniques to verify the physical characteristics and photochemical performance. WO3 and BiVO4 are optimized by nanostructuration, interfacial surface modification, and addition of surface co-catalysts to increase performance and stability in acidic and neutral conditions, respectively. These materials are coupled with a copper (II) oxide p-photocathode to drive the hydrogen evolution reaction in a photoelectrocatalyic cell to complete the water splitting reaction. The photoelectrocatalytic cell constructed is inspired by previous literature reports encompassing an innovative tandem dual photosystem approach. As a result, this research reports one of the only entirely metal oxide based photoelectrocatalytic water splitting cells, fabricated by inexpensive, unexcessive techniques, resulting in a solar-to-hydrogen efficiency of 0.01% and an applied bias to photon efficiency of 0.06%

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MOYA, Johan René González. "Nanotubos de TiO2 sensibilizados com quantum dots de CdS e suas aplicações para a geração de hidrogênio mediante fotocatálise e fotoeletrocatálise." Universidade Federal de Pernambuco, 2016. https://repositorio.ufpe.br/handle/123456789/17768.

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CNPq
No presente trabalho foi investigado o desempenho de nanotubos de TiO2 sensibilizados com quantum dots de CdS na geração de hidrogênio por meio da reação de dissociação da água por meio da fotocatálise e fotoeletrocatálise. Os nanotubos de TiO2 foram obtidos pelo método de anodização (30 V, 1 hora) de chapas de Ti, em etilenoglicol e água contendo íons fluoreto. As amostras anodizadas foram submetidas a tratamento térmico 400°C durante 3 horas. Posteriormente as amostras foram sensibilizadas com quantum dots de CdS via síntese hidrotérmica in situ usando o ácido 3-mercaptopropiônico como agente estabilizante. A eficiência fotocatalítica dos materiais na produção de hidrogênio foi investigada por meio da reação de dissociação da água utilizando como fonte de irradiação um simulador solar. A quantificação do hidrogênio gerado foi determinada por meio de cromatógrafia gasosa. Por outro lado, para estimar a eficiência de geração de hidrogênio via fotoeletrocatálise, as amostras foram avaliadas como fotoânodos e medidas da fotocorrente gerada pela irradiação em uma célula fotoeletroquímica (PEC) de três eletrodos foram realizadas. A sensibilização dos nanotubos de TiO2 com os quantum dots de CdS a partir da síntese hidrotérmica in situ, permitiu uma boa impregnação e distribuição uniforme dos quantum dots ao redor da superfície dos nanotubos, de acordo com as análises de EDS e XPS. O perfil de profundidade de XPS mostrou que a concentração de CdS permaneceu praticamente inalterada (homogênea) ao longo da matriz nanotubular. A presença de ânions sulfato evidenciou a oxidação do material preferentemente na superfície. Os nanotubos conferem uma proteção ao CdS frente à oxidação e protegem também os quantum dots quanto à fotocorrosão na solução de sacrifício S2-/SO32- utilizada. Este comportamento define uma boa estabilidade na fotocorrente gerada como mostrado em experimentos de longa duração (20 horas) sob irradiação. Os resultados experimentais mostraram três comportamentos diferentes para a geração de H2 quando o tempo de síntese dos QDs de CdS aumenta. Foram observados, efeitos similares, antagônicos e sinérgicos frente à atividade fotocatalítica em relação aos nanotubos de TiO2. O efeito antagônico parece estar relacionado com a presença de duas populações de tamanhos de QDs de CdS, onde a população com um band gap menor atua como uma armadilha para os elétrons fotogerados pela população com um band gap maior, diminuindo a atividade fotocatalítica do TiO2 na região ultravioleta. A transferência de elétrons a partir dos QDs de CdS para o TiO2 foi comprovada pelos resultados de UPS combinados com as medidas do band gap óptico. A maior absorção no visível após a sensibilização com o CdS combinada com a transferência de elétrons possibilita um incremento na taxa de geração de hidrogênio por meio da fotocatálise a partir de luz visível de quase zero para os nanotubos de TiO2 até cerca de 0,3 μmol cm-2 h-1 após sensibilização com os QDs de CdS. No caso da fotoeletrocatálise em uma PEC, a taxa de geração de H2 a partir de luz visível estimada pela fotocorrente gerada após a sensibilização (1,79 μmol cm-2 h-1) chega a ser até 12 vezes maior que para os nanotubos de TiO2 sem sensibilizar (0,15 μmol cm-2 h-1).
In the present work, we investigated the performance of TiO2 nanotubes sensitized with CdS quantum dots on the photocatalytic and photoelectrocatalytic H2 production reaction. TiO2 nanotubes were obtained by anodization of Ti foil, followed by annealing to crystallize the nanotubes into anatase phase. Afterwards, the samples were sensitized with CdS quantum dots via an in situ hydrothermal route using 3-mercaptopropionic acid as the capping agent. This sensitization technique permits high loading and uniform distribution of CdS quantum dots onto TiO2 nanotubes. The XPS depth profile showed that CdS concentration remains almost unchanged (homogenous), while the concentration relative to the sulfate anion decreases by more than 80 % with respect to the initial value after ~200 nm in depth. The presence of sulfate anions is due to the oxidation of sulfide and occurs in greater proportion in the material surface. This protection for air oxidation inside the nanotubular matrix also protected the CdS from photocorrosion in sacrificial solution leading to good stability properties proved by a long duration photocurrent measurements. The effect of the sizes of CdS quantum dots attached to TiO2 nanotubes on the hydrogen production via photocatalysis was investigated. The experimental results showed three different behaviors when the CdS size is increased in the sensitized samples, e.g., similar, deactivation and activation effects on the hydrogen production with regard to TiO2 nanotubes. The deactivation effect was related with two populations of sizes of CdS, where the population with a shorter band gap acts as a trap for the electrons photogenerated by the population with a larger band gap. Electron transfer from CdS quantum dots to TiO2 semiconductor nanotubes was proven by the results of UPS combined with optical band gap measurements. This property facilitates an improvement of the visible-light photocatalytic hydrogen evolution rate from zero, for TiO2 nanotubes, to approximately 0.3 μmolcm-2h-1 for TiO2 nanotubes sensitized with CdS quantum dots. The hydrogen generation rate estimated from photocurrents measurements via photoelectrocatalysis in PEC systems was also investigated. The hydrogen generation rate after sensitization was improved from 0,15 μmol cm-2 h-1 to 1,79 μmol cm-2 h-1, near to 12 times better performance under visible-light irradiation.

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Fabrão, Rodrigo Monteiro [UNESP]. "Oxidação fotoeletrocatalítica de glicose a compostos orgânicos com maior valor agregado empregando fotoeletrodos de nanotubos de dióxido de titânio." Universidade Estadual Paulista (UNESP), 2016. http://hdl.handle.net/11449/143107.

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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
A produção de etanol e açúcar a partir de cana-de-açúcar é um atividade de grande importância no Brasil, mas também fonte de grande preocupação ambiental devido ao grande acúmulo de biomassa na forma de bagaço e vinhaça gerados como rejeitos. A biomassa lignocelulósica é constituída de celulose, com estrutura formada de unidades de glicose polimerizadas, deste modo estudos voltados para a conversão de glicose em compostos químicos com maior valor agregado seria relevante para buscar novas formas de aproveitamento destes rejeitos. O objetivo do presente trabalho é investigar a aplicabilidade da técnica de fotoeletrocatálise para promover a oxidação de glicose em meio aquoso utilizando nanotubos de dióxido de titânio (NT-Ti/TiO2) como fotoanodos com vistas a obtenção de compostos com maior valor agregado. Os eletrodos de nanotubos de dióxido de titânio (NT-Ti/TiO2) foram preparados por oxidação eletroquímica de Ti em solução 1,0 mol L-1 de NaH2PO4 + 0,3% (m/m) HF como eletrólito de suporte sob potencial de 20V por 2 h e calcinado a 450 °C. Um método analitico baseado em cromatografia de troca iônica com detecção amperométrica foi desenvolvido para análise de glicose, acido glicônico, acido glicárico, arabitol e arabinose e curvas analíticas foram construídas em concentrações de 1,00 a 20,0x10-6 mol L-1, r = 0,9995, e o método alcançou limites de detecção e determinação ao redor de LD = 0,03x10-6 mol L-1 e LQ = 0,08x10-6 mol L-1 para a determinação de glicose. O método foi utilizado para monitoramento dos produtos gerados durante oxidação fotoeletrocatalítica de 10,0 mmol L-1 de glicose sob potencial de +1,5 V vs Ag/AgCl e irradiação UV/Vis que alcançou 72% de conversão após 180 min de tratamento. Medidas de remoção de carbono orgânico total mostraram que 28% da glicose foi convertida a CO2 e o restante foi transformado em outro produtos, tais como Arabinose, arabinitol, 4-cetoglicose, glucohexodialdose, glucona-δ-lactona, 6-desoxiglucose e o ácido glicônico, cuja maioria foi confirmada por espectrometria de massas. Os resultados demonstram que a técnica de fotoeletrocatálise pode ser uma alternativa simples, econômica e promissora para promover a conversão da glicose em alguns produtos de interesse econômico.
The production of sugar and ethanol from sugarcane is an activity very important in Brazil, but it is also a source of great environmental concern due to the large accumulation of biomass in form of bagasse and vinasse generated as waste of this process. The lignocellulosic biomass is made up of cellulose, wich structure is made of polymerized glucose units. Thereby studies focused on the conversion of glucose into added value chemical compounds would be relevant to seek new ways to use these waste. This work describes the construction electrodes of titanium dioxide nanotubes (NT-Ti / TiO2) and its application in photoeletrocatalytic oxidation of glucose in aqueous media aimed at converting glucose into compounds with higher added value. The electrodes were prepared by electrochemical oxidation of Ti in solution of 1.0 mol L-1 NaH2PO4 + 0.3% (m/m) HF as supporting electrolyte under a potential of 20V for 2 h and calcined at 450 ° C. An analytical method based on ion exchange chromatography with amperometric detection was developed for glucose, gluconic acid, glucarico acid, arabitol and Arabinose analysis and analytical curves were constructed at concentrations of 1.00 to 20,0x10-5 mol L-1, r = 0.9995, and the method achieved detection limits and determination around 0,03x10-6 mol L-1 and 0,08x10-6 mol L-1 for glucose determination, respectively. The method was used for monitoring the generated products due the oxidation photoeletrocatalytic 10.0 mmol L-1 glucose solution under potential of +1.5 V vs Ag / AgCl and irradiating UV / Vis that achieved 72% conversion after 180 min of treatment. Measurements of total organic carbon removal showed that 28% of the glucose was converted to CO2 and the rest was transformed into other products, such as arabinose, arabinitol, 4- ketoglicose, glucohexodialdose, Glucone-δ-lactone, 6-deoxyglucose and acid gluconic, most of which was confirmed by mass spectrometry. The results demonstrate that photoelectrocatalysis technique may be a simple, economical and attractive alternative to promote glucose conversion into some products of economic interest.

