Literatura científica selecionada sobre o tema "Heterostructured photocatalyst"

Heterostructured photocatalysts were fabricated by coupling electrospun n-type ZnO fibres and hydrothermally derived p-type CuCrO2 nanoparticles. The effect of the amount of CuCrO2 nanoparticles on the photocatalytic activity of the heterostructured photocatalyst was systematically investigated. The formation of the heterojunctions between the two semiconductors was revealed via detailed XRD, XPS, TEM and optical property measurements. The experimental results indicated that the optimal CuCrO2 amount in the composite photocatalyst was 1.0wt.% due to the optimum doping and surface coverage, higher absorption onset edge, larger absorption intensity and optimum band gap energy. This composite photocatalyst, fabricated by drop casting of CuCrO2 nanoparticle dispersion on ZnO fibres, displayed 30% higher rate constant (k) value compared to the pure ZnO fibres in the degradation of methylene blue dye molecules and reached 93.4% decomposition in 1 h under UV-visible light exposure. The obtained results are highly encouraging in comparison to only UV/light active p-n heterostructured photocatalysts previously reported in literature. Therefore, we believe that the proposed approach here opened the way for simple synthesis of highly-efficient visible light active heterostructured semiconductor photocatalyst systems.

With the further acceleration in the industrialization process, organic pollutants and gas pollution in the environment have posed severe threats to human health. It has been a global challenge regarding achieving an efficient solution to pollutant degradation. In such a context, photocatalysts have attracted researchers’ attention for their simplicity, efficiency, cleanliness and low cost. However, the single photocatalyst is facing a research bottleneck owing to its narrow light absorption spectrum and high photocarrier recombination rate. Given that heterojunctions can achieve efficient separation of photogenerated carriers in space, constructing heterostructured photocatalysts has become the most perspective method to improve the performance of photocatalysts. Furthermore, nanoparticles prepared through colloidal chemistry have the characteristics of high dispersion, stability and adsorption, further enhancing the degradation efficiency of heterostructured photocatalysts. This article reviews the primary methods for preparing heterostructured photocatalysts through colloidal chemistry, classifies the heterojunction types by transport routes of photogenerated carriers and summarizes the recent progress of heterostructured photocatalysts in pollutant degradation. To implement environmental remediation, it is crucial to explore economical and efficient photocatalysts for practical applications. It is hoped that this review will stimulate further exploration of colloidal heterostructured photocatalysts for pollutant degradation.

A series of AgBr/TiO2visible photocatalysts with heterojunction structure was synthesized using Ti(OC4H9)4, KBr, and AgNO3as precursors. The phase composition, particle morphology and size, microstructures, and absorbance of these photocatalysts were characterized by X-ray diffraction, transmission electron microscope (TEM), high-resolution TEM, and UV-vis spectra. It was found that the coupled AgBr/TiO2was an effective photocatalyst to degrade the methylene blue under visible light irradiation, compared with the other noncoupled photocatalysts of AgBr, AgBr/P25, and P25. The photocatalytic activities of AgBr/TiO2increase first and then decrease with increasing the mass ratio ofmAgNO3/mTiO2and the photocatalyst with the mass ratio of 3.35 has the highest photocatalytic activity. The results showed that the coupled photocatalyst has the particle size of about 15 nm with homogeneous dispersion and has the strongest absorption in whole UV-vis light region (250∼800 nm) originated from the synergetic effect of heterostructured AgBr/TiO2. The coupled AgBr/TiO2photocatalyst can keep stable photocatalytic activity after five-circle runs.

Antibiotic pollution beyond the safety limits poses a significant threat to the environmental sustainability and human health which necessitates the development of efficient methods for reducing antibiotics in pharmaceutical wastewater. Photocatalysis is a proven technology which has drawn considerable attention in semiconductor photocatalysts. Our study aims to develop a highly efficient Cr2O3/ZrO2 photocatalyst for the degradation of tetracycline (TCL) under visible light. The synthesized catalyst was well characterized by XRD, HR-TEM-SAED, XPS, FT-IR, BET and UV-Vis-DRS methods. The effects of various parameters on photocatalytic degradation were evaluated in detail, showing that 97.1% of 50 mgL−1 tetracycline concentrations could be degraded within 120 min at pH 5 with a 0.1 gL−1 photocatalyst-loading concentration under visible light (300 W Xe lamp). The uniform distribution of spherical ZrO2 nanoparticles on the surface of the Cr2O3 nano-cubes efficiently reduced the recombination rate with an energy bandgap of 2.75 eV, which provided a faster photodegradation of tetracycline under visible light. In addition, a plausible degradation pathway and photoproducts generated during the photocatalytic degradation of TCL are proposed based on the LC-ESI/MS results, which suggested that efficient photodegradation was achieved during the visible light irradiation. Thus, our study reveals that the cost-effective Cr2O3-based photocatalyst with multi-reusability and efficient energy consumption could be an efficient photocatalyst for the rapid degradation of TCL during the wastewater treatment process.

