Dissertations / Theses on the topic 'Cobalt acetate'

The development of cheap industrial scale H2 production from renewable sources is highly desirable to meet our future clean-energy demands. One promising route is water splitting using solar radiation. In this thesis, the individual components of a photocatalytic system were explored with the aim of applying earth-abundant and industrially relevant catalyst materials for sustainable chemistry. A family of cobalt acetate compounds was examined as potential water and biomass oxidation catalysts, and TiN nanoparticles were investigated as co-catalysts for photocatalytic hydrogen evolution. A significant challenge for realising industrial scale water splitting is the development of efficient, stable, and earth-abundant catalysts for the water oxidation half reaction. Co(III) species have long been known to facilitate water oxidation and cobalt acetate has been employed as a versatile industrial oxidation catalyst of alkyl aromatic molecules over the last 60 years. This has inspired a series of investigations to evaluate several oligomers from a family of cobalt acetate compounds as water oxidation catalysts (WOCs). Three model Co(III) acetate oligomers of different nuclearity, the Co-cubane, [Co4(μ3-O)4(μ-OAc)4(py)4], Co-trimer, [Co3(μ3-O)(μ-OAc)6(py)3][PF6], and Co-dimer, [Co2(μ-OH)2(μ-OAc)(OAc)2(py)4][PF6] were assessed. Complementary to developing more efficient WOCs, an alternative approach is to employ sacrificial agents, such as aromatic molecules, that are more easily oxidised than water. The ability of cobalt acetate to oxidise a variety of lignin model compounds was also explored. Lastly, commercialised semiconductors (i.e. TiO2) are restricted to absorbing ~ 5% of the energy of the terrestrial solar spectrum. TiN nanoparticles were explored as co-catalysts with TiO2 (P25) for photocatalytic H2 evolution via MeOH reformation due to their unique optical properties.

While the individual need for dosage of nickel and cobalt in anaerobic digesters has been established, together with the biochemistry underpinning such need; their co-requisite in anaerobic digestion of acetate has not been extensively studied. In addition, the balance between the catalytic and toxic concentrations of nickel and cobalt in anaerobic acetate digesters is not well documented. The aim of this study was to examine and evaluate the effects of individual and combined dosage of nickel and cobalt on biogas production as well as on methanogenic population balance of a mesophilic (37°C) anaerobic acetate digester so as to determine their catalytic and toxic concentrations. Four semi-CSTR digesters were daily fed acetate at a loading rate of 1.8 g L-1 d-1 and were operated at a HRT of 10 days for this investigation. Co-dosage of nickel and cobalt in anaerobic acetate digesters were found to lead to increased biogas production in an additive manner, with the sole dosage of nickel resulting in more biogas production than that of cobalt. At a large enough concentration, these elements were found to inhibit biogas production.

The oxidation of 4-t-butyltoluene in glacial acetic acid by hydrogen peroxid in a process catalysed by cobalt(II) acetate tetrahydrate and sodium bromide has been studied with the aim of increasing the selectivity towards 4-t-butylbenzaldehyde.

The oxidation of 4-t-butyltoluene in glacial acetic acid by hydrogen peroxid in a process catalysed by cobalt(II) acetate tetrahydrate and sodium bromide has been studied with the aim of increasing the selectivity towards 4-t-butylbenzaldehyde.

