La séparation photoélectrochimique de l'eau (PEC) est un moyen direct de produire un combustible solaire tel que l'hydrogène à partir de l'eau. Le goulot d'étranglement de ce processus se situe dans la photoanode, qui est responsable du côté oxydation de la réaction1,2. Dans ce travail, l'utilisation de BiVO4 en tant que photoanode a été largement étudiée afin d'améliorer sa photoactivité. L’optimisation de la synthèse de photoanodes BiVO4 par électrodéposition en couche mince sur du FTO a été réalisée. Les facteurs influant sur l'activité photoélectrochimique, tels que le temps d'électrodéposition, le rapport Bi-KI/benzoquinone-EtOH dans le bain de dépôt et la température de calcination, ont été étudiés à l'aide de la conception composite centrale d'expériences. Les états de surface sur la surface de BiVO4 donnent lieu à des niveaux de défaut pouvant induire une recombinaison électron-trou via le mécanisme de Shockley-Read-Hall5. Afin de minimiser les inefficacités dues à la recombinaison électron-trou et passiver les états de surface, des couches de recouvrement ultra-fines d'Al2O3 et de TiO2 ont été déposées sur les électrodes en film mince BiVO4 d'une manière analogue à l'ALD. Cela a également été réalisé afin de protéger la surface de BiVO4 de la photocorrosion et d’augmenter sa stabilité. Une densité de photocourant de 0,54 mA/cm2 à 1,23 V vs RHE a été obtenue pour les 2 cycles de BiVO4 modifié par Al2O3, comme le montre la Figure 2, soit une amélioration de 54% par rapport à la BiVO4 nue qui démontrait une densité de photocourant de 0,35 mA/cm2. à 1,23 V vs RHE. Une augmentation de 15% de la stabilité de l'électrode de BiVO4 modifiée par Al2O3 a également été observée au cours de 7,5 heures d'irradiation continue. De plus, grâce aux mesures de capacité de surface présentées à la Figure 3, il a été montré que la surcouche de Al2O3 passivait effectivement à passiver les états de surface des électrodes de BiVO4. La nature de la surface de BiVO4 a été étudiée en étudiant la réactivité de la poudre de BiVO4 avec un titrant chimique. L’existence de groupes hydroxyle de surface sur BiVO4 a été confirmée et quantifiée (max. 1,5 OH / nm2) par titrage chimique. La réaction de la poudre de BiVO4 avec une impulsion de AlMe3 et une impulsion de H2O a montré qu'il existait 1,2 molécules de CH4 dégagées par Bi-OH. Dans ce travail, nous avons pu mettre en évidence les facteurs importants dans la synthèse de BiVO4 et leur incidence sur la photoactivité résultante. Nous avons également réussi à passiver les états de surface de BiVO4 en utilisant Al2O3, ce qui n’est pas bien exploré dans la littérature. De plus, nous avons pu sonder et discuter de la nature de la surface de BiVO4. Ceci est une connaissance très fondamentale et le premier rapport à ce sujet, à notre connaissance. Une bonne compréhension de cette surface semi-conductrice importante et de ses interactions facilitera la conception d'un photoanode BiVO4 plus efficace / Photoelectrochemical (PEC) water splitting is a direct way of producing a solar fuel like hydrogen from water. The bottleneck of this process is in the photoanode, which is responsible for the water oxidation side of the reaction1,2. In this work, the use of BiVO4 as a photoanode was extensively studied in order to improve its photoactivity. The optimization of BiVO4 photoanode synthesis via thin film electrodeposition on FTO was performed. The factors affecting the photoelectrochemical activity such as the electrodeposition time, ratio of the Bi-KI to benzoquinone-EtOH in the deposition bath, and the calcination temperature, have been investigated by using the Central Composite Design of Experiments.Surface states on the BiVO4 surface give rise to defect levels, which can mediate electron-hole recombination via the Shockley-Read-Hall mechanism5. In order to protect the BiVO4 surface and minimize the inefficiencies due to electron-hole recombination and passivate the surface states, ultrathin overlayers of Al2O3 and TiO2 were deposited to the BiVO4 thin film electrodes in an ALD-like manner. A photocurrent density of 0.54 mA/cm2 at 1.23 V vs RHE was obtained for the 2 cycles Al2O3-modified BiVO4, which was a 54% improvement from the bare BiVO4 that demonstrated a photocurrent density of 0.35 mA/cm2 at 1.23 V vs RHE. A 15% increase in stability of the Al2O3- modified BiVO4 electrode was also observed over 7.5 hours of continuous irradiation. Moreover, through surface capacitance measurements, it was shown that the Al2O3 overlayer was indeed passivating the