Heterogeneous Photocatalysis Research Articles

Carbazole-Based Imine-Linked Covalent Organic Framework for Efficient Heterogeneous Photocatalysis

Carbazole-Based Imine-Linked Covalent Organic Framework for Efficient Heterogeneous Photocatalysis

Effect of detonation spray regimes on photocatalytic activity of Ti-TiO2 coatings

The influence of the regimes of detonation spraying the Ti-TiO2 based coatings on its photocatalytic properties is studied. The spray distance and the speed of passage of the detonation gun are varied when the coatings are applied. The microstructure and phase composition are studied. It is found that proportion of rutile prevails over the other phases in all samples obtained under all spray regimes used. The kinetics of photocatalytic reaction basing on Langmuir-Hinshelwood model of heterogeneous photocatalysis is analyzed. The photocatalytic activity and the rate constant of photocatalytic reaction of the coatings decrease with an increase in the spray distance. New equation describing the dependence observed is proposed. The decrease in the rate constant occurs according to a power law. The photocatalytic activity and the rate constant of the photocatalytic reaction of coatings increase with an increase in the rutile percentage. New equation describing such dependence is proposed. The increase occurs according to an exponential law. The photocatalytic rate constant depends on the speed of passage accordingly with a parabolic law.

Removal of Emerging Organic Pollutants by Zeolite Mineral (Clinoptilolite) Composite Photocatalysts in Drinking Water and Watershed Water

One of the most challenging problems for people around the world is the lack of clean water. In the past few decades, the massive discharge of emerging organic pollutants (EOPs) into natural water bodies has exacerbated this crisis. Considerable research efforts have been devoted to removing these EOPs due to their biotoxicity at low concentrations. Heterogeneous photocatalysis via coupling clay minerals with nanostructured semiconductors has proven to be an economical, efficient, and environmentally friendly technology for the elimination of EOPs in drinking water and watershed water. Natural zeolite minerals (especially clinoptilolites) are regarded as appropriate supports for semiconductor-based photocatalysts due to their characteristics of having a low cost, environmental friendliness, easy availability, co-catalysis, etc. This review summarizes the latest research on clinoptilolites used as supports to prepare binary and ternary metal oxide or sulfide semiconductor-based hybrid photocatalysts. Various preparation methods of the composite photocatalysts and their degradation efficiencies for the target contaminants are introduced. It is found that the good catalytic activity of the composite photocatalyst could be attributed to the synergistic effect of combining the clinoptilolite adsorbent with the semiconductor catalyst in the heterogeneous system, which could endow the composites with an excellent adsorption capacity and produce more e−/h+ pairs under suitable light irradiation. Finally, we highlight the serious threat of EOPs to the ecological environment and propose the current challenges and limitations, before putting the zeolite mineral composite photocatalysts into practice. The present work would provide a theoretical basis and scientific support for the application of zeolite-based photocatalysts for degrading EOPs.

Boosting Gas-Phase TiO2 Photocatalysis with Weak Electric Field Strengths of Volt/Centimeter.

Among semiconductor nanomaterials, titanium dioxide is at the forefront of heterogeneous photocatalysis, but its catalytic activity greatly suffers from the loss of photoexcited charge carriers through deleterious recombination processes. Here, we investigate the impact of an external electric field (EEF) applied to conventional P25 TiO2 nanopowder with or without Au nanoparticles (NPs) to circumvent this issue. The study of two redox reactions in the gas phase, water splitting and toluene degradation, reveals an enhancement of the photocatalytic activity with rather modest electric fields of a few volt/centimeters only. Such an improvement arises from the electric-field-induced quenching of the green emission in anatase, allowing the photoexcited charge carriers to be transferred to the adsorbed reactants instead of pointless radiative recombinations. Applying an EEF across a trap-rich metal oxide material, such as TiO2, which, when impregnated with Au NPs, leads, respectively, to 12- and 6-fold enhancements in the production of hydrogen and the oxidation of toluene for an electric field of 8 V/cm, without any electrolysis, is a simple and elegant strategy to meet higher photocatalytic efficiencies.

