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A single semiconductor employed into photo(electro)catalysis is not sufficient for charge carrier separation. Designing a multiple heterojunction system is a practical method for photo(electro)catalysis. Herein, novel two-dimensional AgInS2/SnS2/RGO (AISR) photocatalysts with multiple junctions were prepared by a simple hydrothermal method. The synthesized AISR heterojunctions showed superior photoelectrochemical performance and photocatalytic degradation of norfloxacin, with a high degradation rate reaching 95%. More importantly, the toxicity of photocatalytic products decreased within the reaction process. High spatial separation efficiency of photogenerated electron-hole pairs was evidenced by optical and photoelectrochemical characterizations. Furthermore, a laser flash photolysis technique was carried on investigating the lifetime of the charge carrier of the fabricated dual heterostructures. In addition, sulfur and oxygen vacancies existed in AISR heterojunctions could largely constrain the recombination of electron-hole pairs. Density functional theory calculations were carried out to analyze the mechanism of photoinduced interfacial redox reactions, showing that reduced graphene oxide and AgInS2 act as electron and hole trappers in the photocatalytic reaction, respectively. Due to the interfacial electric field formed from AISR dual heterojunctions, the effective spatial charge separation and transfer contributed to the boosting photo(electro)catalytic performance.
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Meeting the growing global energy demand is one of the important challenges of the 21st century. Currently over 80% of the world's energy requirements are supplied by the combustion of fossil fuels, which promotes global warming and has deleterious effects on our environment. Moreover, fossil fuels are non-renewable energy and will eventually be exhausted due to the high consumption rate. A new type of alternative energy that is clean, renewable and inexpensive is urgently needed. Several candidates are currently available such as hydraulic power, wind force and nuclear power. Solar energy is particularly attractive because it is essentially clean and inexhaustible. A year's worth of sunlight would provide more than 100 times the energy of the world's entire known fossil fuel reserves. Photocatalysis and photovoltaics are two of the most important routes for the utilization of solar energy. However, environmental protection is also critical to realize a sustainable future, and water pollution is a serious problem of current society. Photocatalysis is also an essential route for the degradation of organic dyes in wastewater. A type of compound with the defined structure of perovskite (ABX3) was observed to play important roles in photocatalysis and photovoltaics. These materials can be used as photocatalysts for water splitting reaction for hydrogen production and photo-degradation of organic dyes in wastewater as well as for photoanodes in dye-sensitized solar cells and light absorbers in perovskite-based solar cells for electricity generation. In this review paper, the recent progress of perovskites for applications in these fields is comprehensively summarized. A description of the basic principles of the water splitting reaction, photo-degradation of organic dyes and solar cells as well as the requirements for efficient photocatalysts is first provided. Then, emphasis is placed on the designation and strategies for perovskite catalysts to improve their photocatalytic activity and/or light adsorption capability. Comments on current and future challenges are also provided. The main purpose of this review paper is to provide a current summary of recent progress in perovskite materials for use in these important areas and to provide some useful guidelines for future development in these hot research areas.
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We report a carbon-air battery for power generation based on a solid-oxide fuel cell (SOFC) integrated with a ceramic CO2-permeable membrane. An anode-supported tubular SOFC functioned as a carbon fuel container as well as an electrochemical device for power generation, while a high-temperature CO2-permeable membrane composed of a CO3(2-) mixture and an O(2-) conducting phase (Sm(0.2)Ce(0.8)O(1.9)) was integrated for inâ situ separation of CO2 (electrochemical product) from the anode chamber, delivering high fuel-utilization efficiency. After modifying the carbon fuel with a reverse Boudouard reaction catalyst to promote the inâ situ gasification of carbon to CO, an attractive peak power density of 279.3â mW cm(-2) was achieved for the battery at 850 °C, and a small stack composed of two batteries can be operated continuously for 200â min. This work provides a novel type of electrochemical energy device that has a wide range of application potentials.
