TiO2 Photocatalysis for the Transformation of Aromatic Water Pollutants into Fuels

The growing world energy consumption, with reliance on conventional energy sources and the associated environmental pollution, are considered the most serious threats faced by man-kind. Heterogeneous photocatalysis has become one of the most frequently investigated technolo-gies, due to its dual functionality, i.e., environmental remediation and converting solar energy into chemical energy, especially molecular hydrogen. H2 burns cleanly and has the highest gravimetric gross calorific value among all fuels. However, the use of a suitable electron donor, in what so-called “photocatalytic reforming”, is required to achieve acceptable efficiency. This oxidation half-reaction can be exploited to oxidize the dissolved organic pollutants, thus, simultaneously improving the water quality. Such pollutants would replace other potentially costly electron donors, achieving the dual-functionality purpose. Since the aromatic compounds are widely spread in the environment, they are considered attractive targets to apply this technology. In this review, different aspects are highlighted, including the employing of different polymorphs of pristine titanium dioxide as pho-tocatalysts in the photocatalytic processes, also improving the photocatalytic activity of TiO2 by loading different types of metal co-catalysts, especially platinum nanoparticles, and comparing the effect of various loading methods of such metal co-catalysts. Finally, the photocatalytic reforming of aromatic compounds employing TiO2-based semiconductors is presented

Solar and Visible Light Driven Photocatalysis for Sacrificial Hydrogen Generation and Water Detoxification with Chemically Modified Ti02

Photocatalysis is a recognized approach where light energy is employed to excite the semiconductor material producing electron/hole pair which eventually involves in the detoxification of pollutants and/or water splitting producing hydrogen. Existing photocatalysts suffer from poor activity or no activity in visible light irradiation which restricts them from solar light utilization. This work is focused on two key applications of photocatalysis (i) sacrificial hydrogen generation, and (ii) phenol degradation in visible and/or solar light. Platinum was loaded on TiO2 photocatalyst by solar photo-deposition method. Eosin Y dye was used as a sensitizer for sensitization of platinum loaded TiO2 photocatalyst. The photocatalyst was irradiated from the top with a solar simulator. The light source was equipped with AM 1.5 G as well as a 420 nm cutoff filter to remove all the UV light. A factorial design at two levels and four factors has been carried out in order to investigate the potential for hydrogen generation using Eosin Y-sensitized TiO2/Pt catalyst under visible solar light in presence of triethanolamine as electron donor. Experimental data were analyzed using both “Pareto analysis” as well as conventional regression analysis techniques. A regression function was proposed that satisfactorily predicts hydrogen generation as a function of various operating parameters. Later, the photocatalytic behavior of the eosin Y–sensitized photocatalyst was studied in solar-UV (300-388 nm), solar-visible (420-650 nm) and full solar spectrum (300-650 nm) to explore the optimum reaction conditions such as (i) light intensity (100 mW cm-2), (ii) solution pH (7.0), (iii) platinum content (wt %) on TiO2 (0.25 %), (iv) mass of eosin Y-TiO2/ Pt (1-1.3 g L-1) , (v) concentration of trietanolamine (0.25 M), and (vi) mass ratio of eosin Y to TiO2/Pt (1:10). The reaction mechanisms were different in solar and visible lights, although in both cases formaldehyde was detected as an intermediate product. Studies in a pulsating flow reactor showed positive effects of pre-sonication, increased flow rate and bi-directional mixing mode in solar hydrogen generation. A detailed study on the photocatalytic behavior of formaldehyde for sacrificial hydrogen generation was performed for better understanding of the process. Photocatalytic hydrogen generation from formaldehyde was influenced by solution pH, platinum content (wt %) on TiO2, catalyst concentration, light intensity, and initial formaldehyde concentration. A Langmuir-type model was well fitted with the experimental data for photocatalytic hydrogen generation from both triethanolamine and formaldehyde as sacrificial agents. Apparent quantum yield (QY) was much higher for UV light driven hydrogen generation. In solar and visible light the QYs were a function of the light intensity and the wavelength range considered for the calculation. Phenol degradation with eosin Y-sensitized TiO2/Pt photocatalyst under solar-visible light was performed with triethanolamine as electron donor. About 93 % degradation of 40 ppm phenol solution was achieved within 90 minutes using Eosin Y-TiO2/Pt photocatalyst at optimum conditions (pH = 7.0, catalyst loading = 0.8 g L-1, triethnolamine concentration = 0.2 M, 0.5 % Pt loading on TiO2, visible solar light of 100 mW cm-2). Kinetic rate constant and adsorption equilibrium constant were determined and a Langmuir-Hinshelwood type equation was proposed to describe phenol degradation on TiO2 at different visible light intensities. The model equation predicts experimental results quite well