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Neste trabalho objetivou-se a síntese e caracterização de oito complexos de cobalto(II) que fossem aptos a atuarem como agentes controladores na Polimerização Radicalar Mediada por Cobalto do monômero acetato de vinila. Através da modulação da esfera de coordenação destes complexos com a alteração dos efeitos estéricos e eletrônicos promovidos pela coordenação de ligantes α-diiminas, buscou-se estabelecer parâmetros para propor a forma como estes complexos mediam a CMRP do referido monômero. Os complexos foram divididos em dois grupos, objetivando uma avaliação mais eficiente da forma como os efeitos estéricos e eletrônicos interferem na capacidade controladora dos mesmos. Após a variação sistemática das proporções molares entre complexo, iniciador e monômero encontrou-se na proporção [Co]/[AIBN]/[VAc] = 1/3,25/542 os resultados mais satisfatórios deste trabalho. O uso de DMSO fora prejudicial para os complexos 2a-c, porém fez com que os complexos 2d-h apresentassem melhorias, reduzindo seus valores de polidispersidade e aumentando as massas moleculares dos polímeros. O complexo 2b fora escolhido como o melhor controlador do grupo do efeito estérico, por reunir em si as características estérias e eletrônicas que o fizeram apresentar os menores valores de polidispersidade (Đmáx = 1,43). Com relação ao grupo de complexos do efeito eletrônico, fora o complexo 2f que, devido à maior estabilidade estrutural conferida ao complexo por seu substituinte cicloexil, apresentara as menores polidispersidades de seu grupo, entre 1,12 e 1,58.
This work aimed the synthesis and characterization of eight cobalt(II) complexes which could be able to act as controlling agents in vinyl acetate radical polymerization mediated by cobalt. By modulating the coordination sphere of these complexes, modifying the steric and electronic effects offered by the α-diimine ligands, we sought to establish parameters to propose how these complexes mediate the CMRP of vinyl acetate. The complexes were split in two groups in way to assess efficiently how the electronic and steric effects can affect the controlling capacity of the CoII(α-diimine).A systematic variation of the molar ratio such as [Co]/[initiator] and [Co]/[monomer] made it possible to choose [Co]/[initiator]/[monomer] = 1/3.25/542 as the ratio that provided certain level of control. The addition of DMSO was detrimental to the complexes 2a-c, but caused an improvement to the activity of complexes 2dh, reducing their polydispersity values and increasing the molecular weights of the polymers. Complex 2b was chosen as the best controller of the steric effect group, its steric and electronic characteristics made possible to reach the lowest polydispersity of its group (Đmax = 1.43).Regarding to the group of complexes of the electronic effect, it was the complex 2f that had the smallest polydispersity of its group, between 1.12 and 1.58, due to the greater structural stability conferred to the complex by its cyclohexyl substituent.

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
O trabalho reporta a síntese de dois novos complexos de cobalto(II), coordenados a ligantes tetraimínicos, estes foram denominados [Co(beb)](PF6)2 e [Co(bfb)](PF6)2. Os complexos foram caracterizados por Espectroscopia de Infravermelho (FT-IR), Espectroscopia de Ultravioleta-visível (UV-Vis) e Voltametria Cíclica (VC). A polimerização radicalar de acetato de vinila (VAc) foi iniciada pelo azobisisobutironitrila (AIBN) e realizada na presença de [Co(beb)](PF6)2 ou [Co(bfb)](PF6)2 como agentes controladores, a temperatura de 65 ºC. As massas moleculares de poliacetato de vinila (PVAc) foram analisadas por GPC e Cg.
This study describes the synthesis of two novel cobalt(II) complexes, coordinated to tetraimine ligands [Co(beb)](PF6)2 and [Co(bfb)](PF6)2, where beb = 1,2-diphenylethane-bis(N2 -benzylidene-N1 -methyleneethane- 1,2-diamine) and bfb = 1,2-diphenylethane-bis(N2 -benzylide-N1 - methylenebenzene-1,2-diamine). The complexes were characterized by FT-IR, UV-Vis and Cyclic Voltammetry. The radical polymerization of vinyl acetate (VAc) initiated by azobisisobutyronitrile (AIBN) was carried out under different reaction conditions in the presence of [Co(beb)](PF6)2 or [Co(bfb)](PF6)2 as mediators. The systematic variation of the reaction conditions, such as [initiator]/[Co] and [monomer]/[Co] molar ratios, affected the polymerization rates and the molecular weights, reaching a certain level of control. The [Co(beb)](PF6)2 complex was shown to be more efficient in controlling the polymerization of VAc when compared to the [Co(bfb)](PF6)2 complex.