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Curutchet, Antton. "Etude par DFT de photocatalyseurs pour des applications en photodissociation de l'eau." Thesis, Lyon, 2019. http://www.theses.fr/2019LYSEN010/document.

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Dans une société qui peine à renoncer à l'utilisation des énergies fossiles, la production d'hydrogène à partir d'eau par photocatalyse solaire est une alternative que les chimistes se doivent d'explorer. La mise en place de cette solution est conditionnée à la résolution de deux problèmes majeurs : augmenter l'efficacité de la conversion solaire par le développement de nouveaux semi-conducteurs, et améliorer la réactivité en surface par le développement de co-catalyseurs efficaces. Dans un premier temps, nous avons contribué à l'étude d'une nouvelle famille de semi-conducteurs par des calculs ab initio DFT. Différentes propriétés clés ont été calculées et comparées aux valeurs expérimentales. Nous avons montré que pour une même famille de matériaux, l'absorption peut être contrôlée par modification de la composition.Ensuite, nous nous sommes focalisés sur la réaction d'oxydation de l'eau (OER). Pour cette réaction les catalyseurs de type oxyhydroxydes et leurs dérivés sont très prometteurs car à la fois efficaces et contenant des éléments abondants sur Terre, mais la compréhension de son mécanisme reste limitée. Sur le composé modèle CoOOH, nous en avons réalisé une analyse approfondie par une étude exhaustive des intermédiaires ainsi que par modélisation explicite du potentiel électrochimique. Nos études ont montré la nécessite de prendre en compte plusieurs sites réactionnels dans la détermination des mécanismes d'oxydation de l'eau sur la surface de ces catalyseurs. Enfin, une étude préliminaire de l'utilisation de la biomasse a été menée, dans le but de combiner valorisation de la biomasse et production d'hydrogène. Le cas de l'oxydation du glycérol est envisagé
In a society struggling to waive the use of fossil fuels, hydrogen production from water by solar photocatalysis is a alternative chemists have to consider. Setting up of this solutions asks to tackle two major issues : increase solar energy conversion by developing new semiconductors, and enhance the surface reactivity by developing efficient cocatalysts.First, DFT \emph{ab initio} calculations were carried out on a new family of semiconductor materials. Different key properties were computed and compared to experimental values. We showed that for a same material family, absorption can be controlled by changing the composition.Then, we focused on Oxygen Evolution Reaction (OER). For this reaction oxyhydroxides catalysts and their derivatives seem promising as both efficient and containing earth-abundant elements, but the understanding of its mechanism still remains unclear. On CoOOH model compound, we realised an extended analysis by a comprehensive study of intermediates and by explicit modelling of electrochemical potential. Our studies showed that taking into account several reactive sites is necessary to determine the OER mechanism on these catalysts' surface.Last, a preliminary study of biomass use was carried, in order to combine its valorization along with hydrogen production. The case of glycerol photoreforming is considered

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Baccaro, Alexandre Luiz Bonizio. "Aperfeiçoamento de sistema de preparo de amostras em microescala por processamento fotoeletrocatalítico de matéria orgânica em célula eletroquímica irradiada com UV-LED, visando à análise de traços de metais." Universidade de São Paulo, 2012. http://www.teses.usp.br/teses/disponiveis/46/46136/tde-28052012-104226/.

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A aplicação do processo de fotoeletrocatálise à eliminação de interferentes orgânicos em baixa concentração na eletroanálise de metais foi abordada tomando o quelato Cu(II)-EDTA como sistema modelo e o restabelecimento da onda voltamétrica do cobre como indicador de efetividade. Desenvolveram-se células eletroquímicas de camada delgada (espessura de 600 micrômetros) nas quais alguns microlitros de amostra são tratados sobre um eletrodo modificado com TiO2 (tipo P25, rico em anatase), cuja superfície é irradiada através de uma janela por um LED (370 nm). Foram construídos e avaliados os seguintes eletrodos: pasta de carbono, TiO2 e óleo parafínico (CPE-TiO2), compósitos de grafite, TiO2 e adesivo epóxi ou de silicone e ouro com oclusão de TiO2 por eletrodeposição. Estudo do efeito de parâmetros como potencial aplicado ao eletrodo, composição do eletrólito e concentração de EDTA sobre a fotocorrente permitiu selecionar condições de trabalho e estabelecer algumas correlações. Por exemplo, observou-se linearidade entre a fotocorrente e a concentração de EDTA até 1,0 mmol/L, aparente limite superior do controle difusional do processo para potência radiante aplicada, acima do qual, a cinética de oxidação passa a sobrepujar o transporte no controle da velocidade de reação. O restabelecimento pleno da onda de Cu(II) 1,0 mmol.L-1 foi observado após a irradiação por 10 min quando a concentração de EDTA não excedia 0,94 mmol.L-1. Descobriu-se um procedimento mais rápido que consiste na aplicação do tratamento fotoeletrocatalítico simultâneo ao registro de voltamogramas cíclicos repetitivos (eletrodo de Au-TiO2, 0,3 a 0,7 V vs. Ag/AgCl, 100 mV.s-1). Após o sexto ciclo, a altura do pico de redissolução anódica do Cu (reduzido durante a varredura no sentido negativo) estabiliza, permitindo a quantificação sem etapa prévia de abertura.
The photoelectrocatalysis process was investigated for the elimination of organic compounds interference on the electroanalysis of trace metals. Cu(II)-EDTA chelate was chosen as model system and the recovery of copper voltammetric peak, as effectiveness indicator. Thin layer cells (thickness of 600 micrometers) were designed for the treatment of some microliters of sample by irradiation (370 nm LED) of an electrode modified with TiO2 (P25, anatase rich). The following modified electrodes were prepared and evaluated: carbon paste with TiO2 and paraffin oil (CPE-TiO2), composites of graphite, TiO2 and epoxy or silicone binders and TiO2 occluded in electrodeposited gold on a gold substrate. The effect of parameters like potential bias, electrolyte composition and EDTA concentration on the photocurrent was evaluated to setup working conditions. Some correlations were observed, e.g., a linear dependence between photocurrent and EDTA concentration up to 1.0 mmol/L. For the irradiance applied, this concentration is possibly the upper limit of operation diffusion transport control, above which, the kinetics of the oxidation at the TiO2 modified electrode becomes the controlling process. For EDTA concentrations not exceeding 0.94 mmol.L-1, full recovery of 1.0 mmol.L-1 Cu(II) voltammetric peaks was observed after 10 min of irradiation. A faster procedure was discovered and consists in recording repetitive cyclic voltammograms (Au-TiO2 electrode, 0,3 to 0,7 V vs. Ag/AgCl scans, 100 mV.s-1) simultaneously with continuous irradiation. After the sixth cycle, the copper anodic stripping peak height stabilizes allowing quantification without previous sample pre-treatment step.

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Araújo, Moisés Albuquerque de. "Síntese, caracterização e estudo das propriedades fotoeletrocatalíticas dos fotoanodos BiVO4 e BiVO4/FeOOH." Universidade Federal de São Carlos, 2015. https://repositorio.ufscar.br/handle/ufscar/7833.