surface states of the BiVO4 electrodes. The nature of the BiVO4 surface was studied by investigating the reactivity of powder BiVO4 with a chemical titrant. The existence of surface hydroxyl groups on BiVO4 was confirmed and quantified (max 1.5 OH/nm2) via chemical titration. The reaction of the BiVO4 powder with one pulse of AlMe3 and 1 pulse of H2O showed that there were 1.2 molecules of CH4 evolved per Bi-OH. In this work, we were able to highlight which factors are important in the synthesis of BiVO4, and how they affect the resulting photoactivity. We have also achieved the passivation of the BiVO4 surface states using Al2O3, which is not well-explored in literature. Moreover, we were able to probe and discuss the nature of the BiVO4 surface. This is a very fundamental knowledge and the first report of such, to the best of our knowledge. A good understanding of this important semiconductor surface and its interactions will aid in the design of a more efficient BiVO4 photoanode

Recently, restaurant employees exposing to cooking oil fume with potential lung cancer was highly concerned, indicating cooking oil fume emitted from restaurants might cause tremendous hazard to human health. This study combined photocatalytic oxidation and ozone oxidation technology to decompose VOCs from the exhaust of cooking oil fume from restaurants. Firstly, this study selected three different types of restaurants to implement air pollutant measurements in the indoor dinning room and stack emission. Indoor TVOCs continuous monitoring data showed that the highest TVOCs concentration was generally observed in the dining peak time. In this study, photocatalyst coated fiberglass filter was prepared by impregnation procedure and its characteristics was analyzed by SEM and XRD. Experimental results showed that the particle size of photocatalyst ranged from 25 to 50 nm and had high percentage of Anatase, suggesting that it had high photocatalytic reactivity. This study designed a continuous-flow reaction system combined nano-sized TiO2 photocatalysis with ozone oxidation technology to decompose VOCs from cooking oil fume. After passing through a fiberglass filter to remove oil droplets, the cooking oil fume then coated with nano-sized titanium oxide (UV/TiO2) fiberglass filter purification system, and then injected ozone into the system to decompose residual VOCs. This study further investigated the influences of operating parameters, including TVOCs initial concentration, O3 injection concentration, and reaction temperature on the decomposition efficiency of TVOCs by using the UV/TiO2/O3 technology. When the photocatalytic reaction temperature was 35~50¢J, the TVOC decomposition efficiency slightly increased with reaction temperature, however, when the reaction temperature went up to 55¢J, the TVOC decomposition efficiency increased only slightly, but did not increased linearly. Combination of photocatalysis and ozone oxidation system performance test results showed that ozone could decompose approximately 34% VOCs, and followed by the photocatalytical reaction of residual pollutants, achieving an overall decomposition efficiency of about 75%; while photocatalytic reaction can remove 64% of TVOCs and followed by O3 for the decomposition of residual pollutants, achieving an overall decomposition efficiency up to 94%. It showed that the combined UV/TiO2+O3 system could effectively remove VOCs in the cooking oil fume from the exhaust of restaurants. By using GC/MS to qualitatively analyze the speciation of TVOCs from cooking oil fume before and after UV/TiO2/O3, the results showed that the composition of VOCs had a decreasing trend. The peak area and dilution factor were applied to estimate the decomposition efficiency of different VOCs species. The decomposition efficiencies of pentane, 2-acrolein, acrolein, heptane, pentanal, hexanal, 2-hexenal, heptanal, heptenal and ethylhexenal were 56.21%, 72.88%, 51.33%, 32.23%, 59.04%, 69.22%, 73.53%, 41.37%, 92.57%, and 96.02%. Finally, a Langmuir-Hinshelwood kinetic model was applied to simulate the photocatalytic decomposition efficiency with the initial concentration of cooking oil fume. Model simulation results showed that the reaction rate increased with the initial TVOCs concentration. However, when TVOCs concentration increased gradually, the reaction rate became constant since the activated sites on the photocatalyst¡¦s surface was limited and cannot allow more VOC molecules diffuse to the activated sites for further photocatalytic reaction.