Analyse approfondie du spectre photoelectronique se(fe(c::(5)h::(5)))::(2)(no)::(2). Etude critique des resultats experimentaux anterieurs concernant le diamagnetisme suppose se(co(c::(5)h::(5)))::(2)(no)::(2). Bon accord avec l'experience dans l'etude theorique de l'etat fondamental du cation dirhodium tetraacetate dihydrate. Etude sur la nature de l'interaction metal-metal dans (v(c::(5)h::(5)))::(2) (c::(8)h::(8))

Orientador: Beatriz Eleutério Goi
Banca: Daniela Martins Fernandes de Oliveira
Banca: Silvânia Lanfredi Nobre
Resumo: O trabalho reporta a síntese de dois novos complexos de cobalto(II), coordenados a ligantes tetraimínicos, estes foram denominados [Co(beb)](PF6)2 e [Co(bfb)](PF6)2. Os complexos foram caracterizados por Espectroscopia de Infravermelho (FT-IR), Espectroscopia de Ultravioleta-visível (UV-Vis) e Voltametria Cíclica (VC). A polimerização radicalar de acetato de vinila (VAc) foi iniciada pelo azobisisobutironitrila (AIBN) e realizada na presença de [Co(beb)](PF6)2 ou [Co(bfb)](PF6)2 como agentes controladores, a temperatura de 65 ºC. As massas moleculares de poliacetato de vinila (PVAc) foram analisadas por GPC e Cg
Abstract: This study describes the synthesis of two novel cobalt(II) complexes, coordinated to tetraimine ligands [Co(beb)](PF6)2 and [Co(bfb)](PF6)2, where beb = 1,2-diphenylethane-bis(N2 -benzylidene-N1 -methyleneethane- 1,2-diamine) and bfb = 1,2-diphenylethane-bis(N2 -benzylide-N1 - methylenebenzene-1,2-diamine). The complexes were characterized by FT-IR, UV-Vis and Cyclic Voltammetry. The radical polymerization of vinyl acetate (VAc) initiated by azobisisobutyronitrile (AIBN) was carried out under different reaction conditions in the presence of [Co(beb)](PF6)2 or [Co(bfb)](PF6)2 as mediators. The systematic variation of the reaction conditions, such as [initiator]/[Co] and [monomer]/[Co] molar ratios, affected the polymerization rates and the molecular weights, reaching a certain level of control. The [Co(beb)](PF6)2 complex was shown to be more efficient in controlling the polymerization of VAc when compared to the [Co(bfb)](PF6)2 complex
Mestre

Orientador: Beatriz Eleutério Goi
Banca: Giovana Gioppo Nunes
Banca: Sérgio Antônio Marques de Lima
Resumo: Neste trabalho objetivou-se a síntese e caracterização de oito complexos de cobalto(II) que fossem aptos a atuarem como agentes controladores na Polimerização Radicalar Mediada por Cobalto do monômero acetato de vinila. Através da modulação da esfera de coordenação destes complexos com a alteração dos efeitos estéricos e eletrônicos promovidos pela coordenação de ligantes α-diiminas, buscou-se estabelecer parâmetros para propor a forma como estes complexos mediam a CMRP do referido monômero. Os complexos foram divididos em dois grupos, objetivando uma avaliação mais eficiente da forma como os efeitos estéricos e eletrônicos interferem na capacidade controladora dos mesmos. Após a variação sistemática das proporções molares entre complexo, iniciador e monômero encontrou-se na proporção [Co]/[AIBN]/[VAc] = 1/3,25/542 os resultados mais satisfatórios deste trabalho. O uso de DMSO fora prejudicial para os complexos 2a-c, porém fez com que os complexos 2d-h apresentassem melhorias, reduzindo seus valores de polidispersidade e aumentando as massas moleculares dos polímeros. O complexo 2b fora escolhido como o melhor controlador do grupo do efeito estérico, por reunir em si as características estérias e eletrônicas que o fizeram apresentar os menores valores de polidispersidade (Đmáx = 1,43). Com relação ao grupo de complexos do efeito eletrônico, fora o complexo 2f que, devido à maior estabilidade estrutural conferida ao complexo por seu substituinte cicloexil,...
Abstract: This work aimed the synthesis and characterization of eight cobalt(II) complexes which could be able to act as controlling agents in vinyl acetate radical polymerization mediated by cobalt. By modulating the coordination sphere of these complexes, modifying the steric and electronic effects offered by the α-diimine ligands, we sought to establish parameters to propose how these complexes mediate the CMRP of vinyl acetate. The complexes were split in two groups in way to assess efficiently how the electronic and steric effects can affect the controlling capacity of the CoII(α-diimine).A systematic variation of the molar ratio such as [Co]/[initiator] and [Co]/[monomer] made it possible to choose [Co]/[initiator]/[monomer] = 1/3.25/542 as the ratio that provided certain level of control. The addition of DMSO was detrimental to the complexes 2a-c, but caused an improvement to the activity of complexes 2dh, reducing their polydispersity values and increasing the molecular weights of the polymers. Complex 2b was chosen as the best controller of the steric effect group, its steric and electronic characteristics made possible to reach the lowest polydispersity of its group (Đmax = 1.43).Regarding to the group of complexes of the electronic effect, it was the complex 2f that had the smallest polydispersity of its group, between 1.12 and 1.58, due to the greater structural stability conferred to the complex by its cyclohexyl substituent
Mestre