Recent advances on the treatment of oilfield-produced water by advanced oxidation processes: A review

ABSTRACT Despite the advancements in alternative fuels and energy sources, there continues to be a significant global dependence on oil production and extraction. A substantial volume of oilfield-produced water (OPW) is generated during the production and extraction processes of oil fields. Recurrent OPW treatments encountered significant challenges in addressing this particular type of wastewater. Advanced oxidation processes (AOPs) are regarded as a promising alternative approach for the degradation of recalcitrant organic compounds in the OPW. This review focuses on the characterization of OPW. The treatment of organic pollutants in wastewater using AOPs, such as ozonation, Fenton oxidation-based processes, heterogeneous photocatalysis, and persulfate oxidation, is comprehensively reviewed in terms of their efficiency for pollutant degradation. The primary challenges in this field and the future directions for development are proposed, with the aim of providing a valuable reference for achieving highly effective treatment of OPW.

High-Speed Circulation Flow Platform Facilitating Practical Large-Scale Heterogeneous Photocatalysis

High-Speed Circulation Flow Platform Facilitating Practical Large-Scale Heterogeneous Photocatalysis

Recent Advances in Advanced Oxidation Processes for Degrading Pharmaceuticals in Wastewater—A Review

A large variety of pharmaceutical compounds have recently been detected in wastewater and natural water systems. This review highlighted the significance of removing pharmaceutical compounds, which are considered indispensable emerging contaminants, from wastewater and natural water systems. Various advanced oxidation processes (AOPs), including UV-H2O2, Fenton and photo-Fenton, ozone-based processes, photocatalysis, and physical processes, such as sonolysis, microwave, and electron beam irradiation, which are regarded as the most viable methods to eliminate different categories of pharmaceutical compounds, are discussed. All these AOPs exhibit great promising techniques, and the catalytic degradation process of the emerging contaminants, advantages, and disadvantages of each technique were deliberated. Heterogeneous photocatalysis employing metal oxides, particularly anatase TiO2 nanoparticles as catalysts activated by UV light irradiation, was reviewed in terms of the electron–hole separation, migration of the charge carriers to the catalyst surfaces, and redox potential of the charge carriers. This brief overview also emphasized that anatase TiO2 nanoparticles and TiO2-based nanomaterials are promising photocatalysts, and a combination of photocatalysis and other AOPs enhanced photocatalytic degradation efficiency. Finally, the challenges of applying anatase TiO2-based photocatalysis in environmental remediation and wastewater treatments to degrade pharmaceutical compounds, including mass spectroscopic analysis and a biological activity test of by-products of the emerging contaminants resulting from photocatalysis, are summarized.

Detailed Insight into Photocatalytic Inactivation of Pathogenic Bacteria in the Presence of Visible-Light-Active Multicomponent Photocatalysts.

The use of heterogeneous photocatalysis in biologically contaminated water purification processes still requires the development of materials active in visible light, preferably in the form of thin films. Herein, we report nanotube structures made of TiO2/Ag2O/Au0, TiO2/Ag2O/PtOx, TiO2/Cu2O/Au0, and TiO2/Cu2O/PtOx obtained via one-step anodic oxidation of the titanium-based alloys (Ti94Ag5Au1, Ti94Cu5Pt1, Ti94Cu5Au1, and Ti94Ag5Pt1) possessing high visible light activity in the inactivation process of methicillin-susceptible S. aureus and other pathogenic bacteria-E. coli, Clostridium sp., and K. oxytoca. In the samples made from Ti-based alloys, metal/metal oxide nanoparticles were formed, which were located on the surface and inside the walls of the NTs. The obtained results showed that oxygen species produced at the surface of irradiated photocatalysts and the presence of copper and silver species in the photoactive layers both contributed to the inactivation of bacteria. Photocatalytic inactivation of E. coli, S. aureus, and Clostridium sp. was confirmed via TEM imaging of bacterium cell destruction and the detection of CO2 as a result of bacteria cell mineralization for the most active sample. These results suggest that the membrane ruptures as a result of the attack of active oxygen species, and then, both the membrane and the contents are mineralized to CO2.

