Photocatalytic Performance Research Articles

An experimental and theoretical validation of dual role of Fe on improving the photocatalytic performance of doped mixed phase titania

The present work proposes a strategic approach of using Fe doping to form a mixed-phase TiO2 direct Z-scheme catalyst at low onset temperature. The doping-induced modifications are explained from the experimental and theoretical viewpoint. Fe-doped Z-scheme-based mixed-phase TiO2 at optimal calcination temperature (TiFe-400) exhibits maximum photon absorption and reduces charge carrier recombination, enhancing photocatalytic and PEC performance. TiFe-400 has the highest rate constant for the degradation of MB (0.084 min−1 under solar irradiation) and showed exceptional photooxidation current (0.8 mA, 1.3 V vs Ag/AgCl). The Z-scheme formation significantly inhibits the recombination of photocarriers, resulting in a directed migration of charge carriers to the high redox potential mixed-phase TiO2. This migration is validated by identifying the primary reactive species participating in the photocatalytic process. This work, demonstrating both experimental and theoretical approaches, may provide valuable insight into designing stable and inexpensive catalysts for dual applications on an industrial scale.

Rational design of Z-scheme configured polymeric carbon nitride-decorated ZnWO4 nanofibers for enhanced visible-light-driven photodegradation of antibiotics

In this study, a Z-scheme heterostructure was meticulously engineered between zinc tungstate (ZnWO4) nanofibers and polymeric carbon nitride (PCN) nanosheets to augment the photocatalytic degradation of tetracycline (TC) under visible light irradiation. A cohesively integrated PCN/ZnWO4 photocatalyst structure was synthesized through an in-situ gas-solid reaction. The quantity and spatial distribution of PCN nanosheets were modulated by fine-tuning the gas precursor and reaction parameters. Relative to pristine ZnWO4 nanofibers and PCN photocatalysts, the distinct three-dimensional PCN/ZnWO4 heterostructure manifests a notable enhancement in photocatalytic performance, attributed to its plethora of active sites and a Z-scheme configuration that bolsters charge separation efficiency, achieving a tetracycline degradation rate of 95.4% upon exposure to simulated sunlight for 160 minutes. The employment of gas-solid reaction as a design paradigm pioneers a fresh paradigm in the strategic assembly of Z-scheme heterostructured photocatalysts, thereby illuminating a promising pathway for advancements in environmental remediation technologies.

Enhanced photocatalytic performance of TiO2 with tunable oxygen vacancies induced by H2/N2 mixture treatment

Surface treatment can effectively modulate the surface properties of a photocatalyst to hasten the separation and transfer of photoinduced charges, ultimately achieving high photocatalytic performance. Herein, surface treatment of anatase-phase TiO2 prepared by a hydrothermal method was performed under H2/N2 mixed atmosphere. The experimental results demonstrate that roasting TiO2 in a H2/N2 atmosphere can effectively reduce partial Ti4+ to Ti3+, thereby facilitating the production of tunable oxygen vacancies (OVs) by disrupting Ti-O-Ti bonds. OVs can construct defective energy levels to bring about a decrease in the bandgap of TiO2 and an extension of light absorption range. Moreover, OVs remarkedly improve the separation of photoinduced charges of TiO2 and accelerate the photocatalytic reaction as active sites. The photocatalytic experimental results demonstrate that TiO2 exhibits the highest performance when roasting TiO2 in a H2/N2 atmosphere for 2 h, and the photocatalytic degradation rate constant of rhodamine B (RhB) and tetracycline (TC) on this sample under simulated solar light irradiation is 2.24 and 1.11 times higher than that on the reference TiO2, respectively. These findings provide valuable insights for designing highly efficient photocatalysts for effective water pollution treatment.