Orientador: Beatriz Eleutério Goi
Coorientador: Valdemiro Pereira de Carvalho Júnior
Banca: Ana Maria Pires
Banca: Patrícia Alexandra Antunes
Resumo: Nas últimas décadas, a polimerização radicalar controlada (CRP) tem se tornado muito importante, pois permite a síntese de macromoléculas de arquiteturas específicas com um controle sobre as propriedades químicas e físicas. Sendo assim, este trabalho tem por objetivo a síntese de novos complexos de Co(II) coordenado a ligantes tipo Salen não simétricos. O precursor, os ligantes e os complexos foram caracterizados pelas seguintes técnicas: espectroscopia de absorção na região do UV-Vis, espectroscopia vibracional na região do infravermelho (FTIR), voltametria cíclica e Ressonância Magnética Nuclear (RMN 1H e 13C). Os complexos não simétricos contendo em sua composição aminas saturadas [CoII(CAYA 02)], [CoII(CAYA 03)] e o complexo contendo amina aromática [CoII(CAYA 04)] foram utilizados como mediadores na reação de polimerização radicalar controlada por organometálicos do acetato de vinila. Foram feitos estudos do efeito da temperatura na reação de OMRP (Polimerização Radicalar Mediada por Complexos Organometálicos) utilizando-se o complexo [CoII(CAYA 03)] sintetizado na razão molar de 1/3,25/542 (Co/AIBN/VAc). Após este estudo foram realizadas as cinéticas de polimerização para todos os complexos, pôde-se observar que cada complexo apresentou um perfil cinético de pseudo-primeira ordem com um aumento de Mn em determinados intervalos de tempo de acordo com a sua reatividade. Os complexos [CoII(CAYA 03)] e [CoII(CAYA 04)] apresentaram um aumento dos valores de Mn juntamente...
Abstract: In the last decades, controlled radical polymerization (CRP) has become very important because it allows the synthesis of macromolecules of specific architectures with a control over the chemical and physical properties. Thus, this work aims to synthesize new Co (II) complexes bound to non-symmetric Salen type ligands. The precursor, ligands and complexes were characterized by the following techniques: absorption spectroscopy in the UV-Vis region, infrared vibration spectroscopy (FTIR), cyclic voltammetry and Nuclear Magnetic Resonance (1H and 13C NMR). The non-symmetric complexes containing saturated amines [CoII (CAYA 02)], [CoII (CAYA 03)] and the aromatic amine-containing complex [CoII (CAYA 04)] were used as mediators in the radical polymerization reaction controlled by organometallic of vinyl acetate. It was studied the effect of temperature on the OMRP (Polymerization Radicalar Mediated by Organometallic Complexes) using the complex [CoII (CAYA 03)] synthesized in the molar ratio of 1 / 3.25 / 542 (Co / AIBN / VAc). After this study the polymerization kinetics were performed for all the complexes, it was observed that each complex presented a kinetic profile of pseudo-first order with an increase of Mn at certain time intervals according to their reactivity. The complexes [CoII (CAYA 03)] and [CoII (CAYA 04)] showed an increase of the Mn values together with the conversion maintaining the values of polydispersity (Ð) between 1 and 1,5 that characterizes the control of ...
Mestre