Nitrate radical formation and reaction with limonene by TiO2 photocatalysis: A kinetic study

The oxidative cleavage and the epoxidation of the endocyclic double bond of limonene can be performed in irradiated suspensions of TiO2 because of the formation of nitrate radical species deriving from the hole-induced oxidation of nitrate ions. The reaction is boosted by electron acceptors such as silver ions or in the presence of silver nanoparticles at the surface of TiO2. A thorough kinetic analysis of the reaction performances under several experimental conditions provided a set of kinetic constants, which characterise the elementary steps of this complex reaction. In particular, for the first time an evaluation of the kinetics of the formation of nitrate radicals in heterogeneous photocatalysis has been provided. Moreover, the effect of silver ions in solution and of silver nanoparticles at the surface of TiO2 could be quantitatively estimated. The developed set of kinetic equations satisfactorily predict the experimental data under several experimental conditions and can be used as the starting point of reactor design activities, in view of a future scale-up of the process. Moreover, the successful fitting of the model corroborates the proposed reaction mechanism, and provides fundamental insights on the elementary reaction steps.

Kinetics of Decolorization of Reactive Textile Dye via Heterogeneous Photocatalysis Using Titanium Dioxide

The textile industry is known for its excessive water consumption and environmental impact. One of the major challenges it faces is managing pollution generated by dyes, particularly bifunctional dyes, such as sumireact supra yellow s-hbu, with a red appearance and sumifix supra lemon-yellow e-xf, with a yellow appearance. This study aimed to investigate the decolorization kinetics of synthetic solutions of said bifunctional dyes, which comprise triazine and vinylsulfon. We conducted various tests, including modifications of pH, the addition of TiO2 P-50 nanoparticles, exposure to solar radiation, limited contact with oxygen, and eolic agitation. The initial solutions had a concentration of 1000 ppm of textile dye. The study showed that the reaction order for the “red” solutions in the R6 and R9 reactors and all the yellow solutions was ½. The concentration of nanoparticles and pH had a significant impact on the reaction rate. The yellow solutions with a concentration of 800 ppm and pH levels of 3.15, 4.13, and 2.25 demonstrated 100% color discoloration, followed by solutions with a concentration of 400 ppm and pH levels of 3.15, 2.25, and 4.13. The analysis of variance confirmed the reaction rate constants for the yellow solutions and emphasized the significance of pH in this process.

Mesoporous copper aluminate-modified tungsten trioxide nanocomposite for boosted photocatalytic H2 generation employing visible light exposure

Semiconductor photocatalysis is the most effective technology for producing “green” hydrogen, achieving sustainability to a high extent. Regrettably, the speedy re-pairing rate of photo-excited holes and electrons still represents the greatest challenge for developing heterogeneous photocatalysis. This contribution used a mixed surfactant-assisted hydrothermal route followed by an impregnation approach to construct mesoporous CuAl2O4/WO3 p-n heterojunction. Furthermore, a detailed investigation of the impact of CuAl2O4 (3.0–12.0 wt%) loading on the phase structure, surface composition, optical, textural, photo-caused charge carriers' separation ability, and photoactivity of WO3 material was provided. It was demonstrated that the constructed heterojunctions displayed improved visible-light-absorbance potential and photo-excited charge carriers' separation owing to reducing the bandgap to 2.15 eV and prompting charges' separation and transfer through forming step (S)-scheme p-n heterojunction. The 9.0 wt% CuAl2O4-loaded tungsten trioxide (1.2 g L–1) generated ∼ 18-fold as much hydrogen as the non-modified WO3 material. Additionally, when the photocatalyst dosage was raised from 1.2 to 1.8 g L–1, the H2 generation was augmented by 1.24 times with interesting sustainability through five consecutive cycles. This study opens the door to using this highly efficient, powerful, and sustainable material to solve numerous daily issues.

Transition metals-doped g-C3N4 nanostructures as advanced photocatalysts for energy and environmental applications

