Photocatalytic Reduction Reaction Research Articles

Synergistic Tuning of Heterovalent States and Oxygen-Vacancy Defect Engineering in Hydrophilic W-Doped Sb2OS2 for Enhanced Nitrogen Photoreduction to Ammonia.

Nitrogen fixation reaction via photocatalysis offers a green and promising strategy for renewable NH3 synthesis, and catalysts with high-efficiency photocatalytic properties are essential to the process. Herein, we demonstrate a W-doped Sb2OS2 bimetal oxysulfide catalyst (labeled as SbWOS) with abundant oxygen vacancies, heterovalent metal states, and hydrophilic surfaces for nitrogen photoreduction to ammonia. The SbWOS-3 with suitable W-doping exhibited excellent nitrogen fixation activity of 408.08 μmol·g-1·h-1 and an apparent quantum efficiency (AQE) of 1.88% at 420 nm and a solar-to-ammonia (STA) conversion efficiency of 0.082% in pure water under AM1.5G light irradiation. The W-doping not only transforms hydrophobic Sb2OS2 into a hydrophilic catalyst, making it easier for H2O molecules adsorbed on the SbWOS surface and catalyzed into protons, but also endows the SbWOS catalyst with rich oxygen vacancies, acting as the active sites for trapping and activating the N2 molecule, and for trapping and activating H2O to produce the protons for the N2 photocatalytic reduction reaction. The hydrazine drives the SbWOS catalyst with the heterovalent metal states, which acts as the photogenerate electrons quickly hopping between W5+ and W6+ to transfer for the N2 reduction reaction. This study provides a feasible scheme for applying oxygen vacancy defects, heterovalent metal states, and surface hydrophobic-to-hydrophilic wetting engineering in bimetal oxysulfide for N2 photoreduction to ammonia.

Modulating Yeager Adsorption Configuration of O2 Through Cd Doping in Zn3In2S6 for Photosynthesis of H2O2

AbstractThe photocatalytic oxygen reduction reaction (ORR) is a key pathway for producing hydrogen peroxide (H2O2). While most previous studies have focused on the two‐step 2e− ORR process, the one‐step two‐electron ORR route offers thermodynamic and kinetic advantages that can significantly enhance 2e− ORR activity and selectivity. In this study, a photocatalyst design is reported by incorporating cadmium into vacancy‐rich Zn3In2S6 (Cd‐SV/ZIS). This catalyst enables H2O2 production via a one‐step 2e− ORR process without the use of sacrificial agents, achieving a high H2O2 yield of 39.42 µmol g−1 min−1 under UV–vis light irradiation, outperforming most reported ZIS‐based photocatalysts. Theoretical simulations and experimental results demonstrate that Cd doping improves the carrier kinetics of the catalyst, broadens its light absorption range, and promotes the Yeager adsorption configuration of O2, leading to highly active and selective H2O2 generation. This study provides insights into the design of efficient ZIS‐based photocatalysts for H2O2 production.

Boosting photocatalytic nitrogen fixation performance by adjusting the intramolecular D-A structure and band gap of thiophene-based COFs

Herein, we successfully synthesized two photoactive donor–acceptor (D-A) covalent organic frameworks by incorporating electric-deficient triazine and electric-rich benzotrithiophene moieties into the framework. The introduction of sulfur atom and triazine unit significantly change the intrinsic band gap of JLNU-COFs, this leads to an expanded range of light absorption, encompassing wavelengths from ultraviolet to visible. The narrow band gap of JLNU-311 allows for efficient utilization of visible light while maintaining the thermodynamic activity required for nitrogen reduction within appropriate energy bands. JLNU-311 modified with strong electron absorbing groups has higher activity to NH3 production without co-catalyst or sacrificial agent, and yield can reach 325.6 µmol/g/h. Theoretical calculation further confirm that acceptor structure can effectively regulate the band gap width, promote the adsorption, dissociation and protonation of N2 molecules on JLNU-COFs, and thus reduce the energy barrier of photocatalytic nitrogen reduction reaction (PNRR). Therefore, this study provides an effective strategy for design of active nitrogen fixing photocatalysts.