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The perovskite SrNb0.1 Co0.7 Fe0.2 O3-δ (SNCF) is a promising OER electrocatalyst for the oxygen evolution reaction (OER), with remarkable activity and stability in alkaline solutions. This catalyst exhibits a higher intrinsic OER activity, a smaller Tafel slope and better stability than the state-of-the-art precious-metal IrO2 catalyst and the well-known BSCF perovskite. The mass activity and stability are further improved by ball milling. Several factors including the optimized eg orbital filling, good ionic and charge transfer abilities, as well as high OH(-) adsorption and O2 desorption capabilities possibly contribute to the excellent OER activity.
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The synthesis of highly nitrogen-doped mesoporous carbon spheres (NMCS) is reported. The large pores of the NMCS were obtained through self-polymerization of dopamine (DA) and spontaneous co-assembly of diblock copolymer micelles. The resultant narrowly dispersed NMCS possess large mesopores (ca. 16â nm) and small particle sizes (ca. 200â nm). The large pores and small dimensions of the N-heteroatom-doped carbon spheres contribute to the mass transportation by reducing and smoothing the diffusion pathways, leading to high electrocatalytic activity.
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Carbono/química , Micelas , Nitrógeno/química , Polímeros/química , Microscopía Electrónica de RastreoRESUMEN
Cobalt-manganese spinel catalysts performed unsatisfactory activity at low-temperature and narrow reaction temperature window, which greatly limited the application in NO reduction by CO. Herein, we synthesize a series of Cu-doped CoMn2O4 catalysts and apply to NO reduction by CO. The Cu0.3Co0.7Mn2O4 exhibited superior catalytic performance, reaching 100% NO conversion and 80% N2 selectivity at 250 °C. Detailed structural analysis showed that the introduced Cu replaces some Co in tetrahedral coordination to induce a strong synergistic effect between different metals. This endows the catalyst with the promotion of both electron transfer and oxygen vacancy generation on the catalyst surface. Importantly, the reaction mechanism and pathway were further revealed by in situ diffusion Fourier transform infrared spectroscopy (DRIFTS) and density functional theory (DFT) calculations. The results indicated that the cycle of oxygen vacancy mainly determines the catalytic activity of NO reduction by CO. Notably, Cu doping significantly lowered the energy barrier of the rate-determining step (*CO + O â *Ov + CO2), facilitating the desorption of the CO2 and exposing the active sites for efficient NO reduction with CO. This work offers an effective way for designing the catalyst in NO reduction by CO and provides a reference for exploring the catalytic mechanism of the reaction.
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CuFe2O4 spinel has been considered as a promising catalyst for the electrochemical reaction, while the nature of the crystal phase on its intrinsic activity and the kind of active site need to be further explored. Herein, the crystal phase-dependent catalytic behavior and the main active sites of CuFe2O4 spinel for electrochemical dechlorination of 1,2-dichloroethane are carefully studied based on the combination of experiments and theoretical calculations. Cubic and tetragonal CuFe2O4 are successfully prepared by a facile sol-gel method combined with high temperature calcination. Impressively, CuFe2O4 with the cubic phase shows a higher activity and ethylene selectivity compared to CuFe2O4 with the tetragonal phase, suggesting a significant facilitation of electrocatalytic performance by the cubic crystal structure. Moreover, the octahedral Fe atom on the surface of cubic CuFe2O4(311) is the active site responsible to produce ethylene with the energy barrier of 0.40 eV. This work demonstrates the significance of crystal phase engineering for the optimization of electrocatalytic performance and offers an efficient strategy for the development of advanced electrocatalysts.