Enhanced photocatalytic performance of (Mg, Cu) Dual-Doped ZnS nanosheets for Solar-Driven water treatment and embedded with PVA polymer membrane for reusability

Photocatalysis uses semiconductor materials to solar energy effectively purify to water by eliminating pollutants. Organic Dye degradation serves as a standard to assess the photocatalytic effects of the materials. In this study Mg, Cu dual-doped ZnS nanosheets were synthesized using the coprecipitation method. The impact of the concentration on the structural, morphology, optical, and degradation efficiency was investigated with XRD, XPS, TEM with EDAX, and UV spectroscopy. The pure ZnS and Zn0.98-xCu0.02MgxS (x = 0, 0.01, 0.02) (ZCM1, ZCM2, ZCM3, and ZCM4) nanosheets, exhibited cubic structure with high phase purity. The average crystalline size was calculated as 1.66, 1.60, 1.45, and 1.47 nm for the ZCM1, ZCM2, ZCM3, and ZCM4 nanosheets, respectively. TEM analysis revealed the presence of crumpled nanosheets. The bandgap of the ZCM1, ZCM2, ZCM3, and ZCM4 nanosheets were 3.99, 3.78, 4.03, and 4.09 eV respectively. This study investigated the photocatalytic activity of crystal violet dye when exposed to natural sunlight irradiation. Notably, ZCM3 nanosheets exhibited a high degradation rate of 99 % over 120 min under sunlight. Furthermore, the proposed dye degradation mechanism, effect of dosage, effect of dye variation, reusability, scavenging activity, and hemolytic activity were comprehensively discussed. The nanosheets embedded with the Polyvinyl alcohol (PVA) polymer membrane for reusability.

Visible-light photocatalytic performance of SrTiO3 nanoparticles modified with cobalt.

In this article, an experimental study on the photocatalytic performance of SrTi1-yCoyO3 nanoparticles (with y = 0.0, 0.03, 0.06, and 0.09) synthesized by the Pechini-type sol-gel method is presented. The crystalline structure analysis revealed that all the samples exhibited the cubic perovskite phase of SrTiO3. In particular, the SrTi0.91Co0.09O3 sample was found to consist of rough spherical-like particles with an average size of 26 ± 0.5 nm. Cobalt ions with 2+ and 3+ oxidation states are responsible for modifying the electronic band structure of the semiconductor and a narrowing of optical band gap from 3.1 to 1.08 eV. The resulting Co-doped SrTiO3 nanoparticles exhibited photocatalytic activity under visible light due to their enhanced light absorption, effective charge transport and effective surface chemisorption. In particular, the SrTi0.91Co0.09O3 sample exhibited the highest photocatalytic activity with 91% degradation efficiency of methylene blue dye within 120 min of simulated solar irradiation.

G-C3N4 coupled with GO accelerates carrier separation via high conductivity for photocatalytic MB degradation

Graphitic carbon nitride (g-C3N4) is widely utilized in photocatalysis due to its responsiveness to visible light, low cost, and non-toxicity. However, its efficiency is limited by factors such as the rapid recombination of photogenerated electron-hole pairs, slow electron transfer rates, and a limited number of active surface sites. In this study, g-C3N4 was synthesized through thermal polymerization, and varying amounts of graphene oxide (GO) were incorporated via physical blending to fabricate composite photocatalysts. The results indicated that the incorporation of GO not only increased the specific surface area and modified the pore size distribution of g-C3N4 but also affected the heptazine ring structure through chemical bonding, thereby enhancing the density of active sites. Photocatalytic degradation experiments with methylene blue (MB) indicated that g-C3N4 containing 2% GO exhibited photocatalytic activity 2.84 times greater than that of pristine g-C3N4. Kinetic simulations indicated that the Kapp value for the 2% GO-g-C3N4 composite was 0.00469min-1, which is 4.34 times higher than that of pure g-C3N4 (0.00108min-1). Furthermore, this composite maintained high photocatalytic activity after four cycles of reuse. An analysis of the photocatalytic degradation mechanism revealed that the incorporation of GO effectively promoted the separation and transfer of photogenerated electron-hole pairs, enhanced photocurrent density, and improved carrier separation efficiency. Electron spin resonance (ESR) and free radical scavenging experiments confirmed that the primary active species involved in the degradation of MB by the composite photocatalyst were ·O2- and h+. This study presents a novel approach for enhancing the photocatalytic performance of g-C3N4 by modifying its electronic structure and surface properties.