Adsorption Performance and Photocatalytic Activity of La-TiO2@kaolin Composites

Abstract La-TiO2@kaolin(LTK) composites were prepared via sol-gel method with kaolin, lanthanum nitrate and tetrabutyl titanate as raw materials. The samples were characterized by XRD, SEM/EDS, and UV-Vis. The visible light photocatalytic reduction activity and adsorption performance of samples for Cr(VI) were studied. The results showed that La doping can refine TiO2 grains, stabilize phase structure of anatase TiO2, and expand its absorption spectrum, thereby enhancing its photocatalytic reduction activity. Due to the composite of kaolin, the dispersion of TiO2 is improves and it is endowed with a large specific surface area lead to enhance its adsorption ability for Cr(VI). The adsorption equilibrium process of LTK for Cr(VI) conforms to the Langmuir equation model. The coupling effect of doping and composite modification improves the adsorption and visible light catalytic reduction activity of Cr(VI) over composite material samples. The adsorption-photocatalytic removal rate of LTK for Cr(VI) under visible light irradiation for 6 hours reached the highest of 96.5%. The apparent first-order kinetic constant of its photocatalytic reduction reaction was 2.6 times that of pure TiO2.

Effect of Surface Anions Adsorbed by Rutile TiO2 (001) on Photocatalytic Nitrogen Reduction Reaction: A Density Functional Theory Calculation

The adsorption of common anions found in water can have a considerable impact on the surface state and optical characteristics of titanium dioxide (TiO2), which has an important impact on the photocatalytic nitrogen reduction reaction (NRR). This work utilizes density functional theory (DFT) computations to examine the electronic and optical characteristics of the TiO2 (001) surface under various anion adsorptions in order to clarify their influence on the photocatalytic NRR of TiO2. The modifications in the structure, optical, and electronic properties of TiO2 before and after anion adsorption are investigated. In addition, the routes of Gibbs free energy for the NRR are also evaluated. The results indicate that the adsorption of anions modifies the surface characteristics of TiO2 to a certain degree, hence impacting the separating and recombining charge carriers by affecting the energy gap of TiO2. More importantly, the adsorption of anions can increase the energy barriers for the NRR, thereby exerting a detrimental effect on its photocatalytic activity. These findings provide a valuable theoretical contribution to understanding the photocatalytic reaction process of TiO2 and its potential application of NRR in the actual complex water phase.

Rational Construction of Cyanide-Functionalized D-A-π-D Covalent Organic Framework for Highly Efficient Overall H2O2 Photosynthesis from Air and Water.

Sacrificial-agent-free overall photosynthesis of H2O2 from water and air represents currently a promising route to reform the industrial anthraquinone production manner, but, still blocks by the requirement of pure O2 feedstock, due to the insufficient oxygen supply from water under air. Herein, we report a rational molecule design on COFs (covalent organic frameworks) equiped with cyanide-functionalized D-A-π-D system for highly efficient overall H2O2 production from air and water through photocatalytic oxygen reduction reactions (ORR) and water oxidation reaction (WOR). Without using any sacrificial agent, the as-synthesized D-A-π-D COF is found to enable a H2O2 production rate as high as 4742 μmol h-1 g-1 from water and air and an O2 utilization and conversion rate up to 88 %, exceeding the other D-A-π-A COF by respectively 1.9- and 1.3-fold. Such high performance is attributed to the tuned electronic structure and prolonged charge lifetime facilitated by the unique D-A-π-D structure and cyanide groups. This work highlights a fundamental molecule design on advanced photocatalytic COFs with complicated D-A system for low-cost and massive H2O2 production.

Rational Construction of Cyanide‐Functionalized D‐A‐π‐D Covalent Organic Framework for Highly Efficient Overall H2O2 Photosynthesis from Air and Water

Sacrificial‐agent‐free overall photosynthesis of H2O2 from water and air represents currently a promising route to reform the industrial anthraquinone production manner, but, still blocks by the requirement of pure O2 feedstock, due to the insufficient oxygen supply from water under air. Herein, we report a rational molecule design on COFs (covalent organic frameworks) equiped with cyanide‐functionalized D‐A‐π‐D system for highly efficient overall H2O2 production from air and water through photocatalytic oxygen reduction reactions (ORR) and water oxidation reaction (WOR). Without using any sacrificial agent, the as‐synthesized D‐A‐π‐D COF is found to enable a H2O2 production rate as high as 4742 μmol h‐1 g‐1 from water and air and an O2 utilization and conversion rate up to 88%, exceeding the other D‐A‐π‐A COF by respectively 1.9‐ and 1.3‐fold. Such high performance is attributed to the tuned electronic structure and prolonged charge lifetime facilitated by the unique D‐A‐π‐D structure and cyanide groups. This work highlights a fundamental molecule design on advanced photocatalytic COFs with complicated D‐A system for low‐cost and massive H2O2 production.