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Dichloromethane (CH2Cl2) hydrodechlorination to methane (CH4) is a promising approach to remove the halogenated contaminants and generate clean energy. In this work, rod-like nanostructured CuCo2O4 spinels with rich oxygen vacancies are designed for highly efficient electrochemical reduction dechlorination of dichloromethane. Microscopy characterizations revealed that the special rod-like nanostructure and rich oxygen vacancies can efficiently enhance surface area, electronic/ionic transport, and expose more active sites. The experimental tests demonstrated that CuCo2O4-3 with rod-like nanostructures outperformed other morphology of CuCo2O4 spinel nanostructures in catalytic activity and product selectivity. The highest methane production of 148.84 µmol in 4 h with a Faradaic efficiency of 21.61% at -2.94 V (vs SCE) is shown. Furthermore, the density function theory proved oxygen vacancies significantly decreased the energy barrier to promote the catalyst in the reaction and Ov-Cu was the main active site in dichloromethane hydrodechlorination. This work explores a promising way to synthesize the highly efficient electrocatalysts, which may be an effective catalyst for dichloromethane hydrodechlorination to methane.
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The floatability of water on oil surface was studied. A numerical model was developed from the Young-Laplace equation on three interfaces (water/oil, water/air, and oil/air) to predict the theoretical equilibration conditions. The model was verified successfully with an oil/water system. The stability of the floating droplet depends on the combination of three interface tensions, oil density, and water droplet volume. For practical purposes, however, the equilibrium contact angle has to be greater than 5° so the water droplet can effectively float. This result has significant applications for biodegrading oil wastes.
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Electroreductive CO coupling provides a prospective strategy for biomass derivative upgrading via reducing the number of oxygen-containing functional groups and increasing their molecular weight. However, exploring superior electrocatalysts with effective reactivity and high selectivity for target products are still a challenge. In this work, single atom Au surface derived NiMn2O4 (SACs Au-NiMn2O4) spinel synergetic composites were fabricated by a versatile adsorption-deposition method and applied in electroreductive self-coupling of benzaldehyde to dibenzyl ether. The SACs Au-NiMn2O4 spinel synergetic composites enhanced electroreductive coupling of benzaldehyde, significantly improved the yield and selectivity of dibenzyl ether. Systematic characterizations and density functional theory calculation revealed that atomically dispersed Au occupied surface Ni2+ vacancies, which played a dominated role in CO coupling of benzaldehyde. Detailed calculation results showed that benzaldehyde preferred to adsorb on Ni octa-hedral sites of NiMn2O4 spinel synergetic structure, single atom Au surficial derivation over NiMn2O4 further reduced the adsorption energy (Eads) of benzaldehyde on SACs Au-NiMn2O4, thus the CO coupling of benzaldehyde to dibenzyl ether was promoted. Moreover, single atom Au surficial derivation lowered the energy barrier of rate-determining step, facilitated the formation of dibenzyl ether species. Our work also paves an avenue for rational design single atom materials using spinel as support.
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Benzaldehídos , Óxido de Magnesio , Óxido de AluminioRESUMEN
CO2 capture from flowing flue gases through adsorption technology is essential to reduce the emission of CO2 to the atmosphere. The rational design of highly efficient carbon-based absorbents with interfacial structures containing interconnected porous structures and abundant adsorption sites might be one of the promising strategies. Here, we report the synthesis of nitrogen-doped carbon aerogels (NCAs) via prepolymerized phenol-melamine-formaldehyde organic aerogels (PMF) by controlling the addition amount of ZnCl2 and the precursor M/P ratio. It has been revealed that NCAs with a higher specific surface area and interconnected porous structures contain a large amount of pyridinic nitrogen and pyrrolic nitrogen. These would act as the intrinsic adsorption sites for highly effective CO2 capture and further improve the CO2/N2 separation efficiencies. Among the prepared samples, NCA-1-2 with a high micropore surface area and high nitrogen content exhibits a high CO2 adsorption capacity (4.30 mmol g-1 at 0 °C and 1 bar) and CO2/N2 selectivity (36.5 at 25 °C, IAST). Under typical flue gas conditions (25 °C and 1.01 bar), equilibrium gas adsorption analysis and dynamic breakthrough measurement associated with a high adsorption capacity of 2.65 mmol g-1 at 25 °C and 1.01 bar and 0.81 mmol g-1 at 25 °C and 0.15 bar. This rationally designed N-doped carbon aerogel with specific interfacial structures and high CO2 adsorption capacity, high selectivity, and adsorption performance remained pretty stable after multiple uses.