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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
Among the variety of semiconductor materials investigated to apply in electrochemical cells bismuth vanadate (BiVO4) is one of the candidate which would be used as photoanode. Thus, this study aimed to synthesize thin films of BiVO4 and their modification with a thin layer of iron (III) oxyhydroxide (FeOOH) by photodeposition and study their photoelectrocatalytic properties. The optimization of BiVO4 synthesis condition was assessed by a factorial design 23 and an analysis of univariate type. The parameters studied were annealing temperature (500 and 600 °C), calcinations time (30, 60, 150 and 270 min.), solvent type employed for dissolving the BiVO4 precursor reagents (poly ethylene glycol 300-PEG 300, PEG 400, ethylene glycol-EG, mixture 1:1 by volume of PEG 300 and EG), deposition method of BiVO4 films (dropping and spin coating) and method of drying layers (heating at 500 °C, heat gun and no drying). From the optimized condition BiVO4 film was prepared by dissolving bismuth (III) nitrate and ammonium metavanadate in a mixture of 1:1 by volume of EG and PEG 300, it was deposited onto glass containing FTO by spin coating and then calcinated directly at 500 °C for 60 min. The photodeposition was carried out in the mixture FeSO4 and sodium citrate medium both 1 mmol L-1 and pH 4.7 by applying the open circuit potential for 5 min. and under light incidence. and then polarizing at 1.2 V for 1 min. BiVO4 and BiVO4/FeOOH films were characterized by XRD, SEM, EDS, UV-vis, voltammetry (cyclic and linear) and electrochemical impedance spectroscopy. The results reveled that photocurrent values increased 2.5 times at 0.71 V and the on set potential shifted to less positive value in the presence of FeOOH, also there was a considerable reduction of the charge transfer resistance in the interface photoanode/solution. The bare BiVO4 films were photostable during the illumination time studied which was 4 h. However, the modified films did not show the same behavior, the photocurrent value decreased 29% after 4 h illuminated. The results in the sulphite presence showed that photocurrent value for bare BiVO4 and BiVO4/FeOOH were less than the maximum photocurrent value which would achieve for this materias.
Dentre os diversos materiais semicondutores estudados para aplicação em células fotoeletroquímicas encontra-se o vanadato de bismuto (BiVO4), o qual pode ser utilizado como fotoanodo. Deste modo, o presente trabalho teve como objetivo principal a síntese de filmes finos de BiVO4 e sua modificação com uma fina camada de oxihidróxido de ferro (III) (FeOOH) por fotodeposição e avaliação das propriedades fotoeletrocatalíticas destes materiais. A otimização das condições de síntese do BiVO4 foi avaliada por um planejamento fatorial 23 e por uma análise do tipo univariada. Os parâmetros estudados foram temperatura de calcinação (500 e 600 °C), tempo de calcinação (30, 60, 150 e 270 min.), tipo de solvente empregado para dissolução dos reagentes precursores do BiVO4 (polietileno glicol 300-PEG 300, PEG 400, etileno glicol-EG, mistura 1:1 em volume de PEG 300 e EG), método de deposição dos filmes de BiVO4 (dropping e spin coating) e método de secagem das camadas dos filmes (aquecimento a 500 °C, soprador térmico e sem secar). Nas condições otimizadas o filme de BiVO4 foi preparado pela dissolução de nitrato de bismuto (III) e metavanadato de amônio em uma mistura de 1:1 em volume de EG e PEG 300, depositado sobre vidro contendo FTO por spin coating e depois calcinado diretamente a 500 ºC por 60 min. A fotodeposição foi realizada em meio da mistura FeSO4 e citrato de sódio ambos a 1 mmol L-1 e pH 4,7, aplicando-se o potencial de circuito aberto por 5 min. e com incidência de luz, seguida de polarização em 1,2 V por 1 min. Os filmes de BiVO4 e BiVO4/FeOOH foram caracterizados por DRX, MEV, EDX, UV-vis, voltametria (cíclica e linear) e espectroscopia de impedância eletroquímica. Os resultados mostram que na presença do FeOOH houve aumento de 2,5 vezes nos valores de densidade fotocorrente em 0,71 V e o potencial de on set deslocou-se para valores menos positivos, bem como uma redução considerável na resistência de transferência de carga na interface fotoanodo/solução. Os filmes de BiVO4 puro apresentaram-se fotoestáveis durante o tempo de iluminação estudado, 4 h. No entanto, os filmes modificados não apresentaram o mesmo comportamento, houve um decréscimo de 29% no valor de densidade de fotocorrente após 4 h de iluminação. O estudo na presença do sulfito mostrou que os valores de fotocorrentes para o BiVO4 puro e o BiVO4/FeOOH estão abaixo do valor máximo que se poderia obter para estes materiais.

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Oliveira, Gisele Augusto Rodrigues de. "Comparação da eficiência do tratamento por fotoeletrocatálise em relação à cloração química convencional na redução da mutagenicidade de azo corantes empregando o ensaio de micronúcleos." Universidade de São Paulo, 2010. http://www.teses.usp.br/teses/disponiveis/60/60134/tde-13042010-112953/.

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Os azo corantes Disperse Red 1, Disperse Orange 1 e Disperse Red 13 são amplamente utilizados para o tingimento de fibras e são mutagênicos para o ensaio de Salmonella/microssoma e para o ensaio de micronúcleos. O aumento da complexidade e dificuldades para o tratamento de efluentes têxteis tem levado à busca constante de novas metodologias para o tratamento destes rejeitos. A cloração é um método amplamente empregado para a desinfecção de águas e efluentes, mas também para remover ou reduzir a cor do efluente a fim de atender o padrão de emissão da legislação brasileira. Porém, muitos trabalhos mostram que este tratamento muitas vezes não é capaz de remover a mutagenicidade dos corantes e em alguns casos pode até aumentar a toxicidade da amostra. Já a fotoeletrocatálise, aparentemente, é eficiente tanto na degradação desses compostos em amostras aquosas como na redução da atividade mutagênica, como demonstraram alguns ensaios preliminares. Este trabalho tem como objetivo a avaliação da eficiência do tratamento por fotoeletrocatálise na remoção da mutagenicidade dos azo corantes Disperse Red 1, Disperse Orange 1 e Disperse Red 13 presentes em amostras aquosas em comparação à cloração química convencional utilizando o teste de micronúcleos (MNs) em células HepG2. Os resultados demonstraram que a freqüência de MNs induzidos pelas diferentes concentrações testadas das soluções dos corantes estudados não foram significativamente diferentes do controle negativo. Nossos dados também revelaram que os índices de proliferação do bloqueio da citocinese (IPBC) em cultura de células HepG2 tratadas com os três corantes após a cloração e fotoeletrocatálise também não apresentaram diferenças estatísticas em relação aos seus respectivos controles negativos. A análise comparativa dos azo corantes Disperse Red 1, Disperse Orange 1 e Disperse Red 13 clorados e fotoeletrocatalisados com os corantes originais estudados pelo nosso grupo (CHEQUER, 2008; CHEQUER et al., 2009) mostrou uma diminuição no número de MNs indicando que após os tratamentos houve a remoção da mutagenicidade a partir da concentração de 1,0 µg/mL para os três corantes estudados. Portanto, podemos concluir que a cloração química convencional e a fotoeletrocatálise, nas condições testadas, são eficientes na remoção da mutagenicidade dos azo corantes Disperse Red 1, Disperse Orange 1 e Disperse Red 13 em relação à indução de micronúcleos.
The azo dyes Disperse Red 1, Disperse Orange 1 and Disperse Red 13 are widely used in dyeing processes and are mutagenic for Salmonella/microsome and micronucleus assays. The increasing of the complexity and difficulties for treatments of textile effluents has led to a constant search for new methodologies for the treatment of these wastewaters. Chlorination is a method extensively used for water and wastewaters disinfection and to remove or reduce the color of effluents in order to respect the standard of discharges issued by the Brazilian legislation. However, a lot of studies have shown that this treatment is not often able to remove the mutagenicity of the dyes, and in some cases it may even increase the toxicity of the sample. On the other hand, photoelectrocatalysis is apparently efficient both in the degradation of these compounds in aqueous samples and in reduction of the mutagenic activity, as demonstrated by some preliminary assays. This study aims to evaluate the efficiency of the photoelectrocatalysis treatment in the removal of the mutagenicity of the azo dyes Disperse Red 1, Disperse Orange 1 and Disperse Red 13 present in aqueous sample in comparison to conventional chemical chlorination using the micronucleus test (MNs) in HepG2 cells. The results showed that the frequency of MNs induced by different tested concentrations of the solutions of the studied dyes were not significantly different from the negative control. Our data also revealed that the cytokinesis-block proliferation index (CPBI) in cultures of HepG2 cells treated with the three dyes after chlorination and photoelectrocatalysis also showed no statistical differences related to the their respective negative controls. The comparative analysis of azo dyes chlorinated and photoelectrocatalysed Disperse Red 1, Disperse Orange 1 and Disperse Red 13 with the original dyes studied by our group (CHEQUER, 2008; CHEQUER et al., 2009) showed a decrease in the number of MNs indicating that after the treatments occurred the removal of the mutagenicity potencial at concentration of 1,0 µg/mL for the three dyes studied. Therefore, we conclude that conventional chemical chlorination and photoelectrocatalysis, under the conditions tested, are effective in removing of the mutagenicity of the azo dyes Disperse Red 1, Disperse Orange 1 and Disperse Red 13 related to induction of micronucleus.

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Morávková, Eva. "Kinetika fotokatalytické a fotoelektrokatalytické degradace modelových polutantů bazénových vod." Master's thesis, Vysoké učení technické v Brně. Fakulta chemická, 2021. http://www.nusl.cz/ntk/nusl-449336.

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This diploma thesis deals with the coating and printing of thin layers based on nanoparticles of titanium dioxide and organosilica binder on various substrates. The influence of the ratio of the both components on the activity of the prepared immobilized layers was studied. Five compositions with different ratios of TiO2 and binder were prepared. The work focuses mainly on the study of photocatalytic and photoelectrocatalytic properties of prepared layers. It was also important to characterize the mechanical properties of the layer such as hardness or adhesion. Both photocatalytic and photoelectrocatalytic activity were determined by monitoring the degradation of the model pollutants in aqueous solutions. The dye Acid Orange 7 and UV filter 2-hydroxy-4-methoxybenzophenone were used in conjunction with UV/VIS spectroscopy or high performance liquid chromatography techniques. Both photocatalytic and photoelectrocatalytic activity were expressed using kinetic characteristics.