Anomalous Reaction Pathways to Methane Production in Photocatalytic Ethanol Oxidation.

Photocatalytic reduction reactions occasionally utilize sacrificial agents to scavenge photogenerated holes, thus enhancing the kinetics and efficiency of electron harvesting. However, exploring alternative hole-mediated oxidation reactions and their potential impact on photoredox processes is limited. This study investigates the products resulting from the oxidation of ethanol, a commonly used hole scavenger, and the underlying mechanisms involved. We examine a homogeneous eosin Y photoreaction scheme containing a Cu complex coordinated with an N-heterocyclic carbene, a combination often employed in CO2 conversion. Under visible-light excitation, this photosystem yields methane as an unusual product, alongside acetaldehyde and carbon monoxide. Mechanistic analysis reveals that ethanol undergoes a catalytic cascade involving oxidative processes, C-C bond cleavage, and intermolecular hydrogen atom transfer. Notably, the Lewis-acidic metal center of the Cu complex activates a novel pathway for ethanol oxidation. This work presents the influence of catalyst selection and reaction condition optimization on the emergence of new or unexpected catalytic processes.

Developing three-dimensional hydrophobic photocatalysts to enhance mass transfer for promoting hydrogen peroxide production

Photocatalytic oxygen reduction reaction (ORR) is a promising approach for hydrogen peroxide (H2O2) production to alternative conventional anthraquinone process. However, the slow O2 diffusion and low-efficiency water oxidation reaction (WOR, limitation of protons) pathways have restricted the H2O2 production efficiency of organic photocatalysts. Therefore, a promising strategy to develop photocatalysts with three-dimensional (3D) architectures possessing high O2 diffusion, high-efficiency WOR pathway, and quick H2O2 desorption is desirable. Herein, a hydrophobic two-dimensional porous organic polymer (2D-POP) based on tetraphenylethylene (TPE) was synthesized as the building block. 3D-POPs (TPE-2 and TPE-3) were subsequently developed through the Friedel-Crafts alkylation reaction to regulate the O2 adsorption and optical properties. The 3D architectures allow O2 to diffuse into the interlayers, leading to efficient extraction of O2 from air, thus an excellent H2O2 production rate of 2.57 mmol g−1 h−1has been achieved by TPE-2 in air and without sacrificial agents, which only decreases by 4% compared to that in O2 due to a suitable specific surface area, good photoelectric properties, and excellent mass transfer of O2, H+, and H2O2. Furthermore, the H2O2 production rate of TPE-2 reaches 2.67 mmol g−1 h−1 in a triphasic system in air, which is higher than that in a traditional diphasic system, and the concentration of H2O2 reaches 1.80 mmol L−1 h−1. Additionally, by adding external Fe2+ or Fe3+ to make the utmost of photogenerated H2O2 and trigger the in-situ Fenton reaction for the formation of ·OH, TPE-2 exhibits extraordinary photodegradation efficiency toward representative organic pollutants, reaching > 99% removal within 60 min for bisphenol A and 2,4-dichlorophenoxyacetic acid with high concentrations (200 ppm).

Unveiling O2 adsorption on non-metallic active site for selective photocatalytic H2O2 production

Photocatalytic oxygen reduction reaction (ORR) offers a promising pathway for sustainable hydrogen peroxide (H2O2) production but faces challenges in developing catalysts with good ORR selectivity. Herein, we report that tailoring O2 adsorption on non-metallic active sites can optimize ORR selectivity. This concept is demonstrated on three carbon nitrides with different atomic configurations: polymeric carbon nitride (PCN), lithium-poly triazine imide (Li-PTI), and sodium-poly heptazine imide (Na-PHI). Na-PHI emerges as a strong candidate for H2O2 production due to the end-on adsorption mode and suitable adsorption strength with O2. Synthesized Na-PHI, PCN, and Li-PTI are characterized, with Na-PHI showing superior light absorption, charge carrier separation, and remarkable selectivity (92 %) for two-electron ORR. Consequently, Na-PHI achieves a high H2O2 generation rate of 3.48 mmol g−1 h−1, surpassing Li-PTI and PCN by 9.2 and 33 times, respectively. This study underscores the importance of O2 adsorption on non-metallic active sites for selective photocatalytic H2O2 generation.