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Electrocatalytic nitrate reduction is an effective strategy to eliminate nitrate's environmental impact and produce high-value-added ammonia products. However, most of the current reports focus on preparation strategies of catalysts, with poor exploration of the mechanism. In this work, we fabricated a binding-free Cu-doped Co3O4 electrode (Cu-Co3O4) to reveal the structure-activity relationship. Cu-Co3O4 exhibited a maximum Faradaic efficiency of ammonia of up to 86.5% at -0.6 V vs reversible hydrogen electrode in a neutral electrolyte, with the corresponding yield rate of 36.71 mmol h-1 g-1. In situ electrochemical Raman spectroscopy confirmed that the structure of Cu-Co3O4 exhibits excellent stability and durability. Theoretical analysis revealed that the interaction between Cu and Co induces the d-band center position of the mono-metal oxide to shift toward the center to optimize the nitrate reduction intermediate hydrodeoxygenation free-energy change, especially of *NOx (x = 1, 2, and 3). These results offer guidelines for the electrochemical reduction of nitrate with transition metal oxide electrocatalysts.
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The interfacial interaction of activated carbon with volatile organic compounds (VOCs) is seriously affected by water vapor. Therefore, it is vital to enhance the hydrophobic performance of activated carbon for expanding its application in industrial and environmental fields. Herein, a series of hydrophobic activated carbon was fabricated by tailored mixed siloxane and applied in dynamic competitive adsorption at 0, 50, and 90% humidity. Simultaneously, the diffusion molecular models and multicomponent adsorption experiments were used to study the adsorption and diffusion mechanisms. The hydrophobicity of activated carbon was significantly improved by loading of mixed siloxane, in which the equilibrium water absorption decreased from 21.9 to 7.2% and the contact angles increased by 70.10°. Meanwhile, dynamic competitive adsorption at different humidities indicated that the siloxane-functionalized activated carbons (SACs) showed much better competitive adsorption performances for VOCs than original activated carbon, which was further confirmed by the theoretical calculations of adsorption energy. In addition, a remarkable adsorption selectivity and reusability could be demonstrated to VOCs with different polarities on SACs. This study not only provides a new strategy for the hydrophobic modification of activated carbon materials but also offers theoretical guidance for the treatment of gas streams with significant water contents.
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The development of bi-functional electrocatalyst with high catalytic activity and stable performance for both oxygen evolution/reduction reactions (OER/ORR) in aqueous alkaline solution is key to realize practical application of zinc-air batteries (ZABs). In this study, we reported a new porous nano-micro-composite as a bi-functional electrocatalyst for ZABs, devised by the in situ growth of metal-organic framework (MOF) nanocrystals onto the micrometer-sized Ba0.5Sr0.5Co0.8Fe0.2O3 (BSCF) perovskite oxide. Upon carbonization, MOF was converted to porous nitrogen-doped carbon nanocages and ultrafine cobalt oxides and CoN4 nanoparticles dispersing inside the carbon nanocages, which further anchored on the surface of BSCF oxide. We homogeneously dispersed BSCF perovskite particles in the surfactant; subsequently, ZIF-67 nanocrystals were grown onto the BSCF particles. In this way, leaching of metallic or organic species in MOFs and the aggregation of BSCF were effectively suppressed, thus maximizing the number of active sites for improving OER. The BSCF in turn acted as catalyst to promote the graphitization of carbon during pyrolysis, as well as to optimize the transition metal-to-carbon ratio, thus enhancing the ORR catalytic activity. A ZAB fabricated from such air electrode showed outstanding performance with a potential gap of only 0.83 V at 5 mA cm-2 for OER/ORR. Notably, no obvious performance degradation was observed for the continuous charge-discharge operation for 1800 cycles over an extended period of 300 h.