Kinetic Insights into Solar-Assisted Fabrication and Photocatalytic Performance of CoWO4/NCW Heterostructure

This work studies the kinetic model for the solar-driven fabrication of CoWO4/NCW heterostructure photocatalysts and investigates their enhanced photocatalytic degradation activity. The synthesis of CoWO4/NCW, its characterization, and the kinetic aspects of photocatalytic degradation under solar light. New nanocomposite prepared from Nano cellulose (NCW) by hydrolysis cotton waste (CW) by nitric acid and cobalt tungstate (CoWO4) prepared from sodium tungstate and cobalt chloride by wet chemical method and characterized through XRD, FTIR, EDX, and FE-SEM analyses. The composite's performance in organic oxidation from refinery wastewater (RWW) was evaluated under solar light. The high removal ratio was 97.4% for organic pollutants (OP) in refinery wastewater. The results indicate that the heterostructure exhibits improved photocatalytic performance compared to individual components, which kinetics model was the best to represent the photocatalytic degradation of organic pollutants from oily wastewater over the heterostructure CoWO4/NCW catalyst. Add future applications of this finding in the relevant industries. Copyright © 2024 by Authors, Published by BCREC Publishing Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0).

Modulation of the Microstructure and Enhancement of the Photocatalytic Performance of g-C3N4 by Thermal Exfoliation

This work explores the impact of reaction temperature during thermal exfoliation treatment of bulk-g-C3N4 in the air atmosphere on the structure and performance of the resulting CN photocatalyst. The analysis conducted using XRD, FT-IR, XPS, SEM, and elements mapping tests, illustrated an increase in nitrogen-vacancy and oxygen content on the surface of the CN photocatalyst, resulting in a porous and sparse structure, changes in crystal size, and improved visible light absorption performance. The photocatalytic reduction experiments of hexavalent chromium (Cr(VI)) showed that the CN-540 showed the highest reduction rate of 96.9%, with a reaction rate constant 6.21 times that of bulk-g-C3N4. After 100 min of illumination, the photocatalytic degradation rates of CN-540 for TC-HCl and RhB were 66.7% and 60.6%, respectively. The TOC test results indicated mineralization rates of 51.5% for TC-HCl and 46.6% for RhB. Room temperature fluorescence spectroscopy (PL), transient photocurrent response (TPC), and electrochemical impedance spectroscopy (EIS) measurements confirmed the excellent photogenerated charge carrier separation and transport efficiency of CN-540. The photocatalytic mechanism for reducing Cr(VI) by CN-540 was elucidated based on the active species •OH and •O2– and Mott-Schottky (M-S) tests. This study provides experimental data for optimizing the photocatalytic performance of g-C3N4 and paves a new way for developing efficient photocatalysts. Copyright © 2024 by Authors, Published by BCREC Publishing Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0).

Enhanced photocatalytic performance of magnetically reclaimable N-doped g-C3N4/Fe3O4 nanocomposites for efficient tetracycline degradation