Bi2S3/SnS2 heterostructured photocatalysts were synthesized from BiOI, SnCl[Formula: see text]5H2O and NH2CSNH2 using an economic and simple hydrothermal method. The as-synthesized samples were characterized by X-ray diffraction, scanning electron microscopy and ultraviolet-visible diffuse reflectance spectroscopy. The photodegradation activities of the Bi2S3/SnS2 heterostructured photocatalysts were estimated by degrading rhodamine B under simulated sunlight supplied by irradiating with a 350[Formula: see text]W Xe lamp. Bi2S3/SnS2 photocatalysts were prepared using varying percentages of Bi2S3. The sample containing 13% Bi2S3 had the most efficient photocatalyst performance among the tested samples. The photocatalytic mechanism involves heterojunctions formed in the Bi2S3/SnS2, which promoted effective separation of photoinduced electrons and holes.

The binary heterostructured semiconducting visible light photocatalyst of the iron-doped graphitic carbon nitride/bismuth molybdate (Fe-g-C3N4/Bi2MoO6) composite was prepared by coupling with Fe-doped g-C3N4 and Bi2MoO6 particles. In the present study, a comparison of structural characteristics, optical properties, and photocatalytic degradation efficiency and activity between Fe-doped g-C3N4 particles, Bi2MoO6 particles, and Fe-g-C3N4/Bi2MoO6 composite was investigated. The results of X-ray diffraction (XRD) examination indicate that the hydrothermal Bi2MoO6 particles have a single orthorhombic phase and Fourier transform infrared (FTIR) spectroscopy analysis confirms the formation of Fe-doped g-C3N4. The optical bandgaps of the Fe-doped g-C3N4 and Bi2MoO6 particles are 2.74 and 2.73 eV, respectively, as estimated from the Taut plots obtained from UV-Vis diffuse reflectance spectroscopy (DRS) spectra. This characteristic indicates that the two semiconductor materials are suitable for absorbing visible light. The transmission electron microscopy (TEM) micrograph reveals the formation of the heterojunction Fe-g-C3N4/Bi2MoO6 composite. The results of photocatalytic degradation revealed that the developed Fe-g-C3N4/Bi2MoO6 composite photocatalyst exhibited significantly better photodegradation performance than the other two single semiconductor photocatalysts. This property can be attributed to the heterostructured nanostructure, which could effectively prevent the recombination of photogenerated carriers (electron–hole pairs) and enhance photocatalytic activity. Furthermore, cycling test showed that the Fe-g-C3N4/Bi2MoO6 heterostructured photocatalyst exhibited good reproducibility and stability for organic dye photodegradation.

Photocatalysis has attracted a lot of attention in recent years due to its potential in solving energy and environmental issues. Efficient light absorption and charge separation are two of the key factors for the exploration of high-performance photocatalytic systems, which are generally difficult to obtain from a single photocatalyst. The combination of various materials to form heterojunctions provides an effective way to better harvest solar energy and facilitate charge separation and transfer, thus enhancing photocatalytic activity and stability. This review concisely summarizes the recent development of visible light responsive heterojunctions, including the preparation and performance of semiconductor/semiconductor junctions and semiconductor/metal junctions and their mechanism for enhancing light harvesting and charge separation/transfer. In this regard, this review presents some unitary, binary and ternary CeO2 photocatalysts used for the degradation of organic pollutants. We expect this review to provide the type of guidelines for readers to gain a clear picture of nanotechnology and the fabrication and application of different types of heterostructured photocatalysts.

Heterostructured photocatalysts associating ZnO nanorods (NRs) sensitized by quaternary Ag-In-Zn-S (AIZS) quantum dots (QDs) were prepared by depositing AIZS QDs at the surface of ZnO NRs followed by thermal treatment at 300 °C. The ZnO/AIZS catalysts were characterized by X-ray diffraction, electron microscopy, UV-vis diffuse spectroscopy and by photoelectrochemical measurements. Their photocatalytic activity was evaluated for the bleaching of the Acid Orange 7 (AO7) dye under visible light irradiation. Results show that the association of ZnO NRs with 10 wt% AIZS QDs affords the photocatalyst the highest activity due to the enhanced visible light absorption combined with the improved charge separation. The ZnO/AIZS(10) photocatalyst degrades 98% AO7 in 90 min under visible light illumination, while ZnO NRs can only decompose 11% of the dye. The ZnO/AIZS(10) photocatalyst was also found to be stable and can be reused up to eight times without significant alteration of its activity. This work demonstrates the high potential of AIZS QDs for the development of visible light active photocatalysts.

In recent decades, the textile industry has contributed to continuous pollution in the environment. Synthetic dyes which are commonly found in waste water are azo, sulfur, anthraquinone, triphenylmethyl, indigoid, and phthalocyanine derivatives. These pollutants block the light penetration in water bodies and prevent photosynthesis activity, thereby affecting aquatic life. As an environmental crisis, several technologies have been explored to control pollution. Among all the techniques, the photocatalysis process is considered as a green, simple, and economical process. To improve the photocatalytic activity, researchers worldwide have investigated various photocatalysts such as metal oxides, metal ferrites, and heterostructured nanocomposites. The major goal of this review article is to propose a high-performing, cost-effective hybrid photocatalyst reported to date for prospective azo dye pollutant remediation. This review article also aimed to highlight the challenges and uncertainties associated with dye degradation in the photocatalytic process.