Recent Developments in Environmental Photocatalytic Degradation of Organic Pollutants: The Case of Titanium Dioxide Nanoparticles—A Review

The presence of both organic and inorganic pollutants in water due to industrial, agricultural, and domestic activities has led to the global need for the development of new, improved, and advanced but effective technologies to effectively address the challenges of water quality. It is therefore necessary to develop a technology which would completely remove contaminants from contaminated waters. TiO2 (titania) nanocatalysts have a proven potential to treat “difficult-to-remove” contaminants and thus are expected to play an important role in the remediation of environmental and pollution challenges. Titania nanoparticles are intended to be both supplementary and complementary to the present water-treatment technologies through the destruction or transformation of hazardous chemical wastes to innocuous end-products, that is, CO2 and H2O. This paper therefore explores and summarizes recent efforts in the area of titania nanoparticle synthesis, modifications, and application of titania nanoparticles for water treatment purposes

Degradation of emerging contaminants using metal organic frameworks (MOFs) by photocatalysis

Tesis Doctoral inédita leída en la Universidad Autónoma de Madrid, Facultad de Ciencias, Departamento de Química Física Aplicada. Fecha de Lectura: 16-12-2022La realización de este trabajo ha sido posible gracias al apoyo económico del Ministerio de Economía y Competitividad (MINECO) a través del proyecto CTQ2016-78576-R, a la Agencia Estatal de Investigación (AEI) por el proyecto PID2019-106186RB-I00/AEI/10.13039/501100011033 y a la concesión de un contrato de Formación de Personal Investigador (FPI) del MINECO (Referencia BES-2017- 082613

Photocatalytic production of hydrogen from biomass-derived feedstocks

[EN] The application of photocatalysis for the utilisation of sunlight energy is intensely investigated in present times, particularly in prospect of generating solar fuels by hydrogen production or CO2 reduction processes as tools for societies aiming to relief their thirst for fossil resources. From the perspective of sustainability, the rational use of biomass-derived feedstocks for photocatalytic H2 production is a feasible, proven and highly efficient process. In this review, in addition to delving into physico-chemical fundamentals of photocatalytic processes on semiconductors, the research activity on this topic related to the design of revolutionary semiconductor-based materials, generally including metallic nanoparticles or complexes as hydrogen-evolving co-catalysts, is outlined and critically evaluated. Moreover, the use of sunlight and renewable feedstocks for the generation of hydrogen, as a compelling opportunity for the energy sector, is emphasised. Special focus is also set on the valorisation of biorefinery products, agricultural residues and industrial or municipal waste.Financial support from the Spanish Government-MINECO through "Severo Ochoa" (SEV 2012-0267) is acknowledged. The European Union is also acknowledged for the SynCatMatch project (ERC-AdG-2014-671093).Puga, AV. (2016). Photocatalytic production of hydrogen from biomass-derived feedstocks. Coordination Chemistry Reviews. 315:1-66. https://doi.org/10.1016/j.ccr.2015.12.009S16631

Novel strategies to design and construct efficient semiconductor-based photocatalyst for enhancing photocatalytic hydrogen evolution and nitrogen fixation under sunlight irradiation