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Batista, Grau Patricia. "Desarrollo de nanoestructuras de ZnO mediante anodizado electroquímico en diferentes condiciones para su aplicación en el área energética." Doctoral thesis, Universitat Politècnica de València, 2021. http://hdl.handle.net/10251/172606.

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Tesis por compendio
[ES] La presente Tesis Doctoral se centra en el desarrollo de nanoestructuras de óxido de zinc (ZnO) mediante anodizado electroquímico en diferentes condiciones para su aplicación en el área energética, en particular, en la producción de hidrógeno mediante la rotura fotelectrocatalítica de la molécula de agua. El hidrógeno es un vector energético que se plantea como solución al problema asociado a la intermitencia diurna y estacional de la energía solar y a la variabilidad en la demanda de energía. Por otra parte, el ZnO es un material semiconductor prometedor como fotocatalizador para la producción de hidrógeno debido a sus características y propiedades. En este contexto, el ZnO es un material muy abundante, y por extensión, relativamente barato, no es tóxico y presenta una energía de banda prohibida de 3,37 eV, lo que le permite la absorción de fotones en la región UV del espectro solar. Asimismo, las posiciones de sus bandas de energía son apropiadas para llevar a cabo la fotoelectrólisis del agua. En la presente Tesis Doctoral la síntesis de nanoestructuras de ZnO se llevó a cabo mediante anodizado electroquímico, puesto que este método presenta múltiples ventajas frente a otros métodos de síntesis habituales. En general, el anodizado electroquímico constituye un método rápido, sencillo y eficaz de síntesis de nanoestructuras de ZnO mediante el que es posible diseñar las características superficiales de las nanoestructuras (tamaño y morfología) a través del control de sus parámetros. Como resultado de una revisión bibliográfica en profundidad, se analizó la influencia de los parámetros del anodizado en las características superficiales de las nanoestructuras. Además, se investigaron aquellos parámetros cuya influencia todavía no había sido analizada. Por una parte, se estudió la influencia de emplear diferentes condiciones hidrodinámicas de flujo (dadas por la variación de la velocidad de rotación del electrodo). Por otra parte, se estudió la influencia conjunta de modificar el electrolito con la adición de un disolvente orgánico (etanol o glicerol en distintas proporciones) y variar la velocidad de rotación del electrodo. Las muestras de ZnO sintetizadas se sometieron a una caracterización morfológica, estructural, electroquímica y fotoelectroquímica y se estudiaron sus propiedades para ser empleadas como fotocatalizadores en la producción de hidrógeno. De acuerdo con los resultados, las diferentes condiciones de anodizado dieron lugar a diversas nanoestructuras de ZnO con diferentes características superficiales y fotoelectrocatalíticas. Así, se obtuvieron nanoestructuras de elevada área superficial con morfologías de nanocables de distintos tamaños, nanotubos, nanoesferas y nanoesponjas. Asimismo, tras el calentamiento térmico las muestras presentaron una estructura cristalina hexagonal wurtzita con elevada cristalinidad y la presencia de defectos estructurales. Igualmente, las nanoestructuras sintetizadas presentaron una elevada fotoactividad, dada por los valores elevados de densidad de fotocorriente, presentando propiedades apropiadas para su utilización en la producción de hidrógeno. La muestra que presentó el valor de densidad de fotocorriente más elevado (0,34 mA/cm2) fue la muestra de nanocables de ZnO anodizada a 0 rpm en un electrolito con un contenido en etanol del 10 % en volumen. En la aplicación de dicha muestra en la producción de hidrógeno se obtuvo un volumen teórico de hidrógeno de 1,55 litros por hora de sol y metro cuadrado de ZnO.
[CA] La present Tesi Doctoral se centra en el desenvolupament de nanoestructures d'òxid de zinc (ZnO) mitjançant anoditzat electroquímic en diferents condicions per a l'aplicació en l'àrea energètica, en particular, en la producció d'hidrogen mitjançant el trencament fotelectrocatalític de la molècula d'aigua. L'hidrogen és un vector energètic que es planteja com a solució al problema associat a la intermitència diürna i estacional de l'energia solar i a la variabilitat en la demanda d'energia. D'altra banda, el ZnO és un material semiconductor prometedor com a fotocatalitzador per a la producció d'hidrogen degut a les seues característiques i propietats. En aquest context, el ZnO és un material molt abundant, i per extensió, relativament barat, no és tòxic i presenta una energia de banda prohibida de 3,37 eV, la qual cosa li permet l'absorció de fotons a la regió UV de l'espectre solar. Així mateix, les posicions de les seues bandes d'energia són apropiades per a dur a terme la fotoelectròlisi de l'aigua. En la present Tesi Doctoral la síntesi de nanoestructures de ZnO es va dur a terme mitjançant anoditzat electroquímic, ja que aquest mètode presenta múltiples avantatges enfront d'altres mètodes de síntesi habituals. En general, l'anoditzat electroquímic constitueix un mètode ràpid, senzill i eficaç de síntesi de nanoestructures de ZnO mitjançant el qual és possible dissenyar les característiques superficials de les nanoestructures (grandària i morfologia) a través del control dels seus paràmetres. Com a resultat d'una revisió bibliogràfica en profunditat, es va analitzar la influència dels paràmetres de l'anoditzat en les característiques superficials de les nanoestructures. A més, es van investigar aquells paràmetres la influència dels quals encara no havia sigut analitzada. D'una banda, es va estudiar la influència d'emprar diferents condicions hidrodinàmiques de flux (donades per la variació de la velocitat de rotació de l'elèctrode). D'altra banda, es va estudiar la influència conjunta de modificar l'electròlit amb l'addició d'un dissolvent orgànic (etanol o glicerol en diferents proporcions) i variar la velocitat de rotació de l'elèctrode. Les mostres de ZnO sintetitzades es van sotmetre a una caracterització morfològica, estructural, electroquímica i fotoelectroquímica i es van estudiar les seues propietats per a ser emprades com fotocatalitzadors en la producció d'hidrogen. D'acord amb els resultats, les diferents condicions d'anoditzat van donar lloc a diverses nanoestructures de ZnO amb diferents característiques superficials i fotoelectrocatalítiques. Així, es van obtindre nanoestructures d'elevada àrea superficial amb morfologies de nanocables de diferents grandàries, nanotubs, nanoesferes i nanoesponges. Així mateix, després del calfament tèrmic les mostres van presentar una estructura cristal·lina hexagonal wurtzita amb elevada cristallinitat i la presència de defectes estructurals. Igualment, les nanoestructures sintetitzades van presentar una elevada fotoactivitat, donada pels valors elevats de densitat de fotocorrent, presentant propietats apropiades per a la seua utilització en la producció d'hidrogen. La mostra que va presentar el valor de densitat de fotocorrent més elevat (0,34 mA/cm²) va ser la mostra de nanocables de ZnO anoditzada a 0 rpm en un electròlit amb un contingut en etanol del 10% en volum. En l'aplicació d'aquesta mostra en la producció d'hidrogen es va obtindre un volum teòric d'hidrogen de 1,55 litres per hora de sol i metre quadrat de ZnO.
[EN] This Doctoral Thesis focuses on the development of zinc oxide (ZnO) nanostructures by electrochemical anodization under different conditions for its application in the energy area, in particular, in the production of hydrogen through photoelectrochemical water splitting. Hydrogen is an energy vector that is proposed as a solution to the problem associated with the diurnal and seasonal intermittency of solar energy and the variability in the energy demand. On the other hand, ZnO is a promising semiconductor material as a photocatalyst for hydrogen production due to its characteristics and properties. In this context, ZnO is a very abundant material, and by extension, relatively cheap, it is non-toxic and has a band-gap energy of 3.37 eV, which allows it to absorb photons in the UV region of the solar spectrum. Besides, the positions of ZnO energy bands are appropriate to carry out photoelectrochemical water splitting. In the present Doctoral Thesis, the synthesis of ZnO nanostructures was carried out by electrochemical anodization, since this method has multiple advantages compared to other common synthesis methods. In general, electrochemical anodization constitutes a fast, simple, and effective method of synthesis of ZnO nanostructures by means of which it is possible to design the surface characteristics of the nanostructures (size and morphology) by controlling anodization parameters. As a result of an in-depth bibliographic review, the influence of anodization parameters on the surface characteristics of nanostructures was analyzed. In addition, those parameters whose influence had not yet been analyzed were investigated. On the one hand, the influence of using different controlled hydrodynamic conditions (given by the variation of the rotation speed of the electrode) was studied. On the other hand, the influence of both modifying the electrolyte with the addition of an organic solvent (ethanol or glycerol in different proportions) and varying the electrode rotation speed was studied. The synthesized ZnO samples were subjected to a morphological, structural, electrochemical and photoelectrochemical characterization and their properties were studied to be used as photocatalysts in hydrogen production. According to the results, the different anodization conditions gave rise to various ZnO nanostructures with different surface and photoelectrocatalytic characteristics. Thus, high surface area nanostructures were obtained with morphologies of nanowires of different sizes, nanotubes, nanospheres and nanosponges. Likewise, after thermal annealing the samples presented a wurtzite hexagonal crystalline structure with high crystallinity and the presence of structural defects. Likewise, the synthesized nanostructures presented high photoactivity, given by the high values of photocurrent density, presenting appropriate properties for their use in the production of hydrogen. The sample that presented the highest photocurrent density value (0.34 mA / cm2) was the ZnO nanowires anodized at 0 rpm in an electrolyte with an ethanol content of 10 % by volume. In the application of this sample in the hydrogen production, a theoretical volume of hydrogen of 1.55 liters per hour of sun and square meter of ZnO was obtained.
Authors would like to express their gratitude for the financial support to the Generalitat Valenciana and to the European Social Fund within the subvention to improve formation and employability of technical and management staff of I+D (GJIDI/2018/A/067) and for its financial support through the project: IDIFEDER/018/044. Authors also thank for the financial support to the Ministerio de Economía y Competitividad (Project Code: CTQ2016-79203-R) and to the Ministerio de Ciencia e Innovación-Agencia Estatal de Investigación (Project Code: PID2019-105844RB-I00) for its help in the Laser Raman Microscope acquisition (UPOV08-3E- 012) and for the co-finance by the European Social Fund.
Batista Grau, P. (2021). Desarrollo de nanoestructuras de ZnO mediante anodizado electroquímico en diferentes condiciones para su aplicación en el área energética [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/172606
TESIS
Compendio

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37

Martins, Alysson Stefan. "Síntese e caracterização de eletrodos de TiO2/WO3, nanotubos de TiO2/WO3 e nanotubos de TiO2/titanato para aplicação no tratamento fotoeletrocatalítico dos interferentes endócrinos bisfenol-A e propil." Universidade de São Paulo, 2017. http://www.teses.usp.br/teses/disponiveis/75/75135/tde-16012018-094702/.