碩士
國立清華大學
化學系
101
Cobalt porphyrins mediated vinyl acetate radical polymerization has been performed in different solvent environments and was found that a high monomer conversion (69%) with linear increased molecular weight versus conversion, narrow molecular weight distribution (Mw/Mn = 1.12 ~ 1.34), and little molecular weight deviation could be approached in bulk condition. However, different levels of molecular weight deviation occurred when polymerization was performed in solution, indicating that the control of vinyl acetate radical polymerization was affected by chain transfer to solvent. Besides, non-coordinating solvents caused a difference in polymerization rate mainly due to the different propagation rate constant (kp), but the coordinating solvents such as THF blocked the reaction site of cobalt porphyrins and interfered the whole polymerization behavior. The effect of radical concentration and the ratio of [VAc]0 / [CoII]0 have been also discussed. The higher radical concentration shortened the induction period, increased the polymerization rate and caused a slight deviation of molecular weight. But the control efficiency of cobalt porphyrins to vinyl acetate polymerization was not significantly affected by the ratio of [VAc]0 / [CoII]0. The coordinating effect of pyridine was demonstrated by the shift of equilibrium from dormant organo-cobalt(III) species to active cobalt(II) species. The equilibrium constant (Keq) was changed from < 10-12 to 5.2 × 10-8 when 25 equivalent of pyridine was added into the polymerization so that the major control process was switched from degenerate transfer to reversible termination. Polymerization of methyl acrylate mediated by cobalt porphyrins has been conducted in different solvents. The polymerization behaviors were similar in non-coordinating solvents. However, the induction period was shortened with coordinating solvents such as acetonitrile, anisole and THF which blocked the reaction site of cobalt porphyrins. When THF was used as an additive, the induction period was slightly decreased, but it showed no effect to the polymerization rate and the controlled efficiency.