Enhancing degradation of novel brominated flame retardants by sulfate modified C3N4: Synergistic effect of photocatalytic oxidation and reduction processes

Novel brominated flame retardants (NBFRs) pose serious risks to aquatic organisms and human health due to their persistence and toxicity. Herein, sulfate ions (SO42-) decorated C3N4 (SO42-@CN) photocatalyst material was synthesized for the rapid degradation of NBFRs by a synergistic effect of photocatalytic oxidation and reduction reactions. Compared with bare C3N4, the SO42-@CN exhibited efficient photocatalytic NBFRs removal performance. The degradation rates constant of hexabromobenzene and pentabromotoluene by SO42-@CN were 0.177 and 0.0906 min-1, respectively, which were 2.9 and 6.7 times higher than that by C3N4. It was confirmed that SO42-@CN could generate more active substances (such as sulfate radicals, and hydroxyl radicals) and promote the oxidation of NBFRs. Meanwhile, SO42- accelerated the separation of photogenerated electron-holes by promoting the formation of hydrogenated structures, allowing more photogenerated electrons to participate in the debromination reduction process. This work provides a new insight for the practical application of visible light driven photocatalytic technology in NBFRs residues degradation.

N-doped carbon dots-modulated interfacial charge transfer and surface structure in FeNbO4 photocatalysts for enhanced CO2 conversion selectivity to CH4

The photocatalytic carbon dioxide reduction reaction (CO2RR) is an innovative and reliable technology to address the issues of energy shortage and climate change simultaneously. However, issues such as insufficient light absorption, rapid electron-hole recombination and low surface activity during CO2RR severely limit the catalysts’ efficiency for photocatalysis. In this study, we present nanohybrid N-CDs/FeNbO4 catalysts to overcome these challenges and achieve high-efficient photocatalytic conversion of CO2 to CH4. The enhancement process starts with the introduction of modified N-CDs, which have a broad light absorption capability. These N-CDs also help to modulate the interfacial charge transfer kinetics, leading to improved charge separation and transfer. This, in turn, enhances the multielectron transfer conversion selectivity of CO2 to CH4. Meanwhile, CO2 adsorption on the photocatalysts is increased due to the creation of oxygen vacancies and lattice stresses resulting from the introduction of N-CDs. This work presents a new approach for improving the photocatalytic performance by adjusting surface structure and interfacial behaviors.

Synthesis of metal-phenanthroline-modified hypercrosslinked polymer for enhanced CO2 capture and conversion via chemical and photocatalytic methods under ambient conditions

Catalytic conversion of CO2 into valuable chemicals is a promising approach to mitigate the greenhouse effect and alleviate energy shortages. Hypercrosslinked polymers (HCPs) offer a scalable and stable platform for this conversion, but they often suffer from low CO2 adsorption and activation capabilities, necessitating high temperatures and pressures for effectiveness. To overcome these limitations, nitrogen-based CO2-philic active sites have been integrated into the structure of HCPs, enhancing CO2 attraction and leading to superior adsorption performance. The incorporation of cobalt ions further bolsters CO2 affinity, with HCP-PNTL-Co-B achieving the highest observed adsorption heat of 33.0 kJ·mol-1 alongside a substantial 2.0 mmol·g-1 CO2 uptake. These modified HCPs exhibit higher yields and reaction rates in cycloaddition reactions with cocatalyst tetrabutylammonium bromide at room temperature and atmospheric pressure, while HCP-1,10-phenanthroline (PNTL)-Co-B demonstrates a higher CO production rate (2,173 μmol·g-1·h-1) and selectivity (84%) in photocatalytic reduction reaction. This research has successfully achieved outstanding carbon dioxide capture and conversion performance at room temperature and atmospheric pressure by introducing CO2-philic active sites and cobalt ions into HCPs via facile one-step polymerization. This study provides a new method to design highly efficient organic catalysts for CO2 conversion.

Nanoporous Heterojunction Photocatalysts with Engineered Interfacial Sites for Efficient Photocatalytic Nitrogen Fixation.