L'énergie solaire est la source d'énergie la plus abondante au monde et elle peut être convertie en énergie chimique via des processus photocatalytiques. Au cours des dernières décennies, la photocatalyse sous la lumière du soleil est apparue comme une alternative innovante aux combustibles fossiles afin de résoudre et prévenir des problèmes graves liés à la crise environnementale et énergétique. Actuellement, les matériaux à base de semi-conducteurs (tels que TiO₂, C₃N₄, In₂O₃, WO₃) sont intensivement étudiés pour diverses applications photocatalytiques, y compris la réaction d’évolution d'hydrogène (HER) et la réduction de l'azote en ammoniac (NRR). Par conséquent, diverses approches telles que l'ingénierie structurelle, les hétérojonctions nanocomposites ont été étudiées afin de surmonter les problèmes de ces matériaux et ainsi augmenter l'activité catalytique. Dans le cadre de cette thèse, nous avons développé des nouvelles stratégies pour la synthèse des quatre types de photocatalyseurs efficaces pour la production d'hydrogène et la fixation de l'azote sous la lumière du soleil. Nos matériaux présentent une structure unique, qui favorise l'absorption de la lumière visible, la séparation des charges électrons-trous et l’augmentation du nombre de sites actifs.Pour l'application de la génération d'hydrogène photocatalytique, nous avons d'abord synthétisé les sphères de type éponge CdI₂nS₄ monophasées via une méthode solvothermique suivie d'un traitement au gaz contenant H₂S. La formation du complexe Cd/In avec une distribution uniforme de Cd²⁺ et In³⁺ a joué un rôle crucial dans la formation du spinelle monophasé CdIn₂S₄. L'énergie de la bande interdite s'est avérée être significativement réduite, ce qui permet une absorption étendue de la lumière visible jusqu'à 700 nm, ceci est principalement attribué à la dispersion d'espèce sulfure sur la bande de valence du CdIn₂S₄ monophasé. Avec le dépôt de Ni métallique comme cocatalyseur de réduction, le photocatalyseur hybride Ni-CdIn₂S₄ a montré une efficacité améliorée pour la production d'hydrogène sous la lumière solaire, ce qui représente une augmentation de l’activité d’environ, respectivement, 5,5 et 3,6 fois que celle des échantillons Pt-CdIn₂S₄ et Pd-CdIn₂S₄. Le deuxième système photocatalytique développé implique la préparation de nitrure de carbone graphitique dopé au S (Ni-SCN). Ce dernier est chimiquement ancré au nickel par une technique connue sous le nom de processus de photo-dépôt assisté par sulfuration. L'origine de la structure distinctive du Ni-SCN est dû à l'existence de liaisons chimiques NiS-C-N dans le système, ce qui favorisait la séparation des charges photogénérées et améliorait la capacité d’absorption lumineuse du photocatalyseur. Par conséquent, l’échantillon NiSCN synthétisé présente une excellente activité photocatalytique pour la production d'hydrogène sous la lumière du soleil. En effet, ce système présente une activité beaucoup plus élevée que celle des systèmes g-C₃N₄ dopés au S, Ni supporté g-C₃N₄ et Pt supporté g-C₃N₄ dopés au S. Pour une application photo (électro) catalytique de fixation de l'azote, nos travaux sont les premiers à rapporter la synthèse de nanoparticules d'Au chargées de nanoparticules W₁₈O₄₉ dopées au Fe (notées WOF-Au) par une synthèse solvothermique suivie d'un dépôt in situ des nanoparticules d'Au. L'incorporation de dopants Fe peut non seulement guérir les états de défaut de masse dans les réseaux non stœchiométriques W₁₈O₄₉, mais également favoriser la séparation et la migration interfaciale des électrons du photocatalyseur vers les molécules N₂ chimisorbées; tandis que les nanoparticules Au décorées sur la surface dopée au Fe W₁₈O₄₉ ont fourni les électrons à haute énergie pour la réduction de N₂ via l'effet de résonance plasmonique de surface localisé (LSPR). Le système WOF-Au plasmonique résultant montre un rendement amélioré pour la production de NH₃, beaucoup plus élevé que celui du W₁₈O₄₉ pur ainsi qu'une très grande stabilité. L'amélioration des performances photoélectrocatalytiques est principalement due à l'effet synergique des dopants Fe et des nanoparticules Au dans l'hôte W₁₈O₄₉. Enfin, les cacahuètes creuses de In₂O₃ dopées au Ru (dénotées Ru-In₂O₃ HPN) ont été fabriquées par la nouvelle stratégie d'auto-matrice suivie de la calcination des précurseurs synthétisés. Les nanoparticules uniformes In₂O₃ sont étroitement agglomérées ensemble pour former une structure de cacahuète creuse, ce qui facilite la séparation et le transport des l'électrons-trous photoexcités, améliorant l’absorption de la lumière par multi-réflexion. De plus, l'introduction des dopants Ru induit de nombreuses lacunes en oxygène à la surface et réduit l'énergie de la bande interdite du système photocatalytique. Ces lacunes d'oxygène agissent comme des centres de piégeage, facilitant la séparation des électrons trous photoexcités. Par conséquent, le taux de production d'ammoniac des Ru-In₂O₃ HPNs est 5,6 fois plus élevé que celui des In₂O₃ HPNs purs et largement supérieur au matériau en vrac d'In₂O₃, lorsqu’il est soumis à l’irradiation solaire.Solar energy is the most abundant energy source in the world, and it can be converted into chemical energy via photocatalytic processes. Over the last decades, sunlight-driven photocatalysis has emerged as an innovative alternative to fossil fuels for solving the severe problems related to environmental diseases and the energy crisis. Currently, semiconductorbased materials (such as TiO₂, C₃N₄, In₂O₃, WO₃, BiVO₄) have been intensively studied for diverse photocatalytic applications, including the