The growing environmental challenge posed by the persistence of tetracycline (TC) antibiotics in natural waters is of increasing concern. To address this, there is an imperative need for advanced methods to mitigate TC residues. Herein, we demonstrate the preparation of nitrogen-doped graphitic carbon nitride integrated with magnetic Fe3O4 (N-g-CN/Fe3O4) composites, showcasing narrow band gaps optimized for TC degradation. These advanced materials, conceived through a thermal poly-condensation approach, utilize citric acid and melamine as precursors for nitrogen and g-CN, respectively. These composites exhibit a face-centered cubic architecture, with particle dimensions between 8 to 12 nm and encompassing both meso and microporous structure. The results of the Brunauer–Emmett–Teller analysis indicated specific surface areas of 6.73 m²/g for g-CN, 69.80 m²/g for N-g-CN, 62.55 m²/g for Fe3O4, and 148.32 m²/g for N-g-CN/Fe3O4. These values demonstrate an increase in surface area upon the incorporation of heteroatom of nitrogen and Fe3O4, into the g-CN matrix, thus influence the photocatalytic performance. Under solar light exposure, the synthesized photocatalysts demonstrated photocatalytic activity with a degradation efficiency of 94.16 % within 120 min. Specifically, the N-g-CN/Fe3O4 (22.5 %) composites exhibited remarkable photocatalytic efficiency due to the narrow band gap energy between N-g-CN and Fe3O4, enhanced light absorption in the visible range, and effective charge carrier separation and transportation to the pollutants. N-g-CN/Fe3O4 (22.5 %) composites demonstrated good recyclability (five cycles), magnetic sustainability, and stability for the degradation of TC and emerging pollutants from wastewater using photocatalysts. Similarly, FGCN composites exhibited good recyclability (five cycles), magnetic retrievability, and stability for degrading organic and emerging pollutants from wastewater through photocatalysis. This efficiency can be attributed to the harmonious combination of nitrogen doping, refined surface area, and the natural heterojunction between N-g-CN and Fe3O4.

Graphdiyne‐Based Nickel–Cobalt Bimetallic Sulfide Cocatalyst for Efficient Photocatalytic Hydrogen Evolution

Initially, CoNiSx is synthesized on the graphdiyne (GDY) surface through a precipitation method, followed by the straightforward physical stirring approach to attach CoNiSx/GDY to the maple leaf CdS. This synthesis method significantly mitigates the accumulation of CoNiSx/GDY and concurrently augments the count of sites that are active for generating hydrogen. This three‐phase composite demonstrates exceptional performance in the area of photocatalytic hydrogen production, achieving a hydrogen evolution rate of 15.37 mmol·h−1 g−1. The employment of various characterization methodologies and density functional theory calculations have demonstrated the formation of a Z‐scheme heterojunction forms between GDY and CdS. This discovery indicates that the combination of GDY and CdS markedly improves the photogenerated carrier separation capability of the composite catalyst. The cocatalyst CoNiSx loaded on GDY effectively accelerates the electron transfer from the conduction band of GDY, thereby reducing the photogenerated carrier complexation of GDY. This phenomenon results in an increased quantity of photogenerated electron holes engaged in the redox reaction, ultimately achieving exceptional photocatalytic performance.

Accelerating Small Electron Polaron Dissociation and Hole Transfer at Solid-Liquid Interface for Enhanced Heterogeneous Photoreaction.

In a photocatalysis process, quick charge recombination induced by small electron polarons in a photocatalyst and sluggish kinetics of hole transfer at the solid-liquid interface have greatly limited photocatalytic efficiency. Herein, we demonstrate hydrated transition metal ions as mediators that can simultaneously accelerate small electron polaron dissociation (via metal ion reduction) and hole transfer (through high-valence metal production) at the solid-liquid interface for improved photocatalytic pollutant degradation. Fe3+, by virtue of its excellent redox ability as a homogeneous mediator, enables the BiVO4 photocatalyst to achieve drastically increased photocatalytic degradation performance, up to 684 times that without Fe3+. The enhanced performance results from Fe(IV) species production (via Fe3+ oxidation) induced by dissociation of small electron polarons (via Fe3+ reduction), featuring an extremely low kinetic barrier (5.4 kJ mol-1) for oxygen atom transfer thanks to the donor-acceptor orbital interaction between Fe(IV) and organic pollutants. This work constructs a high-efficiency artificial photosynthetic system through synergistically eliminating electron localization and breaking hole transfer limitation at the solid-liquid interface for constructing high-efficiency artificial photosynthetic systems.