Photocatalytic N2 reduction reaction (PNRR) offers a promising strategy for sustainable production of ammonia (NH3). However, the reported photocatalysts suffer from low efficiency with great room to improve regarding the charge carrier utilization and active site engineering. Herein, a porous and chemically bonded heterojunction photocatalyst is developed for efficient PNRR to NH3 production via hybridization of two semiconducting metal-organic frameworks (MOFs), MIL-125-NH2 (MIL=Material Institute Lavoisier) and Co-HHTP (HHTP=2,3,6,7,10,11-hexahydroxytripehenylene). Experimental and theoretical results demonstrate the formation of Ti-O-Co chemical bonds at the interface, which not only serve as atomic pathway for S-scheme charge transfer, but also provide electron-deficient Co centers for improving N2 chemisorption/activation capability and restricting competitive hydrogen evolution. Moreover, the nanoporous structure allows the transportation of reactants to the interfacial active sites at heterojunction, enabling the efficient utilization of charge carriers. Consequently, the rationally designed MOF-based heterojunction exhibits remarkable PNRR performance with an NH3 production rate of 2.1 mmol g-1 h-1, an apparent quantum yield (AQY) value of 16.2% at 365 nm and a solar-to-chemical conversion (SCC) efficiency of 0.28%, superior to most reported PNRR photocatalysts. Our work provides new insights into the design principles of high-performance photocatalysts.

Synergy of P doping and crystallinity modulation in carbon nitride for enhancing photocatalytic uranyl reduction

Doping modification is a useful way to promote the catalytic activity of carbon nitride (CN). However, most doped CNs have lower structural symmetry and several edge defects, which hinder the transfer of charge carriers. This work reports a P-doped crystalline carbon nitride (crystalline PCN) for the efficient photoreduction of uranyl. The thermal polymerization and salt post-treatment convert the amorphous PCN into crystalline PCN. Compared to the pristine CN, the crystalline PCN has over 1620 % higher activity for uranyl (U(VI)) reduction, reaching a 97.8 % reduction rate in 60 min. Furthermore, the 2-PCN shows excellent stability and a U(VI) removal efficiency >85.7 % in the pH range of 5–8. Characterization analysis reveal that both the P doping and crystalline modulation do not obviously change their morphology, light absorption property and energy band structure, but markedly promote the delocalization of electrons around the doped P atoms, thereby severely inhibit direct electron-hole recombination. Thus, the more efficient separation of charge carriers generates more reactive specials to participate in the photocatalytic uranyl reduction reaction. This study demonstrates a dual-modification strategy for the rational synthesis of highly active metal-free CN-based photocatalysts for uranyl reduction.

Nanoarchitectonics of S-Scheme Heterojunction Photocatalysts: A Nanohouse Design Improves Photocatalytic Nitrate Reduction to Ammonia Performance.

Photocatalytic nitrate reduction reaction (NitRR) is a promising route for environment remediation and sustainable ammonia synthesis. To design efficient photocatalysts, the recently emerged nanoarchitectonics approach holds great promise. Here, we report a nanohouse-like S-scheme heterjunction photocatalyst with high photocatalytic NitRR performance. The nano-house has a floor of plate-like metal organic framework-based photocatalyst (NH2-MIL-125), on which another photocatalyst Co(OH)2 nanosheet is grown while ZIF-8 hollow cages are also constructed as the surrounding wall/roof. Experimental and simulation results indicate that the positively charged, highly porous and hydrophobic ZIF-8 wall can modulate the environment in the nanohouse by (i) NO3 - enrichment/NH4 + discharge and (ii) suppression of the competitive hydrogen evolution reaction. In combination with the enhanced electron-hole separation and strong redox capability in the NH2-MIL-125@Co(OH)2 S-scheme heterjunction confined in the nano-house, the designed photocatalyst delivers an ammonia yield of 2454.9 μmol g-1 h-1 and an apparent quantum yield of 8.02 % at 400 nm in pure water. Our work provides new insights into the design principles of advanced photocatalytic NitRR photocatalyst.