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Tecnologias efetivas para o tratamento de águas e efluentes representam um dos grandes desafios da nossa sociedade; dentre as opções, a fotoeletrocatálise pode ser considerada como uma técnica alternativa e de interesse. Nesse contexto, o presente trabalho teve como objetivo desenvolver eletrodos de TiO2 modificados visando o tratamento fotoeletrocatalítico de interferentes endócrinos. Realizou-se inicialmente a síntese de nanotubos de TiO2 (TiO2-NT) sobre substrato de Ti metálico via anodização eletroquímica em eletrólito NaH2PO4/HF. Para minimizar as limitações inerentes ao TiO2 realizou-se a eletrodeposição de WO3 sobre os nanotubos de TiO2 (Ti/TiO2-NT/WO3) e diretamente sobre o substrato de Ti metálico. Este último revelou a formação de uma camada fina de TiO2 sobre a superfície, posterior ao tratamento térmico, formando um compósito (Ti/TiO2/WO3). A análise de difração de raios-X confirmou a formação da fase monoclínica de WO3 para ambas as sínteses e a fase anatase para os eletrodos de Ti/TiO2-NT/WO3. Para as duas sínteses, as medidas de energia dispersiva de raios-X revelaram uma quantidade crescente de W na composição dos eletrodos com o aumento do tempo de eletrodeposição. Teores elevados de W (acima de 1,2 %) apresentaram uma diminuição expressiva nos valores de fotocorrente. No entanto, baixos teores de W (entre 0,4 e 1,2 %) indicaram um aumento de 20 % nos valores de fotocorrente para os eletrodos de Ti/TiO2-NT/WO3 (20 mA cm-2) e Ti/TiO2/WO3 (17 mA cm-2) comparados aos não modificados, no potencial de +2,0 V. As análises de reflectância difusa mostraram uma baixa energia de bandgap (≈ 2,90 eV, eletrodos de Ti/TiO2-NT/WO3) e um aumento na absorção da irradiação UV-Vis. Posteriormente, os eletrodos modificados foram aplicados na oxidação fotoeletrocatalítica (FE) dos compostos bisfenol-A (BPA) e propilparabeno (PPB), sob irradiação UV-Vis. O método FE apresentou um excelente desempenho em condições ácidas, aplicando-se potencial de +1,50 V e +0,50 V para os eletrodos Ti/TiO2-NT/WO3 e Ti/TiO2/WO3, respectivamente. A mineralização dos compostos BPA e PPB foi superior a 80 % tanto para o Ti/TiO2-NT/WO3 como para o Ti/TiO2/WO3. Quanto à taxa de remoção, o BPA e PPB foram completamente removidos após 45 e 60 min, respectivamente, para os eletrodos de Ti/TiO2/WO3 e após 30 minutos para os eletrodos de Ti/TiO2-NT/WO3. Adicionalmente, os eletrodos apresentaram um baixo consumo energético e boa estabilidade química. Comparada à técnica de fotocatálise (FC), a FE revelou uma eficiência de mineralização 2 vezes superior para o Ti/TiO2-NT/WO3 e mais de 20 % superior para o Ti/TiO2/WO3. Logo, as modificações dos eletrodos de TiO2 com WO3 constituíram importantes contribuições para o desempenho dos materiais, sendo um passo importante para a aplicação em tratamentos alternativos de descontaminação de águas residuárias. Ainda foi de interesse neste trabalho propor um método para a inserção de nanotubos (TiNT) e nanofolhas (TiNS) de titanatos no interior de nanotubos de TiO2 via eletroforese. O estudo possibilitou o desenvolvimento de um método simples e eficiente para a modificação de nanoestruturas complexas. A movimentação do contra eletrodo sobre a superfície do eletrodo de trabalho, adaptado com uma escova nas laterais, reduziu a espessura da camada de TiNS/TiNT. O potencial aplicado (20 V) e a estimulação mecânica da superfície foram importantes para a incorporação das nanoestruturas dentro dos poros de TiO2-NTs. Como resultado, os eletrodos apresentaram um aumento da hidrofobicidade e uma melhora na capacidade de oxidação direta comparado ao eletrodo não modificado.
Effective technologies for the water and wastewater treatment represent a challenges for our society; among the options, the photoelectrocatalysis can be considered a promising and interesting alternative. In this context, the objective of this study was to develop modified TiO2 electrodes for the photoelectrocatalytic treatment of endocrine disruptors. The synthesis of TiO2 nanotubes (TiO2-NT) on metallic Ti substrate was carried out via electrochemical anodization in NaH2PO4 /HF electrolyte. In order to minimize the limitations inherent of TiO2, the electrodeposition of WO3 was performed on the TiO2 nanotubes (Ti/TiO2-NT/WO3) and also in the metallic Ti substrate. The deposition on the Ti metallic produced a thin layer of TiO2 on the surface, subsequent to the heat treatment, generating a composite (Ti/TiO2/WO3). The X-ray diffraction analysis (XRD) confirmed the monoclinic phase of WO3 for both the syntheses and the anatase phase of TiO2 for the Ti/TiO2-NT/WO3 electrodes. For the two syntheses, the X-ray dispersive energy (EDX) analisys indicated an increasing amount of tungsten (W) in the composition of the electrodes with increasing of electrodeposition time. High W content (above 1.2%) showed a significant decrease in the photocurrent values. However, low content of W (between 0.4 and 1.2 %) indicated an increase of 20 % in the photocurrent values for the electrodes Ti/TiO2-NT/WO3 (20 mA cm-2) and Ti/TiO2/WO3 (17 mA cm-2) compared to the unmodified ones, at the potential of +2.0 V. Difuse reflectance analysis indicated low bandgap energy (≈ 2.90 eV, Ti/TiO2-NT/WO3 electrodes) and an increase in the UV-Vis irradiation absorption. The best electrodes modified with WO3 to the both syntheses were applied in the photoelectrocatalytic oxidation (PEC) of bisphenol-A (BPA) and propylparaben (PPB) compounds, under UV-Vis irradiation. The PEC method presented an excellent performance in acidic conditions, applying a bias potential of +1.50 V and +0.50 V for Ti/TiO2-NT/WO3 and Ti/TiO2/WO3 electrodes, respectively. The mineralization of BPA and PPB compounds was greater than 80% for both Ti/TiO2-NT/WO3 and Ti/TiO2/WO3. In relation to the removal rate, BPA and PPB were completely removed after 45 and 60 min, respectively, for Ti/TiO2/WO3 electrodes and after 30 minutes for Ti/TiO2-NT/WO3 electrodes. Additionally, the electrodes presented a low energy consumption and good chemical stability. Compared to the photocatalysis (PC), the PEC was 2 times higher to the mineralization efficiency for Ti/TiO2-NT/WO3 and almost 20% higher for Ti/TiO2/WO3. Thus, the modifications of the TiO2 electrodes with WO3 represent an important contribution to the performance of materials and, therefore, a positive step for the application in alternative treatments of decontamination of wastewater. It was also of interest in this work to propose a new method for the insertion of nanotubes (TiNT) and nanosheets (TiNS) of titanates inside of TiO2 nanotubes via electrophoretic deposition. In this study was developed a simple and efficient method for the modification of complex nanostructures. The movement of the counter electrode on the surface of the working electrode, adapted with a brush on the edges, reduced the thickness of the TiNS/TiNT layer. The potential applied (20 V) and the mechanical stimulation in the surface were important for the incorporation of TiNS/TiNT into the pores of TiO2-NTs. As a result, the electrodes increased the hydrophobicity and an improvement to the direct oxidation capacity compared to the unmodified electrode.

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Gross, Pierre-Alexandre. "Modification de nanotubes de TiO2 pour la production d’hydrogène par photodissociation de l’eau sous lumière solaire." Thesis, Strasbourg, 2014. http://www.theses.fr/2014STRAF053.