Synopsis of thesis entitled “Electrochemical and Photoelectrochemical Investigations of Co, Mn and Ir-based Catalysts for Water Splitting” by Ahamed Irshad M (SR No: 02-01-02-10-11-11-1-08823) under the supervision of Prof. N. Munichandraiah, Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore (India), for the Ph.D. degree of the Institute under the Faculty of Science. Hydrogen is considered as the fuel for future owing to its high gravimetric energy density and eco-friendly use. In addition, H2 is an important feedstock in Haber process for ammonia synthesis and petroleum refining. Although, it is the most abundant element in the universe, elemental hydrogen is not available in large quantities on the planet. Consequently, H2 must be produced from its various chemical compounds available on earth. Currently, H2 is produced in large scale from methane by a process called steam-methane reforming (SMR). This process releases huge amount of CO2 into atmosphere as the by-product causing serious environmental issues. The development of alternate clean methods to generate H2 is a key challenge for the realization of hydrogen economy. Production of H2 gas by water splitting using electricity or sunlight is known. Low cost, high natural abundance and carbon neutrality make water as the best source of hydrogen. Thermodynamically, splitting of H2O needs 237 kJ mol-1 of energy, which corresponds to 1.23 V according to the equation, ΔG = -nFE. However, commercial electrolyzers usually operate between 1.8 to 2.1 V, due to the need of large overvoltage. The high overvoltage and subsequent energy losses are mainly associated with the sluggish kinetics of oxygen evolution reaction (OER) at the anode and hydrogen evolution reaction (HER) at the cathode. The overvoltage can be considerably reduced using suitable catalysts. Hence, the design and development of stable, robust and highly active catalysts for OER and HER are essential to make water splitting efficient and economical. Attempts in the direction of preparing several novel OER and HER catalysts, physicochemical characterizations and their electrochemical or photoelectrochemical activity are described in the thesis. A comprehensive review of the literature on various types of catalysts, thermodynamics, kinetics and mechanisms of catalysis are provided in the Chapter 1 of the thesis. Chapter 2 furnishes a brief description on various experimental techniques and procedures adopted at different stages of the present studies. Chapter 3 explains the results of the studies on kinetics of deposition and stability of Nocera’s Co-phosphate (Co-Pi) catalyst using electrochemical quartz crystal microbalance (EQCM). The in-situ mass measurements during CV experiments on Au electrode confirm the deposition of Co-Pi at potential above 0.87 V vs. Ag/AgCl, 3 M KCl (Fig.1a and b). The catalyst is found to deposit via a nucleus mediated process at a rate of 1.8 ng s-1 from 0.5 mM Co2+ in 0.1 M neural phosphate solution at 1.0 V. Further studies on the potential and electrolyte dependent stability of the Co-Pi suggest that the catalyst undergoes severe corrosion at high overpotential and in non-buffer electrolytes. Current/ Fig.1 (a) Cyclic voltammograms and (b) mass variations vs. potential of Au-coated quartz crystal in 0.1 M potassium phosphate buffer solution (pH 7.0) containing 0.5 mM Co(NO3)2 Chapter 4 deals with the electrochemical deposition of a novel OER catalyst, namely, Co-acetate (Co-Ac) from a neutral acetate electrolyte containing Co2+ ions. Use of acetate solution instead of phosphate avoids the solubility limitations and helps to get thick layer of the catalyst in a short time from concentrated Co2+ solutions. In addition, the Co-Ac is found to be catalytically superior to Co-Pi (Fig. 2a). It is also observed that the Co-Ac catalyst undergoes ion exchange with electrolyte species during electrolysis in phosphate buffer solution, which results in the formation of a hybrid Co-Ac-Pi catalyst (Fig. 2b). The presence of both acetate and phosphate ions in the catalyst and their synergistic catalytic effect enhance the OER activity. Fig.2. (a) Linear sweep voltammograms of Co-Ac in (i) phosphate and (ii) acetate electrolytes, and that of Co-Pi in (iii) acetate and (iv) phosphate electrolytes. (b) SEM image showing the formation of two layers of the catalysts after electrolysis in phosphate solution. In Chapter 5, high OER activity of an electrodeposited amorphous Ir-phosphate (Ir-Pi) is investigated. The catalyst is prepared by the anodic polarization of a