Nanoarchitectonics of S‐Scheme Heterojunction Photocatalysts: A Nanohouse Design Improves Photocatalytic Nitrate Reduction to Ammonia Performance

AbstractPhotocatalytic nitrate reduction reaction (NitRR) is a promising route for environment remediation and sustainable ammonia synthesis. To design efficient photocatalysts, the recently emerged nanoarchitectonics approach holds great promise. Here, we report a nanohouse‐like S‐scheme heterjunction photocatalyst with high photocatalytic NitRR performance. The nano‐house has a floor of plate‐like metal organic framework‐based photocatalyst (NH2‐MIL‐125), on which another photocatalyst Co(OH)2 nanosheet is grown while ZIF‐8 hollow cages are also constructed as the surrounding wall/roof. Experimental and simulation results indicate that the positively charged, highly porous and hydrophobic ZIF‐8 wall can modulate the environment in the nanohouse by (i) NO3− enrichment/NH4+ discharge and (ii) suppression of the competitive hydrogen evolution reaction. In combination with the enhanced electron‐hole separation and strong redox capability in the NH2‐MIL‐125@Co(OH)2 S‐scheme heterjunction confined in the nano‐house, the designed photocatalyst delivers an ammonia yield of 2454.9 μmol g−1 h−1 and an apparent quantum yield of 8.02 % at 400 nm in pure water. Our work provides new insights into the design principles of advanced photocatalytic NitRR photocatalyst.

Surface Reconstruction-Induced Photocatalytic Methanol Reduction Reaction on a Rutile TiO2(001) Surface.

Photochemistry of methanol on TiO2 surfaces is of great importance both fundamentally and industrially. Methanol was previously reported only to occur photogenerated hole-participating oxidation reactions on TiO2 surfaces. Herein, we report that, upon UV light illumination, the methoxy species formed by methanol dissociation at the 5-fold coordinated Ti4+ sites (CH3O(a)Ti5c) of a reconstructed rutile TiO2(001)-(1 × 1) surface also undergoes the C-O bond cleavage into methyl fragments mediated by photogenerated electrons, in addition to the well-established photogenerated hole-participating oxidation reactions. Upon subsequent heating, the resulting methyl species undergoes hydrogenation and coupling reactions into methane and ethane, respectively. Accompanying theoretical calculations showed that the lowest unoccupied molecular orbital (LUMO) of CH3O(a)Ti5c is localized almost at the conduction band minimum of the CH3O-adsorbed reconstructed rutile TiO2(001)-(1 × 1) surface, indicating the likely TiO2 → CH3O(a)Ti5c interfacial photoexcited-electron transfer. These results greatly broaden the photochemistry of methanol on TiO2 surfaces and demonstrate a photocatalytic methanol-to-hydrocarbon reaction route.

(Invited) Upconverted Hot Electrons from Semiconductor Nanocrystals for Enhancing Photocatalysis

The exciton-to-hot electron upconversion phenomenon in Mn-doped semiconductor quantum dots (QDs) produces highly energetic hot electrons. These electrons have an average energy just a fraction of 1 eV below the vacuum level, with a subpopulation of hot electrons existing above the vacuum level. This hot electron upconversion process is similar to photon upconversion in lanthanide-doped nanoparticles. However, the final state here is a highly excited hot electron in the conduction band of the host QDs, not a state emitting higher-energy photons. These upconverted hot electrons can be harnessed to carry out thermodynamically and kinetically challenging reduction reactions, benefiting from their high excess kinetic energy and long-range transfer capability. The presentation will discuss recent demonstrations of the benefits of these upconverted hot electrons in various photocatalytic reduction and redox-neutral reactions. Additionally, the development of new materials for more efficient hot electron upconversion and the potential to broaden the application of these energetic hot electrons beyond photocatalysis will be discussed.

Synthesis and characterization of Ag/Cu dual-metal-functionalized porous Bi2WO6 microsphere with enhanced N2 photofixation

Semiconductor photocatalytic nitrogen reduction reaction (PNRR) stands as a promising clean technique for ammonia synthesis, yet it confronts numerous challenges. In this study, Ag nanoparticle-modified Cu-doped Bi2WO6 (ACB) porous composite materials with varying mass percentages were successfully synthesized using a solvothermal reduction approach. The incorporation of transition metal Cu effectively modulates the energy band position of Bi2WO6. Furthermore, the introduction of Ag nanoparticles significantly suppresses the recombination of photogenerated carriers. Without adding sacrificial agent, the photocatalytic nitrogen fixation yield of ACB reaches an impressive 184.93 μmol·g−1·h−1, which is 5.44 times higher than that of pristine Bi2WO6. A comprehensive analysis of the experimental results reveals that the combined effect of Cu doping and Ag nanoparticle loading endows ACB with an increased exposure of active sites, thereby significantly enhancing its photocatalytic nitrogen fixation performance. This research offers a promising approach for the design of metal nanoparticle-supported catalysts for PNRR, holding significant implications for the advancement of other material systems.