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Ce travail de thèse traite de la production d’hydrogène par le procédé de photoélectrocatalyse en utilisant une photoanode à base de nanotubes de TiO2 verticalement alignés. L’utilisation du TiO2 étant limité pour des applications solaires en raison de son large gap, il est nécessaire de le modifier. Deux approches sont proposées pour modifier les nanotubes de TiO2 et leur permettre d’absorber la lumière visible. La première est une modification chimique du TiO2 par co-dopage cationique-anionique (Ta-N) ou (Nb-N). Les cations sont insérés durant la croissance des nanotubes grâce à une approche inédite, et l’azote est inséré durant le traitement thermique. Ceci a pour effet la formation d’orbitales hybrides qui entraîne une réduction du gap et une activité sous lumière visible, tout en permettant une stabilité de la structure. La seconde approche consiste à déposer des nanoparticules d’Ag sur la surface des nanotubes de TiO2. Grâce au contrôle de la morphologie des nanoparticules d’Ag, leur résonnance plasmonique permet de stimuler l’absorption du TiO2 et ainsi d’augmenter son rendement à la fois sous lumière UV et sous lumière visible
This work is about the production of hydrogen by photoelectrocatalysis using a vertically aligned TiO2 nanotubes based photoanode. Utilization of TiO2 for solar applications is limited due to its large band gap, it has to be modified. Two approaches are proposed for the modification of the TiO2 nanotubes to make them absorb visible light. The first one is the chemical modification of the TiO2 by (Ta-N) or (Nb-N) cationic-anionic co-doping. Cations are inserted during the growth of the nanotubes by a novel approach, and nitrogen is inserted during heat treatment. This leads to the formation of hybrid orbitals resulting in a band gap reduction and of activity under visible light. The second approach consists of the deposition of Ag nanoparticles on the surface of the TiO2 nanotubes. Thanks to the control of the morphology of the Ag nanoparticles, their plasmonic resonance can enhance the absorption of TiO2 and thus increase its activity both under UV and visible light

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Ferraz, Elisa Raquel Anastácio. "Avaliação da eficiência do tratamento com fotoeletrocatálise e cloração convencional na remoção dos azo corantes Disperse Orange 1, Disperse Red 1 e Disperse Red 13 de amostras aquosas." Universidade de São Paulo, 2011. http://www.teses.usp.br/teses/disponiveis/60/60134/tde-28032012-090020/.

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Os azo corantes atualmente são considerados um assunto preocupante no que se refere à saúde pública e ambiental, pois quando lançados nos efluentes industriais contaminam o meio ambiente. Infelizmente, o método convencional de tratamento de efluentes têxteis, bem como de águas brutas que os recebem não são capazes de remover de maneira eficaz os corantes bem como sua toxicidade. Dentro deste contexto, este trabalho teve como objetivo avaliar a eficiência do tratamento de amostras aquosas por fotoeletrocatálise em comparação com a cloração convencional como método alternativo de degradação de azo corantes, usando os corantes Disperse Orange 1, Disperse Red 1 e Disperse Red 13 como modelo. Adicionalmente, foi avaliada a citotoxicidade dos corantes originais em condrócitos bovinos e células HepG2 em cultura em monocamadas e 3D. Para tanto, soluções desses corantes originais, clorados e fotoeletrocatalisados foram avaliadas utilizando ensaios de genotoxicidade/mutagenicidade, citotoxicidade e ecotoxicidade. Todos os corantes originais e clorados foram genotóxicos para as células HepG2 no ensaio cometa. Para o ensaio com Salmonella, a cloração reduziu a mutagenicidade dos corantes para a linhagem YG1041 e aumentou o efeito para a linhagem TA98, exceto o Disperse Red 13 que teve a mutagenicidade reduzida para as duas linhagens após cloração. A fotoeletrocatálise removeu tanto a genotoxicidade quanto a mutagenicidade. Somente o Disperse Orange 1 induziu apoptose pelo ensaio com anexina V, mas essa citotoxicidade foi removida após os tratamentos. Os corantes Disperse Red 1 e Disperse Red 13 foram tóxicos para D. similis enquanto somente o Disperse Red 1 foi tóxico para V. fischeri, sendo que os tratamentos por cloração e fotoeletrocatálise diminuíram a toxicidade apresentada. Os corantes Disperse Orange 1 e Disperse Red 13 passaram a ser tóxicos para V. fischeri após cloração, sendo que a fotoeletrocatálise do Disperse Red 13 também gerou produtos tóxicos para esse organismo. Assim, embora seja um método de tratamento promissor, atenção deve ser dada na avaliação e aplicação da fotoeletrocatálise como um método alternativo à cloração. Os corantes originais Disperse Orange 1 e Disperse Red 13 diminuíram a atividade mitocondrial dos condrócitos, sendo que o Disperse Red 13 também diminuiu a produção de lactato. Todos os corantes reduziram a atividade mitocondrial das células HepG2 em monocamadas, ao passo que o Disperse Orange 1 deixou de exercer esse efeito no cultivo em 3D. Somente o Disperse Red 13 diminuiu a atividade de desidrogenases das células HepG2 e tal efeito foi observado tanto no cultivo em monocamadas quanto em 3D.
The azo dyes are currently considered as a concern regarding the environmental and public health, since when released in industrial effluents they pollute the environment. Unfortunately, the conventional method of treatment of textile effluents is not able to effectively remove both dyes and their toxicity. Within this context, this study aimed to evaluate the effectiveness of the treatment of aqueous samples by photoelectrocatalysis compared to conventional chlorination as an alternative method of degradation of azo dyes, using the dyes Disperse Orange 1, Disperse Red 1 and Disperse Red 13 as a model. Additionally, we evaluated the cytotoxicity of the original dyes using HepG2 cells and chondrocytes cultured in monolayer and in 3D. To this end, solutions of these original dyes, chlorinated and photoelectrocatalysed were evaluated using tests of genotoxicity / mutagenicity, cytotoxicity and ecotoxicity. All the dyes, original and chlorinated, were genotoxic to HepG2 cells in the comet assay. For the test with Salmonella, chlorination reduced the mutagenicity of the dyes for the YG1041 strain and increased the effect for the TA98 strain, except Disperse Red 13, which had the mutagenic effect reduced for both strains after chlorination. The photoelectrocatalysis removed both genotoxicity and mutagenicity. Only Disperse Orange 1 induced apoptosis by annexin V assay, but this cytotoxicity was removed after treatment. The dye Disperse Red 1 and Disperse Red 13 were toxic to D. similis while only the Disperse Red 1 was toxic to V. fischeri, and the treatment by chlorination and photoelectrocatalysis decreased the toxicity showed. The dyes Disperse Orange 1 and Disperse Red 13 began toxic to V. fischeri after chlorination, and the photoelectrocatalysis of the Disperse Red 13 generated toxic products for this organism. So, while it is a promising treatment method, attention should be given in the evaluation and application of photoelectrocatalysis as an alternative to chlorination. The dyes Disperse Orange 1 and Disperse Red 13 decreased the mitochondrial activity of chondrocytes, and the dye Disperse Red 13 also decreased the production of lactate. All the dyes reduced the mitochondrial activity of the HepG2 cells cultured in monolayer, while the Disperse Orange 1 did no show this effect in 3D. Only Disperse Red 13 decreased the activity of dehydrogenases of HepG2 cells and this effect was observed both in monolayer and in 3D.

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40

Yuh-Fan, Su, and 蘇昱帆. "Photoelectrocatalytic Reaction of Methyl Orange on Semiconductors." Thesis, 2000. http://ndltd.ncl.edu.tw/handle/60944884068279134551.

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碩士
國立成功大學
化學工程學系
88
Titanium dioxide is widely applied in photocatalysis to carry out the redox reaction. Recently, the usage of photoenergy is a significant subject of study in photocatalytic reaction. The usage of photoenergy of tungsten oxide is larger than titanium dioxide due to its smaller energy band-gap. However, the recombination of electron hole pair owing to inadequate reduction potential of conduction band of tungsten oxide results in bad phototcatalysis performance. In this study, using bias potential to improve tungsten oxide photocatalytic capability is investigated. Meanwhile, the influence of the electrode preparation condition and photoelectrocatalytic reaction factors is discussed. The photocatalyst electrode was prepared by deposited the semiconductor on conductive substrate with reactive sputtering. XRD, SEM, Potentiostat/Galvanostat, UV/VIS sepectrophotometer, and profilometer were used to analyze the characteristics of photoelectrode. An Arc lamp for simulating ultraviolet of sunlight used to induce photoelectrocatalytic decolorization of methyl orange. Mehtyl orange is an azo compound in dye wastewater. The prepared TiOx/Ti and WOy/Ti electrode show the excellent crystal structure without calcination. The TiOx film prepared by reactive sputtering is very uniform and it presents a slight blue shift. The blue shift effect means the photocatalyst is needed UV light with larger energy to excite electron hole pair. The best photocurrent of the TiOx/Ti electrode was obtained at the deposited condition with 300 W sputtering power and 3.2´10-2 mbar total sputtering pressure containing 25 % oxygen partial pressure. The results indicate that WOy/Ti film electrode also has excellent photoactivity by applying a bias potential and irradiation simultaneously. Decolorization of methyl orange proceeded through oxidation reaction promoted by the hydroxyl radical (OH·) that was generated from the reaction of holes and hydroxyl groups or water adsorbed on the surface of WO3. Decolorization of methyl orange proceeded through reduction reaction promoted by the electron is not observed. The photoactivity of WOy/Ti film electrode decreases quickly in the alkaline solution due to the WO3 was dissolved. The pH value of the aqueous solution, concentration of methyl orange, and bias potential are the major factors affecting the photoelectrocatalytic decolorization of methyl orange but the effect of power of UV light is minor. The photocurrent efficiency is evaluated by the ratio of concentration change of methyl orange and photocurrent. The photocurrent efficiency is about 1.2% and 12% in alkaline and acidic solution, respectively. The low photocurrent efficiency results from deactivation of hydroxyl radical. Increasing bias potential results in higher reaction rate and lower photocurrent efficiency. Based on the experiment results, the mechanism of photoelectrocatalytic reaction is proposed and a semitheoretical kinetic rate equation is obtained. Theoretical analysis ones correlate well with experimental results. The rate determined step is methyl orange reacted with hydroxyl radical. Langmuir- Hinshlewood adsorption of methyl orange is suitable to this system. The semitheoretical kinetic rate equation is represented as following （I-1） where Ri is decolorization rate of methyl orange (mM/min). P, E, and [MO] represent power of UV light, applied bias potential, and concentration of methyl orange, respectively. a and b are the reaction order of power of UV light and applied bias potential, respectively. The value of rate constants including Kp, K’, and K6 calculated from experimental data are

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41

Chen, Hsin-tien, and 陳忻恬. "Preparation and Photoelectrocatalytic Properties of ZnO Nanorod." Thesis, 2008. http://ndltd.ncl.edu.tw/handle/61987477743532170184.