As the world faces water shortage and pollution crises, the development of novel visible light photocatalysts to purify water resources is urgently needed. Over the past decades, most of the reported photocatalysts have been in powder or granular forms, creating separation and recycling difficulties. To overcome these challenges, a flexible and recyclable heterostructured TiO2/polyvinylidene fluoride/graphitic carbon nitride (TiO2/PVDF/g-C3N4) composite was developed by combining electrospinning, sintering and hydrothermal methods. In the composite, PVDF was used as a support template for removing and separating the photocatalyst from solution. Compared with pure TiO2, the TiO2/PVDF/g-C3N4 composite exhibited the extended light capture range of TiO2 into the visible light region. The photogenerated carriers were efficiently transferred and separated at the contact interface between TiO2 and g-C3N4 under visible light irradiation, which consequently increased the photocatalytic activity of the photocatalyst. In addition, the flexible composites exhibited excellent self-cleaning properties, and the dye on the photocatalysts was completely degraded by the as-prepared materials. Based on the intrinsic low cost, recyclability, absorption of visible light, facile synthesis, self-cleaning properties and good photocatalytic performances of the composite, the photocatalyst is expected to be used for water treatment.

Les photocatalyseurs à base de TiO2 ont été l’objet d’une grande attention comme une méthode durable de purification de l’air ou de l’eau, et de production d’hydrogène par décomposition de l’eau. Une stratégie avantageuse consiste à développer des héterostructures par couplage avec un autre oxyde métallique former une jonction de type Schottky ou avec un autre oxyde métallique pour créer une jonction p-n à l’interface de manière à prévenir les recombinaisons via une séparation de charge « vectorielle » à ces jonctions. De plus, les facettes cristallines jouent un rôle crucial dans le piégeage des porteurs de charge et, donc,dans les réactions rédox photoactivées. Ainsi, le dépôt sélectif de métal ou d’oxyde métallique sur des facettes spécifiques de nanocristaux de TiO2 devrait augmenter l’activité photocatalytique par l’amélioration de la séparation des charges. Dans ce travail, nous avons combiné l’emploi du cocatalyseur de type p NiO pour former des jonctions p-n avec son dépôt sélectif sur des nanocristaux de TiO2 anatase exposant des facettes bien définies. Par ailleurs, des expériences modèles de physique de surface ont été menées pour étudier les propriétés électroniques de ces hétérojonctions
TiO2 photocatalysts have attracted attention as a sustainable method for water/air purification and hydrogen production by water splitting. An advantageous strategy is the development of heterostructures by coupling metal oxides to create a p-n junction at their interface in order to prevent there combination by vectorial charge carrier separation at these energy junctions. In addition, crystal facets play a decisive role in the trapping of charge carriers and thus photocatalytic redox reactions. Thus, selective deposition of metal or metal oxides onto specific facets would enhance the photocatalytic activity by improving charge separation. In this work, we have combined the usage of p-type NiO co-catalyst to form p-n junction with its selective deposition onto the specific facet of oriented TiO2nanocrystal photocatalysts. Furthermore, the physical model experiments have been performed to investigate the electronic properties of these heterojunctions

Photocatalytic processes over semiconducting oxide surfaces have attracted worldwide attention aspotentially efficient, environmentally friendly and low cost methods for water/air purification as well as forrenewable hydrogen production. However, some limitations to achieve high photocatalytic efficiencies havebeen found due to the fast recombination of the charge carriers. Development of heterostucture photocatalystsby depositing metals on the surface of semiconductors or by coupling two semiconductors with suitable bandedge position can reduce recombination phenomena by vectorial transfer of charge carriers. To draw newprospects in this domain, three different kinds of heterostructures such as n-type/n-type semiconductor(SnO2/ZnO), metal/n-type semiconductor (RuO2/TiO2 and RuO2/ZnO) and p-type/n-type semiconductor(NiO/TiO2) heterojunction nanomaterials were successfully prepared by solution process. Their composition,texture, structure and morphology were thoroughly characterized by FTIR, X-ray diffraction (XRD), Ramanspectroscopy, transmission electron microscopy (TEM) and N2 sorption measurements. On the other hand, asuitable combination of UV-visible diffuse reflectance spectroscopy (DRS), X-ray photoelectron spectroscopy(XPS) and ultraviolet photoemission spectroscopy (UPS) data provided the energy band diagram for eachsystem. The as-prepared heterojunction photocatalysts showed higher photocatalytic efficiency than P25 TiO2for the degradation of organic dyes (i.e. methylene blue and methyl orange) and the production of hydrogen.Particularly, heterostructure RuO2/TiO2 and NiO/TiO2 nanocomposites with optimum loading of RuO2 (5 wt %)and NiO (1 wt %), respectively, yielded the highest photocatalytic activities for the production of hydrogen.These enhanced performances were rationalized in terms of suitable band alignment as evidenced by XPS/UPSmeasurements along with their good textural and structural properties. This concept of semiconductingheterojunction nanocatalysts with high photocatlytic activity should find industrial application in the future toremove undesirable organics from the environment and to produce renewable hydrogen.