ABSTRACT The increase of carbon dioxide (CO2) concentration in the atmosphere has become a severe environmental problem, since it could cause global warming due to greenhouse effects. Thus, the reduction of CO2 emission to tackle the greenhouse effect has become one of the most important tasks for sustainable development. The outcomes of this study would be valuable to evaluate the feasibility of applying photocatalytic reduction process to remove CO2 from the atmosphere as well as the flue gas. This study investigated the photocatalytic reduction of CO2 in a self-designed batch UV/TiO2 photocatalytic reactor. The photocatalysts tested included commercial TiO2 (Degussa P-25) and synthesized TiO2 via modified sol-gel process (i.e. NO3-/TiO2 and SO42-/TiO2). Stainless steel supports coated with TiO2 were packed in the batch reactor. The initial concentrations of CO2 ranged from 0.5% to 7.5%. The reductants investigated included hydrogen (H2), water vapor (H2O), and hydrogen with water vapor (H2+H2O). The incident UV light with wavelength of 365 nm was irradiated by a 15-watt low-pressure mercury lamp. The photocatalytic reaction was conducted continuously for approximately 48 hours. Reactants and products were analyzed quantitatively by a gas chromatography with a flame ionization detector followed by a methaneizer (GC/FID-Methaneizer). Experimental results indicated that stainless steel coated with TiO2 had better photoreduction efficiency than that of quartz glass. The optimal operating conditions of CO2 photoreduction were observed by using H2 over SO42-/TiO2, which could produce major products of CO and CH4 and minor products of C2H4 and C2H6. Sulfuric acid used as a stabilizer in the sol-gel process could produce TiO2 of high specific surface area. Results obtained from the operating parameter tests showed that the photoreduction rate increased with the initial concentration of carbon dioxide and resulted in more product accumulation. Higher photoreduction efficiency of carbon dioxide was observed by using the hydrogen (H2) than water vapor (H2O). The photoreduction rate of carbon dioxide increased with reaction temperature, which promoted the formation of products. In addition, proper water vapor (ie. relative humidity of water vapor =25%~75%) could increase the photoreduction efficiency. However, the photoreduction efficiency decreased white it was close to (ie. relative humidity of water vapor =75%~100%). Concurred with previous researches, the reaction rate of major products over SO42-/TiO2 were higher than previous investigations of CO2 photoreduction. This study proposed the reaction pathway using hydrogen and/or water vapor as the reductants. Moreover, a one-site Langmiur-Hinshewood kinetic model (L-H model) was successfully applied to simulate the reaction rate of CO2 during the photoreduction reaction process.

This study investigated the photocatalytic reduction of CO2 in a self-designed closed circulated batch reactor system and a bench-scale batch photocatalytic reactor. The photocatalysts tested included titanium dioxide (TiO2, Degussa P-25) and zirconium oxide (ZrO2). The reductants investigated included hydrogen (H2), water vapor (H2O), and hydrogen plus water vapor (H2+H2O). The wavelengths of incident near ultra-violet (UV) and UV lights for the photocatalysis of TiO2 and ZrO2 were 365 nm and 254 nm, respectively. The initial concentrations of CO2 ranged from 0.2-5.0% and the reaction temperature ranged from 35-95 ¡³C. The incident near-UV (or UV) light with wavelength of 365 nm (or 254 nm) was irradiated by a 15-watt low-pressure mercury lamp. The photocatalytic reaction was conducted continuously for approximately two hours. Reactants and products were analyzed by a gas chromatography with a flame ionization detector followed by a methanizer (GC/FID-methanizer). Experimental results indicated that glass pellets coated with TiO2 had better photoreduction efficiency than ZrO2. The highest yield rates of the photoreduction of CO2 were obtained using TiO2 with H2+H2O and ZrO2 with H2. Photoreduction of CO2 over TiO2 with H2+H2O formed CH4, C2H6, and CO in the yield of 32.95~94.60, 0.80~18.55, 1.12~21.78 £gmol/g, respectively, while the photoreduction of CO2 over ZrO2 with H2 formed CO in the yield of 0.34~4.99 £gmol/g. Results obtained from the operating parameter