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碩士
國立臺灣科技大學
化學工程系
96
Zinc oxide nanorods (ZNR) on substrate were prepared in this study by chemical bath deposition method. In order to obtain ZNR of high aspect ratio and high photocatalytic activity of ZNR, we added polyethylenimine (PEI) and Ag were added. PEI was used to hinder the lateral growth of the nanorods. All the catalysts prepared in this study were characterized by XRD, SEM, UV-vis, and AA. The photocatalytic activity of ZNR arrays was measured by photobleaching of 10 mg/L methylene blue, in a photo-reactor equipped with a light of 128 W and λmax=300 nm. The efficiency of photoconversion of ZNR was evaluated by 100 W Xe arc lamp illuminating the work-electrode in 1 M KOH solution. As the synthesis time increased from 5 to 20 hours, the results showed that, the length of the ZNR increased from 3.3μm to 12.4μm , the diameter increased from 100 nm to 400 nm, the average aspect ratio was about 34. Adding PEI to the synthesis solution would increase the aspect ratio to 60. For ZNR of 10μm length, the photobleaching activity of ZNR prepared with the addition of PEI is higher than that of zinc oxide nanoparticles film (ZNP). The most active photocatalytic catalyst was prepared by adding PEI in the synthesis solution and with the incorporation of Ag. The same catalyst also had the highest efficiency of photoconversion and incident monochromatic photo-to-current conversion in water splitting reaction.

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42

HSU, YUNG-HSIANG, and 徐詠祥. "Photoelectrocatalytic properties of titanium dioxide/silver nanowire hybrid films." Thesis, 2019. http://ndltd.ncl.edu.tw/handle/b23az4.

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碩士
國立雲林科技大學
化學工程與材料工程系
107
With respect to photocatalysis, titanium dioxide plays an important role in the degradation of pollution. Some studies also used electrocatalytic techniques to remove pollutants. Since both photocatalysis and elelctrocatalysis can remove efficiently pollutants, the study aims to combine them on removal of pollutants. In this work, we prepared silver nanowires by the polyol synthesis method and used such silver nanowires to prepare transparent conductive films. A titanium oxide layer was deposited on the transparent conductive films of silver nanowires to form bi-layer TiO2/AgNW films. For photoelectrocatalytic experiments, we used methylene blue as a pollutant and applied a bias voltage between the TiO2/AgNW film and a counter electrode. The effect of thickness of the TiO2 layer, silver nanowires, and forward/reverse bias on photoelectrocatalysis was investigated. The hydroxyl free radicals were analyzed through reaction of terephthalic acid and measurement of fluorescence. Experimental results revealed that the TiO2/AgNW film working as an anode showed significant catalytic activity on the degradation of methylene blue under a 0.5 V bias.

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43

FangShih-Hao and 方世豪. "Photoelectrocatalytic Degradation of Acid Orange 7 on TiO2 / SnO2 Electrode." Thesis, 2005. http://ndltd.ncl.edu.tw/handle/13619355829416590478.

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碩士
崑山科技大學
環境工程研究所
93
The photoelectrochemical (PEC) bleaching of a textile azo dye, acid orange 7 (AO7), on TiO2 or TiO2/SnO2 thin film electrodes prepared by a modified sol-gel method irradiated by xenon or visible light were carried out. The (112) and (110) were the preferred orientations for the anatase and rutile phases of TiO2, respectively. A synergetic effect between rutile and anatase phases on the PEC efficiency was revealed. The particle sizes of TiO2 and TiO2/SnO2 were estimated to be ca. 30nm by FESEM after calcination at 500℃, but the aggregation between particles was also accompanied. Incorporation of SnO2 can prevent TiO2 from aggregation, diminish the particle size and reduce the temperature, at which anatase phase changed into rutile phase. The TiO2/SnO2 electrodes, calcinated at 600℃, with TiO2/SnO2 of 9:1 to 7:3 explored higher performance than other compositions. An optimum thickness of the oxide film was needed to achieve maximum PEC efficiency. The bleaching rate of AO7 in the acidic solution is superior to that in the basic solution by PEC method. The Langmuir-Hinshelwood model can be adopted to describe the adsorption of AO7 on the electrode; however, it can not be simplified to a pseudo first order reaction due to larger AO7 concentration and/or lower surface area of the electrode. TiO2/SnO2 with Ti/Sn of 9:1 exhibited high bleaching rate of AO7 under visible light. Impregnating TiO2/SnO2(7:3) electrode with ethanol followed by calcination significantly enhanced the photodegradation rate of AO7 under visible light inadiation. The decolorization of AO7 may be partly originated from the hydroxyl radical attacking, and partly resulted from the photosensitization by AO7 itself and/or carbon residues followed by the electrons transferring to the electrode.

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Yu, Sheng-Lin, and 游昇霖. "Reduction of Cr(VI) in Aqueous Solution by Photoelectrocatalytic Processes." Thesis, 2014. http://ndltd.ncl.edu.tw/handle/69806997472211008549.

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碩士
國立臺灣科技大學
化學工程系
102
In this study, the photoelectrocatalytic reactor constructed by the structure design of batch reactor was used for the photoelectrocatalytic reduction of hexavalent chromium (Cr(VI)) in aqueous phase. The photocatalytic properties of photocathodes with different TiO2 thickness are examined. The experimental results indicated that the 6.50 μm thickness of TiO2 ﬁlm shows the highest photocatalytic activity among all the thickness investigated. The effects of solution pH, light intensity, initial Cr(VI) concentration, periodic illumination, bias potential and driving modes of bias potential were investigated on the photocatalytic and photoelectrocatalytic processes. The kinetics parameters of photocatalytic reduction of aqueous Cr(VI) was studied and discussed. The photocatalytic reduction of Cr(VI) for experiments conducted with periodic illumination were higher than that conducted with continuous illumination at pH 2. Because the surface fractional coverage is higher than replenished surface coverage of concentration of hydroxide and oxygen during long illumination period. Therefore, the photocatalytic reduction of Cr(VI) became slower at the long illumination period. The extent of electrolytic reduction was increased with decreasing applied bias potential. The bigger negative value of bias potential which provided more electron to reduce Cr(VI). Reduction of aqueous Cr(VI) was efficiently enhanced by photoelectrocatalytic process because the photoinduced electrons efficiently accumulate on TiO2-coated photocathode. The driving mode of half-rectified square wave mode (HR-SW) for electrolytic reduction also was investigated. However, the reduction of Cr(VI) under HR-SW mode was lower than which with constant DC mode when the negative bias potential. It is considered that when turning the bias potential from negative value to zero, the electrons which accumulating on the surface of cathode are drown to anode via external circuit under HR-SW mode.

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Tien, Chao-Cheng, and 田照正. "Photoelectrocatalytic Degradation of Dyes using Graphene Composite Titanium Dioxide Electrodes." Thesis, 2014. http://ndltd.ncl.edu.tw/handle/23723560957186331834.

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碩士
朝陽科技大學
環境工程與管理系
102
The ultrasonic and Hummers method were used in this study to prepare graphene oxide. The cyclic voltammetry was used for reduction of graphene oxide to graphene and deposition of graphene on the TiO2 nanotube array film. Thus, the graphene composited TiO2 nanotube array film was prepared. The photoelectrocatalysis of dye solution and its degradation efficiency was implemented with visible light and UV. The open-circuit voltage, closed circuit current and AC impedance of electrochemical analysis were implemented. The results showed that the dye degradation efficiency of the graphene composite TiO2 nanotube array film in UV-irradiation is better than that of TiO2 nanotube array film. With bias of 1 V, the addition of 0.1 M potassium chloride resulted in the optimum photoelectrocatalytic degradation efficiency. The degradation efficiency is still good when the methyl orange solution concentration is increased to 30 mg/L. The photocurrent of graphene composite TiO2 nanotube array film was increased compared with TiO2 nanotube array film. The results proving that the graphene composite TiO2 nanotube array film can increase the overall photoelectrocatalytic efficiency. In the same way, photocatalysis and photoelectrocatalysis of methyl orange solution with the visible light showed that the graphene composite TiO2 nanotube array film also has better catalytic efficiency than TiO2 nanotube array film.

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46

CHO, FENG-HSUAN, and 卓逢軒. "High efficiency Photoelectrocatalytic formic acid oxidation on Pt-modified dendritic gold." Thesis, 2017. http://ndltd.ncl.edu.tw/handle/7hv833.