The photocatalytic production of hydrogen from water and biomass derivatives such as ethanol, glycerol and sugars is a highly attractive strategy to generate environmentally benign hydrogen. Ethanol is more easily oxidized than water by holes in the valence band (VB) of photoexcited semiconductors, which also helps to suppress the recombination of electron-hole pairs, thus increasing the usage of electrons in the conduction band (CB) of photoexcited semiconductors to yield hydrogen. Titanium dioxide (TiO2) has been widely investigated in the field of photocatalysis due to its photosensitivity, low cost, natural abundance, non-toxicity, and good chemical and thermal stability. However, the solar energy conversion efficiency of TiO2 is hindered by its large bandgap (3.2 eV). Here, we demonstrate that the combination of TiO2 with Ni, Co and Cu can substantially promote local spatial charge separation and proton activation in TiO2, achieving high-efficiency for H2 photoproduction. In chapter 2, we present a strategy to produce porous NiTiO3/TiO2 nanostructures with excellent photocatalytic activity toward hydrogen generation. Nickel-doped TiO2 needle bundles were synthesized by a hydrothermal procedure. Through the sintering in air of these nanostructures, porous NiTiO3/TiO2 heterostructured rods were obtained. Alternatively, the annealing in argon of the nickel-doped TiO2 needle bundles resulted in NiOx/TiO2 elongated nanostructures. Porous NiTiO3/TiO2 structures were tested for hydrogen evolution in the presence of ethanol. Such porous heterostructures exhibited superior photocatalytic activity toward hydrogen generation, with hydrogen production rates up to 11.5 mmol h-1 g-1 at room temperature. In chapter 3, CoTiO3/TiO2 composite catalysts with controlled amounts of highly distributed CoTiO3 nanodomains for photocatalytic ethanol dehydrogenation are developed and studied. To take advantage of solar light, the CoTiO3 nanoparticles with a band gap around 2.3 eV were synthesized by a hydrothermal procedure. We demonstrate these materials to provide outstanding hydrogen evolution rates under UV and visible illumination. The origin of this enhanced activity is extensively analysed. In contrast to previous assumptions, UV-vis absorption spectra and ultraviolet photoelectron spectroscopy (UPS) prove CoTiO3/TiO2 heterostructures to have a type II band alignment, with the CB minimum of CoTiO3 below the H+/H2 energy level. Additional steady-state photoluminescence (PL) spectra, time-resolved PL spectra (TRPLS), and electrochemical characterization prove such heterostructures to result in enlarged lifetimes of the photogenerated charge carriers. These experimental evidences point toward a direct Z-scheme as the mechanism enabling the high photocatalytic activity of CoTiO3/TiO2 composites toward ethanol dehydrogenation. The optimization of photodehydrogenation of ethanol requires the use of highly active, stable and selective photocatalytic materials based on abundant elements, and the proper adjustment of the reaction conditions, including temperature. In chapter 3, Cu2O-TiO2 type-II heterojunctions with different Cu2O amounts are obtained by a one-pot hydrothermal method. The structural and chemical properties of the produced materials and their activity toward ethanol photodehydrogenation under UV and visible light illumination are evaluated. The structural and chemical properties of the produced materials and their activity toward ethanol photodehydrogenation under UV and visible light illumination are evaluated. The Cu2O-TiO2 photocatalysts exhibit high selectivity toward acetaldehyde production and up to tenfold higher hydrogen evolution rates compared to bare TiO2. We further discern here the influence of temperature and visible light absorption on photocatalytic performance.
La producció fotocatalítica d’hidrogen a partir de derivats de l’aigua i de la biomassa com l’etanol, el glicerol i els sucres és una reacció atractiva per proporcionar hidrogen benigne per al medi ambient. L’etanol s’oxida més fàcilment que l’aigua mitjançant forats de la banda de valència dels semiconductors fotoexcitats, suprimint la recombinació de parells electró-forat i, per tant, augmentant la reactivitat dels electrons en la banda de conducció dels semiconductors fotoexcitats per produir hidrogen. El diòxid de titani (TiO2) ha estat àmpliament investigat en el camp de la fotocatàlisi a causa de la seva fotosensibilitat, baix cost, abundància natural, no toxicitat i bona estabilitat química i tèrmica. No obstant això, l'eficiència de conversió d'energia solar de TiO2 es veu obstaculitzada per la seva gran amplada de banda (3,2 eV) i la alta taxa de recombinació dels portadors fotogenerats. Aquí demostrem que el Ni, Co i Cu poden promoure substancialment la separació de càrregues i l’activació de protons en el TiO2, aconseguint una alta eficiència per a la fotoproducció d¿H2. En el capitol 2, presentem una estratègia per produir nanoestructures poroses de NiTiO3/TiO2 amb una excel·lent activitat fotocatalítica cap a la generació d’hidrogen. Al capítol 2, es van sintetitzar agulles de TiO2 dopades amb níquel itjançant un procediment hidrotermal. Mitjançant la sinterització a l'aire d'aquestes nanoestructures es van obtenir agulles heterostructurades poroses de NiTiO3/TiO2. Com a alternativa, el tractament tèrmic en argó de les agulles de TiO2 dopades amb níquel va donar lloc a nanoestructures allargades de NiOx/TiO2. Es van provar les estructures poroses de NiTiO3/TiO2 per a la producció d’hidrogen en presència d’etanol. Aquestes heteroestructures poroses presentaven una activitat fotocatalítica superior cap a la generació d’hidrogen, amb taxes de producció de fins a 11.5 mmol h-1 g-1 d’hidrogen a temperatura ambient. Per aprofitar la il·luminació solar, es van sintetitzar nanopartícules de CoTiO3 amb una banda adequada al voltant de 2,3 eV mitjançant un procediment de sinterització hidrotermal. Al capítol 3, els catalitzadors compostos CoTiO3/TiO2 amb quantitats controlades de nanodominis distribuïts de CoTiO3 es van provarper a la deshidrogenació fotocatalítica d’etanol. Demostrem que aquests materials proporcionen velocitats devolució d’hidrogen excepcionals sota il·luminació UV i visible. S’analitza a fons l’origen d’aquesta activitat millorada. En contrast amb els supòsits anteriors, els espectres d’absorció UV-vis i l’espectroscòpia de fotoelectrons ultraviolats (UPS) demostren que les heteroestructures CoTiO3/TiO2 tenen una alineació de banda de tipus II, amb la banda de conducció mínima de CoTiO3 per sota del nivell d’energia H+/H2. Els espectres addicionals de fotoluminescència en estat estacionari (PL), espectres PL resolts en el temps (TRPLS) i caracterització electroquímica demostren que aquestes heteroestructures donen lloc a una vida més gran dels portadors de càrrega fotogenerats. Aquestes evidències experimentals apunten cap a un esquema Z directe com el mecanisme que permet l’alta activitat fotocatalítica dels compostos CoTiO3/TiO2 cap a la deshidrogenació de l’etanol. L’optimització de la fotodehidrogenació de l’etanol requereix l’ús de materials fotocatalítics altament actius, estables i selectius basats en elements abundants i l’adequat ajust de les condicions de reacció, inclosa la temperatura. Al capítol 3, s’obtenen heterojuncions de tipus Cu2O-TiO2 tipus II amb diferents quantitats de Cu2O mitjançant un mètode hidrotermal en una etapa. S’avaluen les propietats estructurals i químiques dels materials produïts i la seva activitat cap a la fotodehidrogenació d’etanol sota la il·luminació UV i llum visible. Els fotocatalitzadors Cu2O-TiO2 presenten una alta selectivitat cap a la producció d’acetaldehid i hidrogen fins a deu vegades més altes que el TiO2. Aquí també discernim la influència de la temperatura i l’absorció de llum visible en el rendiment fotocatalític. Els nostres resultats apunten a la combinació de fonts d’energia en reactors termofotocatalítics com una estratègia eficient per a la conversió d’energia solar. Els resultats es van publicar en Nanomaterials el 2021
La producción fotocatalítica de hidrógeno a partir de agua y derivados de biomasa como etanol, glicerol y azúcares es una reacción atractiva para proporcionar hidrógeno sin apenas impacto ambiental. El etanol se oxida más fácilmente que el agua por los huecos en la banda de valencia de los semiconductores fotoexcitados, suprimiendo la recombinación de pares electrón-hueco y, por lo tanto, aumentando la reactividad de los electrones en la banda de conducción de los semiconductores fotoexcitados para producir hidrógeno. Además, el etanol es un recurso renovable que se produce fácilmente mediante la fermentación convencional de azúcares y almidón. El dióxido de titanio (TiO2) ha sido ampliamente investigado en el campo de la fotocatálisis debido a su fotosensibilidad, bajo costo, abundancia natural, no toxicidad y buena estabilidad química y térmica. Sin embargo, la eficiencia de conversión de energía solar del TiO2 se ve obstaculizada por su gran banda prohibida (3,2 eV). Aquí, demostramos que la incorporación de Ni, Co y Cu puede promover sustancialmente la separación de cargas locales y la activación de protones por el TiO2, logrando una alta eficiencia en la fotoproducción de H2. En el capítulo 2, presentamos una estrategia para producir nanoestructuras porosas de NiTiO3/TiO2 con excelente actividad fotocatalítica hacia la generación de hidrógeno. En el capítulo 2, se sintetizaron agujas de TiO2 dopado con níquel mediante un procedimiento hidrotermal. Mediante la sinterización al aire de estas nanoestructuras se obtuvieron heteroestructuras en forma de varillas de NiTiO3/TiO2 porosas. Alternativamente, el tratamiento térmico bajo argón de las varillas de TiO2 dopado con níquel dió como resultado nanoestructuras alargadas de NiOx/TiO2. Las estructuras porosas de NiTiO3/TiO2 se ensayaron para determinar la producción de hidrógeno en presencia de etanol. Tales heteroestructuras porosas exhibieron una actividad fotocatalítica superior hacia la generación de hidrógeno, con tasas de producción de hasta 11,5 mmol h-1 g-1 de hidrógeno a temperatura ambiente. Este excelente rendimiento se relaciona con las propiedades optoelectrónicas y los parámetros geométricos del material. Los resultados se publicaron en Journal of Materials Chemistry A en 2019. Para aprovechar la luz solar, se sintetizaron nanopartículas de CoTiO3 con un intervalo de banda de alrededor de 2.3 eV mediante un procedimiento de sinterización hidrotermal. En el capítulo 3, se prepararon catalizadores compuestos CoTiO3/TiO2 con cantidades controladas de nanodominios CoTiO3 altamente distribuidos para la deshidrogenación fotocatalítica de etanol. Demostramos que estos materiales presentan una actividad fotocatalítica de generación de hidrógeno excepcionales bajo iluminación UV y visible. El origen de esta actividad se analiza ampliamente. En contraste con las suposiciones anteriores, los espectros de absorción UV-vis y la espectroscopia de fotoelectrones ultravioleta (UPS) demuestran que las heteroestructuras de CoTiO3/TiO2 tienen una alineación de banda de tipo II, con la banda de conducción del CoTiO3 por debajo del nivel de energía H+/H2. Los espectros de fotoluminiscencia (PL), los espectros de PL resueltos en el tiempo (TRPLS) y la caracterización electroquímica demuestran que tales heteroestructuras dan como resultado una mayor vida útil de los portadores de carga fotogenerados. Estas evidencias experimentales apuntan hacia un esquema Z directo como el mecanismo que permite la alta actividad fotocatalítica de los compuestos CoTiO3/TiO2 hacia la deshidrogenación del etanol. Además, se analizó el efecto de la temperatura en la actividad fotocatalítica de los materiales probados, lo que podría usarse para promover aún más el rendimiento en un reactor solar termo-fotocatalítico. Los resultados se publicaron en ACS Applied Materials & Interfaces en 2021. La optimización de la fotodeshidrogenación del etanol requiere el uso de materiales fotocatalíticos altamente activos, estables y selectivos basados en elementos abundantes y el adecuado ajuste de las condiciones de reacción, incluida la temperatura. En el capítulo 3, se obtuvieron heterouniones Cu2O-TiO2 tipo II con diferentes cantidades de Cu2O mediante un método hidrotermal en un solo paso. Se evalúan las propiedades estructurales y químicas de los materiales producidos y su actividad hacia la fotodeshidrogenación de etanol bajo iluminación UV y con luz visible. Los fotocatalizadores Cu2O-TiO2 muestran una alta selectividad hacia la producción de acetaldehído e hidrógeno hasta diez veces más altas en comparación con el TiO2. También discernimos aquí la influencia de la temperatura y la absorción de luz visible en el rendimiento fotocatalítico. Nuestros resultados apuntan a la combinación de fuentes de energía en reactores termo-fotocatalíticos como una estrategia eficiente para la conversión de energía solar. Los resultados se publicaron en nanomateriales en 2021
Enginyeria de processos químics