carbon paper electrode in neutral phosphate solution containing Ir3+ ions (Fig. 3). The Ir-Pi film deposited on the electrode has Ir and P in an approximate ratio of 1:2 with Ir in an oxidation state higher than +4. Phosphate ions play a major role for both the electrochemical deposition process and its catalytic activity towards OER. The Ir-Pi catalyst is superior to similarly deposited IrO2 and Co-Pi catalysts both in terms of onset potential and current density at any potential in the OER region. Tafel measurements and pH dependence studies identify the formation of a high energy intermediate during oxygen evolution. Fig.3. (a) Cyclic voltammograms during the Ir-Pi deposition and (b) SEM image of Ir-Pi on C. Chapter 6 is on the preparation of a composite of Mn-phosphate (MnOx-Pi) and reduced graphene oxide (rGO) and its utilization as an OER catalyst. The composite is prepared by the simultaneous electrochemical reduction of KMnO4 and graphene oxide (GO) in a phosphate solution (pH 7.0). Various analytical techniques such as TEM, XPS, Raman spectroscopy, etc. confirm the formation of a composite (Fig. 4) and electrochemical studies indicate the favourable role of rGO towards OER. Under identical conditions, MnOx-Pi-rGO gives 6.2 mA cm-2 at 2.05 V vs. RHE whereas it is only 2.9 mA cm-2 for MnOx-Pi alone. However, the catalyst is not very stable during OER which is ascribed to slow oxidation of Mn3+ in the catalyst. Fig.4. (a) Raman spectrum and (b) TEM image of MnOx-Pi-rGO. In Chapter 7, an amorphous Ni-Co-S film is prepared by a potentiodynamic deposition method using thiourea as the sulphur source. The electrodeposit is used as a catalyst for the HER in neutral phosphate solution. The composition of the catalyst and the HER activity are tuned by varying the ratio of concentrations of Ni2+ and Co2+. The bimetallic Ni-Co-S catalyst exhibits better HER activity than both Ni-S and Co-S (Fig. 5a). Under optimized deposition conditions, Ni-Co-S requires just 150 mV for the onset of HER and 10 mA cm-2 is obtained for 280 mV overpotential. The Ni-Co-S shows two different Tafel slopes, indicating two different potential dependent HER mechanisms (Fig. 5b). Presence of two different catalytic sites which contribute selectively in different potential regions is proposed. Fig.5. (a) Linear sweep voltammograms of HER at 1 mV s-1 in 1 M phosphate solutions (pH 7.4) using (i) Ni-S, (ii) Co-S and (c) Ni-Co-S. (b) Tafel plot of Ni-Co-S showing two Tafel slopes. Photoelectrochemical OER using ZnO photoanode and Co-acetate (Co-Ac) cocatalyst is studied in Chapter 8 of the thesis. Randomly oriented crystalline ZnO nanorods are prepared by the electrochemical deposition of Zn(OH)2 followed by heat treatment at 350 ºC in air. Co-Ac is then photochemically deposited onto ZnO nanorods by UV illumination in the presence of neutral acetate buffer solution containing Co2+ ions. The hybrid Co-Ac-ZnO shows higher photoactivity in comparison with bare ZnO towards PEC water oxidation (Fig. 6). Co-Ac acts as a cocatalyst and reduces the charge carrier recombination at the electrode/electrolyte interface. Fig.6. (a) Linear sweep voltammograms of ZnO under (i) dark and (ii) light conditions, and that of Co-Ac-ZnO in (iii) dark and (iv) light in 0.1 M phosphate (pH 7.0) electrolyte. Chapter 9 deals with PEC water oxidation using α-Fe2O3 photoanode and Ir-phosphate (Ir-Pi) cocatalyst. α-Fe2O3 is prepared by direct heating of Fe film in air which in turn is deposited by the electrochemical reduction of Fe2+. Thickness of the film as well as calcination temperature is carefully optimized. In order to further enhance the OER kinetics, Ir-Pi is electrochemically deposited onto α-Fe2O3. Under optimized conditions, Ir-Pi deposited α-Fe2O3 shows around 3 times higher photocurrent than that of bare α-Fe2O3 at 1.23 V vs. RHE (Fig. 7). Ir-Pi acts as a cocatalyst for OER and reduces the photogenerated charge carrier recombination. Fig.7. Photocurrent variation of α-Fe2O3 electrode at 1.23 V vs. RHE for (i) front and (ii) back side illuminations, against Ir-Pi deposition time. The thesis ends with a short summary and future prospectus of studies described in the thesis. The research work presented in the thesis is carried out by the candidate as the part of Ph.D. program. Some of the results have already been published in the literature and some manuscripts are under preparation. A list of publications is included at the end of the thesis. It is anticipated that the studies reported in the thesis will constitute a worthwhile contribution.