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碩士
東海大學
化學系
105
The deposited gold dendrites (Au-Ds) on the GC electrode shows a three-fold symmetric structure, which grows all along the <111> direction. Due to crystalline Au-Ds have special texture nano structures, such as sharp edges or tips, high surface areas, and junctions between neighboring tips, which brought potential applications in catalysis. In addition, surface plasmon resonance (SPR) effect of Au-Ds can provide a beneficial electric field nearby to facilitate the separation of photo-excited carriers and to enhance the photoelectrocatalytic performance. We select copper under-potentials deposition (UPD) and platinum redox replacement technique to prepare Pt sub-monolayer on Au-Ds surface. Using two kinds of Pt(II, IV) precursors and controlling redox times to adjust Pt amounts and coverage on Au-Ds. Electrochemical activity surface areas (EASA) of Au-Ds is 50.40 cm2. For AP(II)-f substrates, Pt has 54 % coverage and EASA of Pt is 10.86 cm2. The multifunctional utilities of Au-Ds effective to sub-monolayer Pt durability and photo-absorption benefit the promotion of photocatalytic activity and stability. AP(IV)-i can restrict FAOR to perform on direct pathway. What is more, under irradiation, the ratio of P1/P2 can achieve 13.12 and current density of EASAPt can reach 12.1 mA/cm2. Besides, when AP(IV)-f under irradiation with CA at 0.35 V, the current density can increase to 26.65 %.

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47

Chang, Chia-Hao, and 張家豪. "Photoelectrocatalytic degradation of aqueous ammonia using TiO2 by Anodization and Immobilization." Thesis, 2015. http://ndltd.ncl.edu.tw/handle/83333495986898911317.

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碩士
國立勤益科技大學
化工與材料工程系
103
In this study, two different substrates (titanium sheet, titanium mesh) were prepared by using anodic oxidation and immobilization. On the other hand, discussion two substrates (titanium sheet, titanium mesh) were prepared by using anodic oxidation and immobilization with different pH values, ammonia removal efficiency of the bias potential. The results show that the prepared by using immobilization(Catalyst amount is 0.413g) at pH values 7.5 and bias potential is 2.0V have the best efficiency of 70.13%, when the pH is higher than the titanium dioxide pHpzc, NH4+ easier to adsorbed on the surface of titanium dioxide, so the reaction faster. At pH values 7.5 and bias potential is 1.5V has efficiency of 68.1% Considering the energy conservation issues and efficiency not differ much, therefore, as a condition of bias potential of 1.5V. Titanium mesh was prepared by using anodic oxidation and immobilization degradation solution of ammonia + anion and cation ions in different concentrations,observed any change and the impact of the target pollutant degradation effect. the results show that titanium mesh was prepared by using a immobilization degradation solution of ammonia + 1.5M phosphoric acid have the best efficiency of 81.90%.

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48

Wang, Yu-Jyun, and 王瑜鈞. "Photoelectrocatalytic Degradation of Sulfadiazine by TiO2 Composited with Nano-carbon Material." Thesis, 2015. http://ndltd.ncl.edu.tw/handle/98899122544944080710.

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碩士
國立高雄第一科技大學
環境與安全衛生工程研究所
103
This study aimed to investigate both photocatalysis (PC) and photoelectrocatalysis (PEC) of typical sulfonamides under illumination of near-UV (l= 365 nm) or LED blue light (l= 470 nm) by using TiO2/Ti composite thin-films as photocatalysts. The photocatalyst were prepared with EPD electrophoretic deposition processes by compositing P-25 TiO2 powder with carbon nano tube (CNT) and graphene plates. Sulfadiazine (SZD), a widely using antibiotic but concerned as an emerging contaminant, was tested as a target compound. Three major types of TiO2 composite thin-film photocatalysts including bare TiO2, carbon nanotubes doped TiO2, and graphene doped TiO2 on pure Ti substrates were prepared in the study. Other than investigating decomposition rate of SDZ, both physical and chemical properties of these prepared photocatalysts including absorption spectra, surface morphology and crystallinity were also measured by UV-Vis、SEM、TED、EDS and XRD. This study also measured flat-band potential of the prepared photocatalysts for correlating their oxidation capabilities with SDZ degradation rates. Several reacting variables including solution pH levels (pH= 7), applied external bias (0 to 1.0 V), types of photocatalysts and light sources (l= 365 nm and l= 470 nm) were examined in the study. All of tests were conducted in a bench-scale photoelectrocatalytic reactor. The experimental results indicated that the SDZ degradation rate was enhanced with increasing applied bias. Higher SDZ degradation rate was achieved by PEC reaction than by simple PC reaction. In comparison of simple PC reaction, the SDZ degradation rate could be increased up to 5.5 times by the PEC reaction. In addition, it was observed that the carbon nanotubes doped TiO2 and graphene doped TiO2 had a higher degradation rate for SDZ than the simple TiO2 sample. More hydroxyl radicals were expected to be produced by the TiO2 after doping with carbon nanotubes or graphene plates. It was also found that more visible light could be adsorbed by TiO2 while composited with nano carbon material, causing fast decomposition of SDZ under illumination of LED blue light. This study successfully demonstrates the enhanced photocatalytic degradation rate of typical antibiotic, SDZ, by providing an external bias to the reaction system. It is also interesting to find that the provided biases not only can increase SDZ reaction rate, but also can promote the mineralization of SDZ. For achieving the highest degradation rate of SDZ, both carbon nano tube and graphene had an optimum doping amount of about 1% (by wt) to the amount of TiO2 for the catalyst preparation.

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49

Seger, Brian J. "Electrocatalytic and photoelectrocatalytic aspects of proton exchange membrane based nanostructured assemblies." 2009. http://etd.nd.edu/ETD-db/theses/available/etd-06192009-110724/.

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Thesis (Ph. D.)--University of Notre Dame, 2009.
Thesis directed by Prashant V. Kamat for the Department of Chemical and Biomolecular Engineering. "June 2009." Includes bibliographical references (leaves 155-169).

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50

Yan, You-Ting, and 顏佑庭. "Photoelectrocatalytic Oxidation of Toluene in Indoor Environment by Using Modified TiO2." Thesis, 2017. http://ndltd.ncl.edu.tw/handle/2a288a.

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碩士
國立臺灣大學
環境工程學研究所
105
Volatile organic compounds (VOCs) are the major indoor air pollutant which are associated with indoor air quality (IAQ). It is considered as a cause of sick building syndrome (SBS). Source of VOCs indoor including upholstery materials, outdoor motor vehicle, consumer products and smoking, etc., will produce different levels of toluene emission, causing human health hazards. Currently, the technology of indoor VOCs treatment is based on photocatalytic oxidation (PCO) with UV light, but still have the problem of insufficient mineralization rate. The intermediate products produced by photocatalytic reaction may be more toxic, causing health hazards to indoor personnel instead. In addition, there are still have safety doubt for UV light apply to the indoor environment. In this study, toluene was degraded by photoelectrocatalytic (PEC) reaction in the photoreaction chamber, and a honeycomb metal monolith was placed inside, which can make the current flow through the whole reactor uniformly to ensure the process of photoelectrocatalytic reaction. The UV and visible light were controlled at 254nm and 420nm, and the photocatalyst was choosed the Degussa P25 TiO2 and modified Ag/AgBr/TiO2. The temperature was controlled at 25±1℃ and the humidity was maintained 30%. The impact factors of the experiment including toluene concentration, gas flow rate, light wavelength and voltage. In this study, Ag/AgBr/TiO2 was prepared with high reaction efficiency ratio (139.2%), and compared photocatalytic and photoelectrocatalytic activity with the P25 titanium dioxide. When Ag/AgBr/TiO2 was irradiated with ultraviolet light, the photoelectrocatalytic conversion of toluene was 95.9% at 0.5LPM flow rate and 0.2ppm toluene concentration. The photoelectrocatalytic conversion was significant increase from 59.9% to 97.4% after added voltage under visble light irradiation. And the highest conversion is 97.7% under the same conditions with using TiO2. The experimental results show that the higher the concentration of toluene is, the higher the conversion rate is. The reason is that active site of the photocatalyst surface is insufficient, causing the incomplete reaction , and reducing the photocatalytic efficiency. The products and mineralization rate of photoelectrocatalytic reaction were measured by GC-MS. It was found that the main byproduct of photocatalytic degradation of toluene was benzaldehyde and benzoic acid. The accumulation of benzoic acid on the surface of photocatalyst was the main reason of photocatalyst deactivation. In addition, part of the benzaldehyde form acetophenone by substitution reaction. When TiO2 was irradiated with ultraviolet light, the mineralization was 85% to 89%, resulting in more by-products. Mineralization can be maintained at more than 95% when using Ag/AgBr/TiO2 as photocatalyst, improving that it was helpful to increase the mineralization of toluene by modified photocatalyst. In the five times circulaing experiments, the TiO2 with poor reusability which was gradually deactivation after irradiated with ultraviolet light for 2 hours. It showed good stability and reproducibility that maintain at more than 80% conversion after 5 cycles when using Ag/AgBr/TiO2 as photocatalyst. The results of experiment showed the potential of processing indoor VOCs for future development by photoelectrocatalysis with modified photocatalyst and visible light. According to the result of energy efficiency, the energy efficiency of Ag/AgBr/TiO2 with visible light is the highest. The value are 0.2714mg kW-1 h-1 and 2.5891mg kW-1 h-1 respectively in two different concentration. And the energy efficiency are very close between two kinds of catalysts with UV light. Finally, evaluating the toluene conversion and energy efficiency, Ag/AgBr/TiO2 with visble light photoelectrocatalytic treatment of indoor VOCs has thepotential for future development.

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