Semiconductor-based heterogeneous photocatalysis, as one of the advanced oxidation processes that makes use of semiconductors and inexhaustible solar light, has recently been extensively studied and applied to water decontamination. However, due to low light absorption efficiencies and severe electron-hole recombination, modifications on semiconductor structures are required in order to enhance their photocatalytic performance. Heterogeneous photocatalyst composites, taking advantage of the improved light absorption efficiency as well as the facilitated electron-hole separation at the interface between different semiconductors, have been proven to be a promising strategy. In this study, novel NaNbO3/Bi2WO6 photocatalyst composites with a type-II heterogeneous alignment were successfully prepared via a facile wet impregnation method. The as-prepared photocatalysts were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), diffuse reflectance UV-Vis spectroscopy (DRS), photocurrent (PC) and electrochemical impedance spectroscopy (EIS) analyses. The 30 wt% NaNbO3/Bi2WO6 composite exhibited the best performance for degrading an RhB (rhodamine B) aqueous solution under visible light irradiation (λ > 410 nm), which was ca. 40 times and ca. 2.5 times that of the pristine NaNbO3 and Bi2WO6, respectively. The improved photocatalytic activity may be attributed to the enhanced electron-hole separation efficiency in Bi2WO6 with the assistance of NaNbO_3, as well as the dye-sensitization effect of RhB itself. Radical quenching experiments revealed that h+ played the predominant role, and O2•- functioned as well to some degree. The produced intermediates during the reaction and RhB degradation pathway were speculated and investigated as well. The excellent stability and reusability were verified by repetitively running for five times. Based on experimental results, a plausible functioning mechanism was proposed. Effects of several operation parameters on the catalyst performance including initial RhB concentration, catalyst dosage, reaction temperature and initial pH were also discussed. This study provides solid evidence for NaNbO3 to be a promising candidate for photocatalysis and gives out a novel photocatalytic mechanism of Bi2WO6-based type-II heterostructures.