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Volatile organic compounds (VOCs), as hazardous gaseous pollutants, have attracted much attention due to their potential threat to both human health and the environment. Accordingly, photocatalysis technology is seen as a promising technology to control low concentration VOCs due to its mild operation conditions, low energy consumption, and mineralization ability. However, there are some issues with photocatalysts, such as low light utility and fast photogenerated carrier recombination, which need to be addressed for practical applications. In this work, novel nitrogen-doped carbon dot (NCD)-modified ZnFe2O4 yolk-shell nanostructure photocatalysts were fabricated for the first time. The yolk-shell structure of ZnFe2O4 efficiently shortened the photogenerated carrier migration path and enhanced light scattering in its void, while the decorated NCDs accelerated the charge transfer from the bulk to the surface. A series of characterizations was conducted to investigate the crystal structure, elemental status, optical properties, and photocatalytic performance of the obtained composite photocatalysts. The NCD-modified ZnFe2O4 yolk-shell photocatalysts exhibited both a wide spectral absorbance and low carrier recombination, resulting in high photocatalytic activity and degradation ability towards gaseous o-dichlorobenzene. Density functional theory (DFT) calculations further revealed that the NCDs effectively promoted charge transfer and weakened the recombination of photo-generated electron-hole pairs. Additionally, in situ Fourier transform infrared (FTIR) spectroscopy was performed to investigate the degradation path in the photocatalytic process, and an electron paramagnetic resonance (EPR) radical trapping experiment was conducted to unveil the reactive oxygen species involved in the system. Combining the results obtained, the synergistic effect in the enhancement of photocatalysis between NCDs and yolk-shell ZnFe2O4 was schematically proposed.
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We investigate the dynamics of a damped harmonic oscillator with delayed feedback near zero eigenvalue singularity. We perform a linearized stability analysis and multiple bifurcations of the zero solution of the system near zero eigenvalue singularity. Taking the time delay as the bifurcation parameter, the presence of steady-state bifurcation, Bogdanov-Takens bifurcation, triple zero, and Hopf-zero singularities is demonstrated. In the case when the system has a simple zero eigenvalue, center manifold reduction and normal form theory are used to investigate the stability and the types of steady-state bifurcation. The stability of the zero solution of the system near the simple zero eigenvalue singularity is completely solved.
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Algoritmos , Simulación por Computador , Dinámicas no Lineales , Oscilometría/métodosRESUMEN
Perovskite oxides are highly promising electrodes for oxygen-ion-intercalation-type supercapacitors owing to their high oxygen vacancy concentration, oxygen diffusion rate, and tap density. Based on the anion intercalation mechanism, the capacitance is contributed by surface redox reactions and oxygen ion intercalation in the bulk materials. A high concentration of oxygen vacancies is needed because it is the main charge carrier. In this study, we propose a B-site cation-ordered Ba2Bi0.1Sc0.2Co1.7O6-δ as an electrode material with an extremely high oxygen vacancy concentration and oxygen diffusion rate. A maximum capacitance of 1050 F g-1 was achieved, and a high capacitance of 780 F g-1 was maintained even after 3000 charge-discharge cycles at a current density of 1 A g-1 with an aqueous alkaline solution (6 M KOH) electrolyte, indicating an excellent cycling stability. In addition, the specific volumetric capacitance of Ba2Bi0.1Sc0.2Co1.7O6-δ reaches up to 2549.4 F cm-3 based on the dense construction and high tap density (3.2 g cm-3). In addition, an asymmetric supercapacitor was constructed using activated carbon as a negative electrode, and it displayed the highest specific energy density of 70 Wh kg-1 at the power density of 787 W kg-1 in this study.
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Water-stable and active metal organic frameworks (MOFs) are important materials for mitigation of water contaminants via adsorption and catalytic reactions. In this study, a highly water-stable Co-based MOF, namely bio-MOF-11-Co, was synthesized by a simplified benign method. Moreover, it was used as a catalyst in successful activation of peroxymonsulfate for catalytic degradation of sulfachloropyradazine (SCP) and para-hydroxybenzoic acid (p-HBA) as representatives of pharmaceuticals and personal care products, respectively. The bio-MOF-11-Co showed rapid degradation of both p-HBA and SCP and could be reused multiple times without losing the activity by simply water washing. The effects of catalyst and PMS loadings as well as temperature were further studied, showing that high catalyst and PMS loadings as well as temperature produced faster kinetic degradation of p-HBA and SCP. The generation of highly reactive and HO radicals during the degradation was investigated by quenching tests and electron paramagnetic resonance. A plausible degradation mechanism was proposed based on the functionalities in the bio-MOF-11-Co. The availability of electron rich nucleobase adenine reinforced the reaction kinetics by electron donation along with cobalt atoms in the bio-MOF-11-Co structure.