tests showed that the photoreduction rate increased with the initial concentration of carbon dioxide and resulted in more product accumulation. The photoreduction rate of carbon dioxide increased with reaction temperature, which promoted the formation of products. Concurred with previous researches, the reaction rate of major products over TiO2 and ZrO2 were higher than previous investigations of CO2 photoreduction. Furthermore, the spectra of FTIR showed that formic acid (HCOOHads), methanol (CH3OHads), carbonate (CO32−ads), bicarbonate (HCO32−ads), formate (HCOO−ads), formic acid (HCOOH ads), formaldehyde (HCOHads) and methyl formate (HCOOCH3 ads) formed on the surface of TiO2 and ZrO2 photocatalysts. The detected reaction products supported the proposal of two reaction pathways for the photoreduction of CO2 over TiO2 and ZrO2 with H2 and H2O, respectively. A modified bimolecular Langmuir-Hinshelwood kinetic model was developed to simulate the reaction temperature, CO2 initial concentration and relative humidity promotion and inhibition of the photoreduction of CO2. Additionally, the modified L-H kinetic model was successfully applied to simulate the photoreduction rate of CO2. The result showed that CO2 could be reduced by used solar light over TiO2 and ZrO2 photocatalysts. The reaction products of CO2 photoreduction over TiO2 were CH4, C2H6, and CO in the yield of 2.16~2.995, 0.057~0.128, 0.078~0.134 £gmol/g, respectively, while the photoreduction of CO2 over ZrO2 formed only CO in the yield of 0.023~0.051 £gmol/g. Furthermore, experimental results indicated that TiO2 gave the highest average photo energy efficiency (AEf) of ~4.13%, and apparent quantum efficiency (£pA) of ~1.05%. However, the ZrO2 gave the highest average photo energy efficiency (AEf) of 5.07¡Ñ10-3%, and apparent quantum efficiency (£pA) of ~1.54¡Ñ10-2%.

The focus of this doctoral thesis is the atomic level design of photocatalysts and gas sensing materials. The band gap narrowing in the metal oxides for the visible-light driven photocatalyst as well as the interaction of water and gas molecules on the reactive surfaces of metal oxides and the electronic structure of kaolinite has been studied by the state-of-art calculations. Present thesis is organized into three sections. The first section discusses the possibility of converting UV active photocatalysts (such as Sr2Nb2O7, NaTaO3, SrTiO3, BiTaO4 and BiNbO4) into a visible active photocatalysts by their band gap engineering. Foreign elements doping in wide band gap semiconductors is an important strategy to reduce their band gap. Therefore, we have investigated the importance of mono- and co-anionic/cationic doping on UV active photocatalysts. The semiconductor's band edge position is calculated with respect to the water oxidation/reduction potential for various doping. Moreover, the tuning of valence and conduction band edge position is discussed on the basis of dopant's p/d orbital energy. In the second section of thesis the energetic, electronic and optical properties of TiO2, NiO and β-Si3N4 have been discussed to describe the adsorption mechanism of gas molecules at the surfaces. The dissociation of water into H+ or OH- occurs on the O-vacancy site of the (001)-surface of rutile TiO2 nanowire, which is due to the charge transfer from Ti atom to water molecule. The dissociation of water into OH- and imino (NH) groups is also observed on the β-Si3N4 (0001)-surface due to the dangling bonds of the lower coordinated N and Si surface atoms. Fixation of the SO2 molecules on the anatase TiO2 surfaces with O-deficiency have been investigated by Density Functional Theory (DFT) simulation and Fourier Transform Infrared (FTIR) spectroscopy. DFT calculations have been employed to explore the gas-sensing mechanism of NiO (100)-surface on the basis of energetic and electronic properties. In the final section the focus is to describe the optical band gap of pristine kaolinite using the hybrid functional method and GW approach. Different possible intrinsic defects in the kaolinite (001) basal surface have been studied and their effect on the electronic structure has been explained. The detailed electronic structure of natural kaolinite has been determined by the combined efforts of first principles calculations and Near Edge X-ray Absorption Fine Structure (NEXAFS).