La dépollution de l'eau est un des enjeux majeurs du XXIème siècle. Si différentes techniques de retraitement existent déjà, nous investiguons une nouvelle méthode associant les propriétés des membranes filtrantes à celles des matériaux photocatalytiques. Ainsi, nous avons étudié la croissance et l'activité photocatalytique de structures de type noyau/coquille de ZnO/SnO2 intégrées dans des membranes méso-poreuses (alumine poreuse) et macro-poreuses (fibres de verre). L'activité photocatalytique de ces matériaux a été évaluée sur des polluants modèles tels que le bleu de méthylène ou l'acide salicylique, mais aussi sur des polluants organiques identifiés dans les eaux de la rivière luxembourgeoise Alzette. L'impact environnemental des matériaux développés a été déterminé grâce a des analyses de cytotoxicité sur des cellules colorectales de type Caco-2, ainsi que sur des bactéries marines de type Vibrio Fischeri
Water treatment is one of the main challenge to overcome on the XXIst century. If many different techniques already exist, we investigate a new process associating the properties of porous membranes and photocatalytic materials. Thus, we studied the growth and photoactivity of core/shell structures of ZnO/SnO2 integrated into mesoporous (AAO) and macro-porous (glass fiber) membranes . The photocatalytic activity of these materials has been evaluated on organic pollutants like methylene blue or salicylic acid, but also on molecules found in the Luxembourgish Alzette river. The environmental impact of the synthesized structures has been determined with cytotoxic analyses on Caco-2 cells and Vibrio Fischeri bacteria