碩士
中原大學
化學研究所
103
The presenting study can be divided into two parts. The first part of the study of sulfamate esters compound containing (six ring、five ring、four ring and Acetal group) as the starting materials in PdCo(OAc)4 catalyzed C - H amination reaction. Starting material with radical clock (cyclopropyl group) was alse tested in the C - H amination reaction to determine the possibility of radical mechanism. The second part is about using (diacetoxyiodo)benzene an oxidant for the oxidation of phenyl acetal compounds to form orthoesters.

M. Tech. (Department of Chemistry, Faculty of Applied and Computer Science), Vaal University of Technology
Cadmium and cobalt complexes of urea and thiourea were synthesized using ethanol as a solvent. All complexes were refluxed at 70 - 80 °C, left to cool at room temperature, washed with methanol and acetone to remove impurities and dried at an open environment. The characterization of complexes was done using FTIR spectroscopy, elemental analysis and TGA. The complexes were found to coordination with the ligands through sulphur and oxygen atoms to the metal, instead of nitrogen. These were as results of wavelength shifting from high to low frequency from spectra of the complexes as compare to their free ligands. These observations make these complexes good candidates for the possible use in synthesis of metal sulphides or oxides nanoparticles. Thermogravimetric analyses of all the complexes were conducted to check the stability of use as precursors for nanoparticles at low and high temperature. A number of thiourea and urea complexes with cadmium and cobalt have been prepared and used in the preparation of metal sulphides/oxides nanoparticles. Complexes start to decompose at low temperature about 100°C and the last decomposition step was at about 800-900°C, which is convenient to thermal decomposition of precursors in the high boiling solvents or capping agent to prepare surface capped metal sulphides/oxides nanoparticles. The complexes were easy to synthesize, low cost and stable in air and were obtained in reasonable yields. All the complexes reported in this study have been used as single source molecular precursor in the preparation of cadmium oxide, cadmium sulphide, cobalt oxide, cobalt sulphide nanoparticles (normal) and as mixture of any two complexes to form core-shells nanoparticles. Quality nanoparticles synthesis requires three components: precursors, organic surfactants and solvents. The synthesis of the nanoparticles can be thought of as a nucleation event, followed by a subsequent growth period. Both the nucleation and growth rates were found to be dependent upon factors such as temperature, growth time, and precursor concentration. For a continuous flow system the residence time (at nucleation and growth conditions) was also found to be important. In order to separate the nucleation and growth events, injection techniques were employed to achieve rapid nucleation of nanoparticles with final size dictated by the growth temperature and/or residence time through the growth zone of the reaction system. Good crystalline normal nanoparticles were obtained from thermolysis of the precursors in hexadecylamine (HDA) as the capping agent at fixed concentrations, temperature and time. All nanoparticles showed a blue-shift in band edges with good photoluminescence behaviour which is red-shifted from their respective band edges and XRD patterns, the crystal structure are in hexagonal phase. The particles showed rods, spheres and hexagonal shapes. Nucleation and growth mechanism brings new avenue in nanostructures called core-shells, which have been reported to have improved luminescence, quantum yields, decreased fluorescence lifetimes, and benefits related to the tailoring of the relative band-gap positions between the two materials. In this study cadmium and cobalt complexes of urea and thiourea were separately dispersed in TOP and injected separately (allowing nucleation/core to occur, followed by the shell) in hot HDA at 180ºC for 1hour to yield core-shell nanoparticles. Parameters, such as concentration, temperature and capping molecule as factor affecting nucleation and growth of the core-shells were monitored. The core-shell nanoparticles were characterized by UV/Vis spectroscopy, XRD and TEM. We observed spherical, tripod, bipods, hexagonal and irregular shaped nanoparticle as the concentration of the precursors was increasing, however we were able to form core-shells nanoparticles in one set of experiment 1:3 CdS-CdO, which are assumed to be a reverse type I coreshells nanoparticles. Exciton absorption peaks at higher energy than the fundamental absorption edge of bulk indicate quantum confinement effect in nanoparticles as a consequence of their small size. XRD patterns, crystals range from hexagonal, cubic and mixture of hexagonal and orthorhombic. A low temperature studies were also conducted a mixture of hexagonal and sphererical shapes with sheets like onion morphology were observed.
NRF HUB & SPOKES (VUT)

Bacteria were previously isolated from two separate sites, one contaminated with lead and the other with Polycyclic Aromatic Hydrocarbons (PAHs). Alcaligenes sp. AO22 and Arthrobacter sp. E9 were identified from the lead contaminated site, while Stenotrophomonas maltophilia was identified from the PAH contaminated site. Minimum Inhibitory Concentration assays (MICs) were previously performed on Alcaligenes sp. AO22 and Arthrobacter sp. E9 and they were found to be resistant to varying levels of heavy metals and polymerase chain reactions suggesting the presence of mercury (mer), copper (pco) and cadmium, zinc and cobalt (czc) resistance genes. S. maltophilia VUN 10010, was previously investigated for its ability to degrade pyrene and other HMW PAHs as a sole carbon and energy source. The purpose of the current project was to further characterise the MICs of these isolates, along with biofilm capabilities. The genetic basis of their heavy metal resistance was also investigated.