Graphitic carbon nitride (g–C3N4)–based heterostructured photocatalysts have received significant attention for its potential applications in the treatment of wastewater and hydrogen evolution. The utilization of semiconductor materials in heterogeneous photocatalysis has recently received great attention due to their potential and eco-friendly properties. Doping with metal ions plays a crucial role in altering the photochemical characteristics of g-C3N4, effectively enhancing photoabsorption into the visible range and thus improving the photocatalytic performance of doped photocatalysts. As an emerging nanomaterial, nanostructured g-C3N4 represents a visible light-active semiconducting photocatalyst that has attracted significant interest in the photocatalysis field, particularly for its practical water treatment applications. To the best of our knowledge, investigations of functionalized photocatalytic (PC) materials on 3d transition metal-doped g-C3N4 remain unexplored in the existing literature. g-C3N4 based heterohybrid photocatalysts have demonstrated excellent reusability, making them highly promising for wastewater treatment applications. This paper describes the overview of numerous studies conducted on the heterostructured g-C3N4 photocatalysts with various 3d metals. Research studies have revealed that the introduction of element doping with various 3d transition metals (e.g., Ti, Mn, Fe, Co, Ni, Cu, Zn, etc.) into g-C3N4 is an efficient approach to enhance degradation efficacy and boost photocatalytic activity (PCA) of doped g-C3N4 catalysts. Moreover, the significance of g-C3N4 heterostructured nanohybrids is highlighted, particularly in the context of wastewater treatment applications. The study concludes by providing insights into future perspectives in this developing area of research, with a specific focus on the degradation of various organic contaminants.

Metal-Free Heterogeneous Photocatalysis for Carbocarboxylation of Alkenes: Efficient Synthesis of γ-Amino Carboxylic Derivatives.

A metal-free heterogeneous protocol is established herein for the synthesis of value-added γ-amino acid scaffolds via carbocarboxylation of alkenes with CO2 and alkylamines under visible light irradiation. The protocol shows broad substrate scope under mild reaction conditions and good stability of the catalyst for recycle tests. Moreover, the methodology could be feasible to the late-stage derivatization of several natural products, enriching the chemical arsenal for practical application.

Photocatalytic Degradation Using TiO2 P25: A Comparative Study for Different Textile Dyes

The photocatalytic degradation of textile dyes using metallic oxides has been extensively studied due to the remarkable results. This promising approach offers a more sustainable alternative for treating textile effluents contaminated with dyes and other chemicals, intending to mitigate the environmental impact caused by the textile industry. In this context, this study aimed to investigate the degradation of different classes of synthetic dyes used in industry through the heterogeneous photocatalysis process. For this purpose, TiO2 P25 dispersed in an aqueous dye medium exposed to an isolated source of artificial UV light was used. The significance of this research lies in understanding photodegradation phenomena and studying heterogeneous catalysis mechanisms applied to the degradation of textile dyes. Furthermore, the importance of sustainability in the textile industry is highlighted, emphasizing the need for new solutions to reduce waste emissions. This study contributes significantly to understanding the degradation of textile dyes through photodegradation, providing detailed information on the reaction processes and key factors influencing the efficiency of TiO2-catalyzed degradation. The results demonstrate real application potential and support sustainable strategies for treating textile effluents, aiming to reduce the environmental impact caused by dyes.

Facile construction of multifunctional xNiCo2O4/BiVO4 heterojunction with accelerated charge transfer for efficient photocatalytic treatment of Cr (VI), MB and TC under visible light

The release of industrial effluents, comprising of organic dyes, antibiotics, and heavy metals poses substantial environmental and ecological threats. Among the different approaches, the utilization of heterogeneous photocatalysis based on semiconducting metal oxides is of paramount important to removal of organic ( MB dye and TC antibiotic) and inorganic pollutants ( Cr (VI) ) in wastewater. In this work, a new approach for creating type-II heterojunction photocatalysts named xNiCo2O4/BiVO4 or BNC is suggested. The as-prepared samples were thoroughly examined by means of several sophisticated analytical tools to investigate their physicochemical properties. These composites were utilized in the decomposition of MB dye, TC drug and the reduction of Cr (VI) under visible light irradiation. According to the findings, the creation of type-II heterojunction at BiVO4–NiCo2O4 interface greatly improved charge transportation while successfully preventing electron-hole recombination. Among the various composites studied, BNC-2 demonstrated an enhanced photocatalytic activity towards degradation of MB and TC, which were found to be 91 % over a period of 150 min and 95 % within only 60 min, respectively. Moreover, the photocatalytic reduction of Cr (VI) was accomplished 96 % within just 25 min. Additionally, it is discovered that BNC-2 displayed promising photostability and recyclability with a retention of >90 % after five consecutive cycles. The enhanced photocatalytic activity of BNC-2 is evidently attributed to the expedited separation and transfer of charges, as proven by photocurrent measurement, photoluminescence and electrochemical impedance spectroscopy analyses. Hence, the current amalgamation of NiCo2O4 and BiVO4 heterojunction composite has paved novel paths towards photocatalytic removal of organic as well as inorganic contaminants.