Recently, the increasing level of atmospheric CO₂ has been widely noticed due to its association with global warming, provoking a growth in environmental concerns toward the continued use of fossil fuels. To mitigate the concentration of atmospheric CO₂, various strategies have been implemented. Among options to turn waste CO₂ into useful fuels and chemicals, carbon capture and utilisation along with renewable hydrogen production as the source materials for methanol production is more preferable. In the 1960s, the highly active and economic Cu/ZnO/Al₂O₃ catalyst was developed for CO₂ hydrogenation reaction to methanol, since then, metal nanoparticles and nanocomposites have been extensively investigated and applied. Especially, bimetallic catalysts have emerged as an important class of catalysts due to their unique properties and superior catalytic performances compared to their monometallic counterparts. This thesis presents the evolution of the catalyst development for CO₂ hydrogenation to methanol: Firstly, we introduced the CuZn-based catalysts with Zn content increased in the bimetallic CuZn system via a heterojunction synthesis approach. Secondly, we increased the active CuZn sites via introducing ultra-thin layered double hydroxide as the catalyst precursor for methanol production from CO₂ and H₂. Thirdly, a new class of Rh-In bimetallic catalysts were studied, which shows high methanol yield and selectivity under thermodynamically unfavourable methanol synthesis conditions owing to the strong synergies of Rh-In bimetallic system. Fourthly, for the renewable methanol production from H₂ and CO₂, the hydrogen source must come from the green production routes. Therefore, an in-depth study of a nanocomposite system, CdS-carbon nanotubes-MoS₂, for photocatalytic hydrogen production from water has been demonstrated. Finally, the conclusion of this thesis is given and an outlook is presented for the future development in this research area.

No presente trabalho, três tipos de fotocatalisadores híbridos nanométricos, CdS, CdS/TiO2, e CdS/TiO2/SiO2, foram preparados e utilizados em três aplicações fotoquímicas: fotodegradação macro e microscópica de um corante, fotólise da água para geração de H2 com acompanhamento via espectrometria de massas in situ e estudo de uma reação redox via microscopia de fluorescência de campo largo. As análises por microscopia eletrônica de varredura (MEV) e de transmissão (MET) apresentaram esferas de sílica com diâmetro em torno de 300 nm e nanopartículas de CdS e TiO2 com diâmetro da ordem de 5 nm e com alta aglomeração. O recobrimento da sílica com TiO2 e CdS não foi uniforme, resultando em \"ilhas\" preferencialmente isoladas. Apesar da morfologia heterogênea, os fotocatalisadores foram eficientes na degradação da safranina O, apresentando cinética de 1ª ordem em relação à concentração do corante. No que se refere à fotólise da água, o sistema ternário (CdS/TiO2/SiO2) apresentou a maior taxa de produção de H2 (0,79 mmol h-1 g-1), o que indica maior eficiência na transferência ou injeção de carga entre CdS e TiO2, devido ao melhor contato entre os dois semicondutores na superfície das nanopartículas (NPs) de sílica. Esse sistema também foi o mais eficiente na fotorredução do corante não fluorescente resazurina no corante fluorescente resorufina, acompanhada através de medidas de intermitência de fluorescência utilizando microscopia de fluorescência de campo largo. Em geral, os sistemas após adição do corante apresentaram intermitência de fluorescência mais lenta, com maiores tempos de relaxação de off. A fotorredução do corante estabeleceu um método interessante para o mapeamento das regiões de injeção de carga CdS/TiO2, inicialmente escuras e a seguir com alta intensidade de emissão. / In the present work, three types of nanosized hybrid photocatalysts, CdS, CdS/TiO2 and CdS/TiO2/SiO2, were synthesized and used in three photochemical applications: macro and microscopic photodegradation of a dye, photolysis of water to generate H2 monitored by in situ mass spectrometry and study of a redox reaction by wide-field fluorescence microscopy. Scanning (SEM) and transmission (TEM) electronic microscopies showed quasi-monodispersed silica spheres with a diameter of about 300 nm and CdS and TiO2 nanoparticles with a diameter of approximately 5 nm highly agglomerated. The coating of the silica with CdS and TiO2 was not uniform, resulting in \"islands\" preferentially isolated. Despite the heterogeneous morphology of the photocatalysts, they were efficient in the degradation of a safranine O solution, showing kinetics of first order with respect to dye concentration. With regard to water photolysis, the ternary system (CdS/TiO2/SiO2) showed the highest rate of H2 production (0.79 mmol g-1 h-1) , which indicates more efficient charge transfer or injection between CdS and TiO2 due to better contact between the two semiconductors on the surface of the silica nanoparticles (NPs). This system also was the most efficient photocatalyst in the photorreduction of the nonfluorescent dye resazurin into the fluorescent dye resorufin, monitored by fluorescence intermittency measurements using wide-field microscopy. In general, the systems after adding the dye presented slower fluorescence intermittency, with higher times of off relaxation. The photoreduction of the dye provided an interesting method for mapping the regions of CdS/TiO2 charge injection, initially dark and then with high emission intensity.