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Restauración y Remediación Ambiental/métodos , Estructuras Metalorgánicas/química , Parabenos/química , Peróxidos/química , Preparaciones Farmacéuticas/química , Sulfaclorpiridazina/química , Contaminantes Químicos del Agua/química , Adsorción , Catálisis , Cobalto/química , Electrones , Agua/químicaRESUMEN
This work reported that novel highly oriented and vertically aligned stoichiometric copper- and zinc-based ferrites, i.e., Cu0.5Zn0.5Fe2O4 quantum dots (QDs) anchored with TiO2 nanotube array electrode (NAE) composites, with n-n nano-heterojunctions and highly effective simulated solar light harvesting could be successfully achieved via electrochemical anodization followed by a vacuum-assisted impregnation strategy. It has been observed that Cu0.5Zn0.5Fe2O4 QDs/TiO2 NAE composites exhibit distinctly enhanced visible light photoelectrocatalytic (PEC) performance toward the degradation of typical pollutants including sulfamethoxazole (SMX) and methylene blue (MB) as compared to that of pristine TiO2 NAEs, which can be attributed to the synergistic effect of heterostructures with strong interfacial interaction and abundant 1D nanotube array structures to facilitate efficient spatial charge separation and interfacial transfers. The cocatalyst-anchoring of ternary oxides with derived spinel crystal structures onto nanotube arrays forming novel nanocomposites have obviously achieved remarkably enhanced photoelectrochemical (PE) conversion efficiencies, up to a dedicated value of 3.75%, under visible light irradiation as compared to that of 0.88% for aligned standalone TiO2 NAEs. Transient absorption spectroscopy quantitatively indicated long-lived photo-holes with lifetimes exceeding 72.23 µs generated among Cu0.5Zn0.5Fe2O4 QDs/TiO2 NAE nanocomposites. Electron spinning resonance (ESR) demonstrated that more ËO2- species derived from molecular uptake played the predominant role in the PEC oxidations of SMX and MB species. Moreover, the binding energy of the onset edge (Evf) and Fermi level (Ef) of Cu0.5Zn0.5Fe2O4 QDs/TiO2 NAEs indicated that Cu0.5Zn0.5Fe2O4 QDs modification could considerably enhance the visible light harvesting and adsorption properties of TiO2 NTs. Furthermore, Cu0.5Zn0.5Fe2O4 QDs/TiO2 NAEs achieved up to 50% PEC degradation efficiency and 52.4% COD removal with regard to practical textile wastewater when irradiated by simulated sunlight. This work has provided new insights into the molecular tailing and coupling of multiple spinels with TiO2 NTs possessing remarkable visible light harvesting and sensitization characteristics, which would offer a prospective strategy toward designing highly efficient and easily recyclable photocatalytic materials for environmental remediation and solar energy utilizations and conversions both simultaneously and standalone.
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Volatile organic compounds (VOCs) are the major pollutants in indoor air, which significantly impact indoor air quality and thus influencing human health. A long-term exposure to VOCs will be detrimental to human health causing sick building syndrome (SBS). Photocatalytic oxidation of VOCs is a cost-effective technology for VOCs removal compared with adsorption, biofiltration, or thermal catalysis. In this paper, we review the current exposure level of VOCs in various indoor environment and state of the art technology for photocatalytic oxidation of VOCs from indoor air. The concentrations and emission rates of commonly occurring VOCs in indoor air are presented. The effective catalyst systems, under UV and visible light, are discussed and the kinetics of photocatalytic oxidation is also presented.