Regulation of Exciton Effects in Functionalized Conjugated Polymers by B‐N Lewis Pairs for Visible‐Light Photocatalysis

Strong excitonic effects are common in organic conjugated polymer semiconductors, severely hindering the generation of free charge carriers for conducting photocatalysis. Therefore, exploring new channels to modulate exciton dissociation in polymers is far‐reaching in facilitating photocatalysis. A series of B‐N Lewis pair functionalized conjugated polymers have been developed to minimize exciton effects by modulating charge transfer pathways. Theoretical studies have shown that introducing B‐N Lewis pairs can dramatically increase the distance of charge transfer (D index) and the amount of electron transfer and reduce the Coulomb attraction energy (EC), which contributes to breaking the equilibrium of the coexistence of excitons and charge carriers. Further experimental results show that the singlet excitons are efficiently dissociated into more free‐charge carriers under photoexcitation to participate in surface reactions. The optimized polymer PyPBM shows an exponential increase in photocatalytic hydrogen and hydrogen peroxide production performance by visible light illumination.

Regulation of Exciton Effects in Functionalized Conjugated Polymers by B-N Lewis Pairs for Visible-Light Photocatalysis.

Strong excitonic effects are common in organic conjugated polymer semiconductors, severely hindering the generation of free charge carriers for conducting photocatalysis. Therefore, exploring new channels to modulate exciton dissociation in polymers is far-reaching in facilitating photocatalysis. A series of B-N Lewis pair functionalized conjugated polymers have been developed to minimize exciton effects by modulating charge transfer pathways. Theoretical studies have shown that introducing B-N Lewis pairs can dramatically increase the distance of charge transfer (D index) and the amount of electron transfer and reduce the Coulomb attraction energy (EC), which contributes to breaking the equilibrium of the coexistence of excitons and charge carriers. Further experimental results show that the singlet excitons are efficiently dissociated into more free-charge carriers under photoexcitation to participate in surface reactions. The optimized polymer PyPBM shows an exponential increase in photocatalytic hydrogen and hydrogen peroxide production performance by visible light illumination.

General Synthesis of Single-Crystalline Ta2O5 Nanorods Towards Enhanced Photocatalytic H2 Production Activity.

As a potential candidate for photocatalytic H2 production from water splitting, Ta2O5 catalyst presents suitable conduction and valence band positions, but suffers from poor charge transfer ability, which seriously limits its photocatalytic performance enhancement. Here, a facile and eco-friendly hydrothermal method was developed for the fabrication of one-dimensional (1D) Ta2O5 nanorods using the freshly precipitated tantalic acids as the precursors. An oriented attachment mechanism was proposed for the growth of Ta2O5 nanorods. Moreover, the present synthetic approach was further extended to direct synthesis of nine kinds of alkaline tantalates and alkaline-earth tantalates nanostructures, suggesting its general applicability. A significant increase in activity in photocatalytic H2 production was revealed on 1D Ta2O5 nanorods. The improved photocatalytic H2 production activity of Ta2O5 nanorods was mainly attributed to its 1D nanorods structure with high crystallization and large specific surface areas as well as excellent charge transfer efficiency.

Microemulsion Templating Synthesis of Hierarchical Porous Ag‐Doped SiO2‐TiO2 Composites for Efficient Degradation of Noxious Methylene Blue Dye: Effect of Calcination Environment

AbstractWe report herein a dual function mesoporous structure of titanium oxide based porous carbon with large surface‐to‐volume ratios for efficient degradation of noxious methylene blue dye (MB) from an aqueous environment. The mesoporous photocatalysts is fabricated via direct template synthesis of highly ordered silica‐titania monolith doped with Ag0/Ag2O starting from a quaternary microemulsion liquid crystalline phase. The produced monoliths are subjected in‐situ to doping by growing silver, in the cubic cavities, and on the silica/titania structure's domain. This study investigated the efficiency of novel composite materials, consisting of silver‐doped silica‐titania (SiO2/TiO2), which is synthesized using the microemulsion templating approach. The photocatalytic performance of the synthesized composite in the photodegradation of MB has been studied. The procedure of photodegradation was employed to achieve decolorization of the cationic MB dye using visible light. The catalyst effectively achieved the decolorization of the dyed solution through the processes of adsorption and photodegradation. The composite consisting of SiO2, TiO2, and Ag2O at a ratio of 1 : 1:0.5, which underwent calcination in an air environment (AgOST), exhibited a removal efficiency of 99 % compared to its calcined state under argon (AgSTC).