hydrogen evolution reaction (HER) and the nitrogen reduction reaction (NRR) to produce ammonia. However, the drawbacks of weak visible light absorption, low electron-hole separation with high recombination rate, and lack of surface active-sites have limited the photocatalytic performance of these semiconductorbased photocatalysts. Therefore, various approaches such as structural engineering, nanocomposite heterojunctions have been applied to overcome the limitations of these materials and boosting the catalytic activity. In this thesis, we employed novel strategies to develop four efficient photocatalytic systems for hydrogen production and nitrogen fixation. Our materials possessed a unique structure, which is advantageous to promote the visiblelight absorption, facilitate the separation of charge carrier, and increase the number of surface-active sites. For the photocatalytic hydrogen evolution application, we firstly synthesized the singlephase CdIn₂S₄ sponge-like spheres via solvothermal method followed by H₂S gas treatment. The formation of CdIn-complex with uniform distribution of Cd²⁺ and In³⁺ played a crucial role in achieving the spinel structured-single phase CdIn₂S₄. The bandgap energy was found to be significantly reduced, resulting in the extended visible light absorption up to 700 nm, which was primarily attributed to the sulfide species-mediated modification of the valence band in CdIn₂S₄ single-phase. With the deposition of Ni metal as a reduction cocatalyst, the hybrid Ni-CdIn₂S₄ photocatalyst showed enhanced solar light-driven photocatalytic hydrogen evolution efficiency, which is around 5.5 and 3.6 folds higher than that of Pt-CdIn₂S₄ and Pd-CdIn₂S₄ samples, respectively. The second developed photocatalytic system involved the preparation of chemically bonded nickel anchored S-doped graphitic-carbon nitride (Ni-SCN) through a technique known as sulfidation assisted photo-deposition process. The origin of the distinctive structure of Ni-SCN was due to the existence of Ni-S-C-N chemical bonds in the system, which fundamentally favored the separation of photogenerated electron-hole and improved the light-harvesting capabilities of the photocatalyst. Consequently, the synthesized Ni-SCN exhibited an excellent sunlight-driven photocatalytic activity toward hydrogen evolution, which was several times higher than Sdoped g-C₃N₄, Ni supported g-C₃N₄ and Pt loaded S-doped C₃N₄ systems. For photo(electro)catalytic nitrogen fixation application, our work is the first to report the synthesis of Au nanoparticles loaded Fe doped W₁₈O₄₉ (denoted as WOF-Au) nanorods through a solvothermal synthesis following by in situ deposition of Au nanoparticles. The incorporation of Fe dopants can not only heal the bulk-defect-states in nonstoichiometric W₁₈O₄₉ lattices but also promote the separation and interfacial migration of electrons from photocatalyst to chemisorbed N₂ molecules; while Au nanoparticles decorated on the Fe doped W₁₈O₄₉ surface provided the high energetic electrons for N₂ reduction via the localized surface plasmon resonance effect (LSPR). The obtained plasmonic WOF-Au system shows an enhanced NH₃ yield, which is much higher than that of the bare W₁₈O₄₉, as well as very high stability. The enhancement in photoelectrocatalytic performance is mainly contributed by the synergetic effect of Fe dopants and plasmonic Au nanoparticles on the W₁₈O₄₉ host. Lastly, Ru doped In₂O₃ hollow peanuts (demoted as Ru-In₂O₃ HPNs) were fabricated by the novel self-template strategy followed by the calcination of the as-synthesis precursors. The uniform In₂O₃ nanoparticles were closely packed together to form a hollow peanut structure, which facilitated the separation and transportation of photoinduced electron-hole and favored the light-harvesting ability by the internal multi-reflection process. Furthermore, the introduction of Ru dopants induced numerous surface oxygen vacancies and narrow down the bandgap energy of the photocatalytic system. These oxygen vacancies act as trapping centers, facilitating the separation of photoexcited electrons and holes. Consequently, the ammonia production rate of Ru-In₂O₃ HPNs was 5.6 times and much higher as compared to pure In₂O₃ HPNs and bulk material of In₂O₃ under solar light irradiation

Treatment of Perfluorinated Compounds and Nitroaromatics by Photocatalysis in the Presence of Ultraviolet and Solar Light

Nitroaromatic compounds (NACs) and perfluorinated compounds (PFCs) are two classes of water contaminants of DoD concern due to their risk to the environment, personnel, and mission. This study investigated the potential of an innovative technology, oxidation using titanium dioxide (TiO2) and TiO2 doped with silver (Ag-TiO2) as photocatalyst, to effectively and energy efficiently treat NAC and PFC-contaminated water. Three model contaminants, 2,4-DNT (NAC), and PFOA and PFOS (PFCs), were degraded using TiO2 and Ag-TiO2 immobilized on glass slides under sunlight and UV light in atmospheric conditions and at neutral pH. 2,4-DNT degraded 14% and 15% in the presence of Ag-TiO2 and TiO2, respectively, under sunlight after 8 hours. After 8 hours under UV light, 2,4-DNT degraded 13% and 29% in the presence of Ag-TiO2 and TiO2, respectively. Results indicate that PFOA and PFOS do not degrade under the conditions of the experiment. Further study is needed to investigate the viability of the technology to treat NAC- and PFC-contaminated water

3rd International Conference on Nanomaterials Science and Mechanical Engineering: book of abstracts

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