La modification du TiO₂ P25 par un ou deux métaux a connu un intérêt considérable ces dernières années, car ils constituent des catalyseurs et photocatalyseurs très actifs à la fois sous lumière UV et visible. Des nanostructures à un ou deux métaux, comme Au, Ag, Ag@CuO et CuO déposés sur le TiO₂ P25 ont la capacité d’absorber la lumière visible sur un large domaine de longueurs d’onde. Le TiO₂ modifié par des nanoparticules métalliques (comme, Cu, Au ou Ag) absorbe la lumière visible grâce à la résonance de plasmon de surface localisée (LSPR) des métaux. Dans le cas d’une hétérojonction de semi-conducteurs, la lumière visible est absorbée grâce à l’énergie du gap plus faible du second semi-conducteur (par rapport à celle du TiO₂ P25). La modification par une ou deux nanoparticules métallique induit une plus grande activité photocaralytique sous lumière visible par rapport au TiO₂ P25 pur, par transfert d’électrons vers la bande de conduction du P25. De plus sous lumière UV, la vitesse de capture d’électrons photo-excités peut être améliorée, ce qui inhibe les processus de recombinaison et permet de stocker ces électrons photo-excités.Cette thèse présente une synthèse des récentes avancées dans la préparation de TiO₂ modifié en surface par un ou deux métaux et ses applications environnementales. Des nanoparticules d’or ont été synthétisées par une méthode chimique à partir de chlorure de tetrakis(hydroxymethyl) phosphonium (THPC), des nanoparticules de Ag, Ag@CuO et CuO ont été synthétisées sur TiO₂ par radiolyse. L’effet de nombreux paramètres (comme la taille et la forme des particules ou la quantité de métal déposé) sur l’activité photocatalytique (oxydation du phénol, du 2-propanol et de l’acide acétique et génération d’hydrogène) a été étudié. La dynamique de porteurs de charge a été étudiée par conductivité microonde résolue en temps (TRMC). / The modification of TiO₂-P25 with one or two metal-based nanoparticles, have attracted considerable attention in recent years, as a new class of highly active catalysts and photocatalysts under both UV and visible light irradiation. One or two-metal-based structures, such as Au, Ag, Ag@CuO and CuO deposited on TiO₂-P25 have the ability to absorb visible light in a wide spectral range. Surface modified TiO₂ with metal nanoparticles (such as Cu, Au, Ag) absorb visible light due to the localized surface plasmon resonance (LSPR). In the case of semiconductor heterojunctions, they absorb visible light due to the narrow band gap of the second semiconductor, lower than TiO₂-P25. The modification with one or two metal-based nanoparticles induces a higher activity under visible light compared to pure TiO₂-P25, due to the transfer of electrons to the conduction band of TiO₂-P25. On the other hand, under UV irradiation, the speed of trapping photoexcited electrons can be improved, and inhibit the recombination process and have the capability of the storage of photoexcited electrons.This thesis presents recent advances in the preparation and environmental application of the surface modification of TiO₂-P25 with one or two-metal-based nanoparticles: The Au-NPs were synthesized by chemical method using tetrakis(hydroxymethyl) phosphonium chloride (THPC), and the nanoparticles of Ag, Ag@CuO and CuO-NPs were synthesized by gamma irradiation. Moreover, the effects of various parameters (such as particle size, shape of the nanoparticles and amount of metals) on the photocatalytic activity (phenol, 2-propanol and acetic acid oxidation, as well as hydrogen generation) were also studied. The charge carrier dynamics was studied by time resolve microwave conductivity (TRMC).

No description available.

In this doctoral thesis, we have studied the oxidation of carboxylic acids to obtain the corresponding acyloxy radicals, using visible light and non-toxic and inexpensive organic dyes, as photocatalysts. On the one hand, we study the photooxidation of aromatic carboxylic acids to obtain acyloxy radicals, whose decarboxylation is relatively slow (Chapter I and Chapter II). On the other hand, we describe the photooxidation of aliphatic carboxylic acids, to take advantage of the rapid decarboxylation of the corresponding acyloxy radicals, to generate nucleophilic radicals that were trapped by different reagents (Chapter III to Chapter V). It should be noted that all the protocols are free of expensive and toxic noble metals, the reactions were promoted with visible light at room temperature and the scalability of some reactions was demonstrated in batch conditions or using flow chemistry. In addition, mechanistic studies were carried out to propose plausible photocatalytic routes to all the reactions studied.