Two-Dimensional Covalent Organic Frameworks with Carbazole-Embedded Frameworks Facilitate Photocatalytic and Electrocatalytic Processes

Catalytic technologies are pivotal in enhancing energy efficiency, promoting clean energy production, and reducing energy consumption in the chemical industry. The pursuit of novel catalysts for renewable energy is a long-term goal for researchers. In this work, we synthesized three two-dimensional covalent organic frameworks (COFs) featuring electron-rich carbazole-based architectures and evaluated their catalytic performance in photocatalytic organic reactions and electrocatalytic oxygen reduction reactions (ORRs). Pyrene-functionalized COF, termed as FCTD-TAPy, demonstrated excellent photocatalytic performance for amino oxidation coupling and showed a remarkable preference for substrates with electron-withdrawing groups (up to >99% Conv. and >99% Sel). Furthermore, FCTD-TAPy favored a four-electron transfer pathway during the ORR and exhibited favorable reaction kinetics (51.07 mV/dec) and a high turnover frequency (0.011 s−1). In contrast, the ORR of benzothiadiazole-based FCTD-TABT favored a two-electron transfer pathway, which exhibited a maximum double-layer capacitance of 14.26 mF cm−2, a Tafel slope of 53.01 mV/dec, and a hydrogen peroxide generation rate of 70.3 mmol g−1 h−1. This work underscores the potential of carbazole-based COFs as advanced catalytic materials and offers new insights into the design of metal-free COFs for enhanced catalytic performance.

Joint Electrons and Photons Transfer from Dual‐Functional WO3:Yb,Er to Zn0.5Cd0.5S for Efficient H2 Evolution

AbstractUtilization of the near‐infrared (NIR) light in the solar spectrum is critical for efficiency improvement of photocatalytic H2 evolution. However, common semiconductors have low response to the NIR light and narrow bandgap semiconductors have inappropriate redox potentials. Here, the study presents a new dual‐functional up‐conversion strategy in one sensitizer for promoting photocatalytic hydrogen production reactions by converting NIR light to visible light and high‐energy electrons simultaneously, via photon‐photon conversion and photo‐electronic process, respectively. Using WO3:Yb,Er as the sensitizer and Zn0.5Cd0.5S as the hydrogen evolution reaction catalyst, a photocatalytic hydrogen release rate of 24.3 mmol g−1 h−1 under simulated solar‐light has been achieved without using any co‐catalyst. After loading Ni2P as a co‐catalyst, the photocatalytic hydrogen production performance can be further improved to 41.3 mmol g−1 h−1 at 10 °C and 93.3 mmol g−1 h−1 under non‐temperature‐controlled conditions, exceeding most photocatalysts. This work offers a new strategy to improve the NIR light utilization of the solar‐light for promoting photocatalytic hydrogen generation through synergistic photo‐optical, photo‐electronic, and photo‐thermal effects.

Vinylene-Linked Donor-π-Acceptor Metal-Covalent Organic Framework for Enhanced Photocatalytic CO2 Reduction.