L'objectif de ce travail est d'améliorer les performances photocatalytiques de deux oxydes mixtes de bismuth, Bi2WO6 et BiOBr, présentant une activité sous lumière visible. Leurs activités photocatalytiques sont en effet majoritairement limitées par un taux de recombinaison des charges photoinduites élevé. Deux stratégies différentes ont été respectivement appliquées pour chaque matériau. La première consiste à former une hétérostructure entre Bi2WO6 et un métal noble, le platine, pour assurer une séparation efficace des charges. La seconde consiste à réduire la taille des particules de BiOBr afin d'augmenter la surface spécifique et de diminuer le parcours moyen des charges jusqu'à la surface du photocatalyseur. Les synthèses ont été réalisées par chimie douce. La répartition et la quantité de platine déposé sur Bi2WO6 a ainsi pu être modulée et des particules de BiOBr sous forme de microfleurs ou de plaquettes de différentes tailles ont été obtenues. La dégradation de la rhodamine B en solution sous irradiation bleue a permis d'évaluer les propriétés photocatalytiques des matériaux. La dégradation de molécules non photosensibles a également été réalisée afin de confirmer l'activité photocatalytique observée. Dans le but d'évaluer la potentialité de Bi2WO6 et BiOBr pour la purification de l'air intérieur, des tests de dégradation photocatalytique de polluants modèles gazeux ont été effectués. L'ensemble de ces tests ont mis en évidence les relations entre les paramètres physico-chimiques des matériaux et leurs performances photocatalytiques et ont souligné les potentialités et les limitations de Bi2WO6 et BiOBr pour la dépollution de l'air et de l'eau
The aim of this work is to improve photocatalytic performance of two mixed bismuth oxides, Bi2WO6 and BiOBr, which have an activity within visible range of the electromagnetic spectrum. Two different strategies have been developed for each material. First one consists in designing a heterostructure between Bi2WO6 and a noble metal, platinum, which ensures an efficient charge separation at the interface. Second one aims at lowering BiOBr particle’s size in order to boost specific surface and shrink mean free path of charges to the surface of the photocatalyst. Syntheses of the materials were carried out using soft chemistry method. Platinum particle distribution and quantity on Bi2WO6 were thus successfully tuned and BiOBr microspheres or plates with different size were obtained. Photocatalytic properties of our materials were characterized by rhodamine B degradation in solution under blue light (λ = 445 nm). Degradation test of non-photosensitive compounds were also performed to show their photocatalytic activity. In order to evaluate Bi2WO6 and BiOBr potential in purifying indoor air photocatalytic degradation tests of model gaseous pollutant were performed. All these photocatalytic tests highlight the relationship between physicochemical and photocatalytic properties of the materials. They also enable us to determine the potentials and limitations of Bi2WO6 and BiOBr as photocatalysts for water and air depollution