Heterogeneous Photocatalysis for Efficient Degradation of Lamivudine and Zidovudine Antiretroviral Drugs: Assessment Toxicological in Carrot and Tomato Seeds

Heterogeneous Photocatalysis for Efficient Degradation of Lamivudine and Zidovudine Antiretroviral Drugs: Assessment Toxicological in Carrot and Tomato Seeds

Synthesis of Cerium-Doped Zinc Oxide Nanocomposites and Their Application for Photocatalytic Degradation of Lambda-Cyhalothrin in Agricultural Runoff Under Natural Solar Irradiation

Heterogenous photocatalysis is one of the promising methods of degradation of organic pollutants in the environment. This study developed a suitable and efficient method for photocatalytic degradation of Lambda-cyhalothrin LCY pesticide using Ce–ZnO nanocomposites under natural solar irradiation. Ce–ZnO was synthesized using the coprecipitation method and was ascertained through structural characterization. The crystal structure and crystallite size, surface morphology, functional groups present, and the elemental composition of the synthesized nanocomposites were determined by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and energy dispersive X-ray spectroscopy (EDAX), respectively. The average crystallite size of the nanocomposites was found to be 31.42 nm. The photocatalytic degradation of LCY was conducted in batches to obtain and determine the optimal conditions for the degradation of the pesticide. It was found that at optimum conditions; 100 ppm LCY initial concentration, 20 mg dose of the photocatalyst, and 10–11 UV index, Ce–ZnO were found to degrade about 92% of the initial concentration of LCY after 3 h of exposure to solar irradiation. It was found that Ce–ZnO possesses high photocatalytic activity against LCY and the kinetic of the degradation was found to fit the pseudo-first-order kinetic model.

A Guide to Chemical Reactions Design in Carbon Nitride Photocatalysis

AbstractGraphitic carbon nitride semiconductors are inexpensive and reusable photocatalysts, which are actively studied in organic synthesis. Successful design of photocatalytic reactions is based on the next considerations. i) Thermodynamic feasibility of photoinduced processes, which involve transfer of electrons or electron‐proton couples. ii) Redox activity of reagents. iii) Reactivity of the open‐shell intermediates generated from the reagents. Herein, we summarize current understanding of how local chemical structure of graphitic carbon nitrides and their redox potentials are used to design photocatalytic reactions. This work intends to serve as a guideline for materials scientists, who are willing to apply their carbon nitride semiconductors in reactions involving organic substrates, and for organic chemists, who are interested to dive into heterogeneous carbon nitride photocatalysis.

Heterogeneous Photocatalytic Strategies for C(sp3)−H Activation

AbstractActivation of ubiquitous C(sp3)−H bonds is extremely attractive but remains a great challenge. Heterogeneous photocatalysis offers a promising and sustainable approach for C(sp3)−H activation and has been fast developing in the past decade. This Minireview focuses on mechanism and strategies for heterogeneous photocatalytic C(sp3)−H activation. After introducing mechanistic insights, heterogeneous photocatalytic strategies for C(sp3)−H activation including precise design of active sites, regulation of reactive radical species, improving charge separation and reactor innovations are discussed. In addition, recent advances in C(sp3)−H activation of hydrocarbons, alcohols, ethers, amines and amides by heterogeneous photocatalysis are summarized. Lastly, challenges and opportunities are outlined to encourage more efforts for the development of this exciting and promising field.

Heterogeneous Photocatalytic Strategies for C(sp3 )-H Activation.

Activation of ubiquitous C(sp3 )-H bonds is extremely attractive but remains a great challenge. Heterogeneous photocatalysis offers a promising and sustainable approach for C(sp3 )-H activation and has been fast developing in the past decade. This Minireview focuses on mechanism and strategies for heterogeneous photocatalytic C(sp3 )-H activation. After introducing mechanistic insights, heterogeneous photocatalytic strategies for C(sp3 )-H activation including precise design of active sites, regulation of reactive radical species, improving charge separation and reactor innovations are discussed. In addition, recent advances in C(sp3 )-H activation of hydrocarbons, alcohols, ethers, amines and amides by heterogeneous photocatalysis are summarized. Lastly, challenges and opportunities are outlined to encourage more efforts for the development of this exciting and promising field.