Intramolecular charge separation driving force and linkage chemistry between building blocks are critical factors for enhancing the photocatalytic performance of metal-covalent organic framework (MCOF) based photocatalyst. However, robust achieving both simultaneously has yet to be challenging despite ongoing efforts. Here we develop a fully π-conjugated vinylene-linked multivariate donor-π-acceptor MCOF (D-π-A, termed UJN-1) by integrating benzyl cyanides linker with multiple functional building blocks of electron-rich triphenylamine and electron-deficient copper-cyclic trinuclear units (Cu-CTUs) moieties, featuring with strong intramolecular charge separation driving force, extended conjugation degree of skeleton, and abundant active sites. The incorporation of Cu-CTUs acceptor with electron-withdrawing ability and concomitantly giant charge separation driving force can efficiently accelerate the photogenerated electrons transfer from triphenylamine to Cu-CTUs, revealing by experiments and theoretical calculations. Benefiting from the synergistically effect of D-π-A configuration and vinylene linkage, the highly-efficient charge spatial separation is achieved. Consequently, UJN-1 exhibits an excellent CO formation rate of 114.8 μmol g-1 in 4 h without any co-catalysts or sacrificial reagents under visible light, outperforming those analogous MCOFs with imine-linked (UJN-2, 28.9 μmol g-1) and vinylene-linked COF without Cu-CTU active sites (UJN-3, 50.0 μmol g-1), emphasizing the role of charge separation driving force and linkage chemistry in designing novel COFs-based photocatalyst.

Evaluating the Photocatalytic Activity of Green Synthesized Iron Oxide Nanoparticles

Water pollution from dyes is a major environmental challenge, demanding advanced materials for efficient degradation. In this study, we synthesized iron oxide nanoparticles (IONPs) using an aqueous extract of Senegalia catechu leaves and evaluated their photocatalytic activity in methylene blue (MB) dye degradation under sunlight irradiation. The IONPs were characterized by UV-visible spectroscopy (UV–vis), Fourier Transform Infrared Spectroscopy (FT-IR), X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), and Energy Dispersive X-ray Spectroscopy (EDS). XRD pattern showed a highly crystalline structure with an average crystallite size of 34.7 nm, while SEM images revealed predominantly spherical particles with uneven surface texture. Photocatalytic efficiency exceeded 80% MB dye degradation after 120 min of sunlight exposure. Optimization of catalyst dose, pH, dye concentration, and other parameters is essential for maximizing degradation efficiency. The IONPs demonstrated reusability over four degradation cycles, retaining effective photocatalytic performance. This study underscores the potential of green-synthesized IONPs as eco-friendly photocatalysts for wastewater treatment and environmental remediation.

Unraveling the roles of atomically-dispersed Au in boosting photocatalytic CO2 reduction and aryl alcohol oxidation

Atomically-dispersed metal-based materials represent an emerging class of photocatalysts attributed to their high catalytic activity, abundant surface active sites, and efficient charge separation. Nevertheless, the roles of different forms of atomically-dispersed metals (i.e., single-atoms and atomic clusters) in photocatalytic reactions remain ambiguous. Herein, we developed an ethylenediamine (EDA)-assisted reduction method to controllably synthesize atomically dispersed Au in the forms of Au single atoms (AuSA), Au clusters (AuC), and a mixed-phase of AuSA and AuC (AuSA+C) on CdS. In addition, we elucidate the synergistic effect of AuSA and AuC in enhancing the photocatalytic performance of CdS substrates for simultaneous CO2 reduction and aryl alcohol oxidation. Specifically, AuSA can effectively lower the energy barrier for the CO2→*COOH conversion, while AuC can enhance the adsorption of alcohols and reduce the energy barrier for dehydrogenation. As a result, the AuSA and AuC co-loaded CdS show impressive overall photocatalytic CO2 conversion performance, achieving remarkable CO and BAD production rates of 4.43 and 4.71 mmol g−1 h−1, with the selectivities of 93% and 99%, respectively. More importantly, the solar-to-chemical conversion efficiency of AuSA+C/CdS reaches 0.57%, which is over fivefold higher than the typical solar-to-biomass conversion efficiency found in nature (ca. 0.1%). This study comprehensively describes the roles of different forms of atomically-dispersed metals and their synergistic effects in photocatalytic reactions, which is anticipated to pave a new avenue in energy and environmental applications.