La croissance rapide de la population ainsi que l'industrialisation ont suscité des inquiétudes majeures quant à la disponibilité de l'énergie et à la pollution de l'environnement. La résolution de ces problèmes est au cœur de nombreuses recherches à l'échelle mondiale. L'énergie solaire, en tant que source d'énergie propre et pratiquement inépuisable, devrait être efficacement exploitée, notamment via des processus photocatalytiques, pour améliorer la dépollution environnementale. Les nanomatériaux hybrides, tels que ZnO/métal noble et ZnO/oxydes métalliques, se positionnent comme des candidats prometteurs pour atteindre ces objectifs car ils absorbent efficacement la lumière visible et permettent une séparation efficace des porteurs de charge. Ce mémoire est consacré au développement de nouveaux photocatalyseurs hétérostructurés pour la dégradation des polluants organiques. L'étude a exploré deux voies novatrices de synthèse de ZnO associé soit à des nanoparticules d'argent métallique soit à des oxydes de cuivre. Dans la première partie de cette mémoire, un procédé a été développé pour préparer des particules de ZnO d'environ 87 nm associées à des nanoparticules d'argent d'une taille moyenne de 2.7 nm. Cette stratégie met en œuvre la synthèse d'hydroxydes doubles lamellaires de zinc dopés à l'argent, suivie de la photodéposition des ions Ag+ en Ag(0), et enfin, la conversion par thermolyse de l'hydroxyde double lamellaire en oxyde de zinc. Dans la deuxième partie de la thèse, la photodéposition de nanoparticules de CuO-Cu₂O à la surface de ZnO a permis le développement d’hétérostructures avec une jonction p-n entre CuO-Cu₂O et ZnO. Les nouvelles méthodes de synthèse de catalyseurs hétérostructurés développées dans le cadre de cette thèse ont permis le développement de matériaux photocatalytiquement actifs pour la dégradation de polluants persistants en milieux aqueux. En termes de stabilité, ces catalyseurs peuvent être utilisés sur plusieurs cycles de dégradation sans perte notable d'efficacité. Le projet comporte également l'étude des différents paramètres expérimentaux afin d'optimiser les propriétés structurales, électroniques, optiques et photocatalytiques de ces matériaux
The fast growth of the population and industrialization have produced major concerns regarding energy availability and environmental pollution. Addressing these issues is at the forefront of global research. Solar energy, as a clean and almost infinite source, can be effectively harnessed through photocatalytic processes to contribute to environmental remediation. Hybrid nanomaterials, such as ZnO/noble metal and ZnO/metal oxides, emerge as promising candidates to achieve these goals due to their enhanced light absorption capability and excellent charge carrier separation. This thesis is dedicated to the development of new hybrid photocatalysts designed for the degradation of organic pollutants. The study explores two innovative synthesis pathways of ZnO, combined with photodeposited nanoparticles of metallic silver or copper oxide, onto ZnO. In the first part of the study, a solvothermal method was developed to prepare ZnO particles of approximately 87 nm associated with silver nanoparticles with an average size of 2.7 nm. This strategy involves the synthesis of silver-doped zinc double-layered hydroxides, followed by the photodeposition of Ag+ ions into Ag(0), and ultimately, the conversion through thermolysis of the double-layered hydroxide into ZnO. In the second part, the preparation via an environmentally friendly and easy photodeposition method was used to create heterostructured photocatalysts featuring a p-n junction between CuO-Cu₂O and ZnO. The novel synthesis methods for ZnO-based heterostructured catalysts developed in the framework of this thesis have led to the creation of nanohybrid materials exhibiting high efficiency in degrading persistent pollutants in aqueous environments. In terms of stability, these hybrid photocatalysts can be used over multiple degradation cycles without a significant loss of effectiveness. The project also involves the study of various experimental parameters to optimize the structural, electronic, and optical properties of the photocatalysts

With an increasing demand for alternative clean energy solutions, much effort is being invested in the progression of nanoscale semiconductor materials in hopes of better harnessing solar energy. ZnO and TiO2 remain the most prominent photocatalytically active materials. This thesis reports on a comparison between nanoscale core-shell and hierarchical Zn-Ti-O/ZnO heterostructures. After a seed layer thickness optimization, hydrothermally grown ZnO nanorods were coated with mixed concentrations of Ti and Zn within an oxygen rich sputtering environment at two distinct temperature zones. Core-shell structures resulted from low temperature (23°C) depositions while hierarchical branch structures grew at high temperature (800°C). Excluding deposition temperature and the strategic variation of Zn and Ti gun power, every fabrication process remained identical between the two resultant heterostructure groups. Amongst the variety of samples produced, one from each heterostructure group proved notably similar in structural dimension, composition, and crystallization, yet demonstrated distinct differences in photoluminescence and dye degradation via UV-visible light spectroscopy. While photoluminescence results indicated core-shell heterostructure more photocatalytically promising, hierarchical heterostructure prevailed as the more powerful photocatalyst. Increased surface area due to hierarchical branching in conjunction with enhanced light exposure was believed responsible for the improved photocatalytic effectiveness.

Charge separation in ZnO/ZnS type II heterostructures may prove useful as a photocatalyst support. This work used cathodoluminescence spectroscopy to explore whether thermal annealing of ZnO and ZnS powders can synthesize such heterostructures.