Photocatalytic Water Oxidation Research Articles

Bioinspired Water Preorganization in Confined Space for Efficient Water Oxidation Catalysis in Metallosupramolecular Ruthenium Architectures.

ConspectusNature has established a sustainable way to maintain aerobic life on earth by inventing one of the most sophisticated biological processes, namely, natural photosynthesis, which delivers us with organic matter and molecular oxygen derived from the two abundant resources sunlight and water. The thermodynamically demanding photosynthetic water splitting is catalyzed by the oxygen-evolving complex in photosystem II (OEC-PSII), which comprises a distorted tetramanganese-calcium cluster (CaMn4O5) as catalytic core. As an ubiquitous concept for fine-tuning and regulating the reactivity of the active site of metalloenzymes, the surrounding protein domain creates a sophisticated environment that promotes substrate preorganization through secondary, noncovalent interactions such as hydrogen bonding or electrostatic interactions. Based on the high-resolution X-ray structure of PSII, several water channels were identified near the active site, which are filled with extensive hydrogen-bonding networks of preorganized water molecules, connecting the OEC with the protein surface. As an integral part of the outer coordination sphere of natural metalloenzymes, these channels control the substrate and product delivery, carefully regulate the proton flow by promoting pivotal proton-coupled electron transfer processes, and simultaneously stabilize short-lived oxidized intermediates, thus highlighting the importance of an ordered water network for the remarkable efficiency of the natural OEC.Transferring this concept from nature to the engineering of artificial metal catalysts for fuel production has fostered the fascinating field of metallosupramolecular chemistry by generating defined cavities that conceptually mimic enzymatic pockets. However, the application of supramolecular approaches to generate artificial water oxidation catalysts remained scarce prior to our initial reports, since such molecular design strategies for efficient activation of substrate water molecules in confined nanoenvironments were lacking. In this Account, we describe our research efforts on combining the state-of-the art Ru(bda) catalytic framework with structurally programmed ditopic ligands to guide the water oxidation process in defined metallosupramolecular assemblies in spatial proximity. We will elucidate the governing factors that control the quality of hydrogen-bonding water networks in multinuclear cavities of varying sizes and geometries to obtain high-performance, state-of-the-art water oxidation catalysts. Pushing the boundaries of artificial catalyst design, embedding a single catalytic Ru center into a well-defined molecular pocket enabled sophisticated water preorganization in front of the active site through an encoded basic recognition site, resulting in high catalytic rates comparable to those of the natural counterpart OEC-PSII.To fully explore their potential for solar fuel devices, the suitability of our metallosupramolecular assemblies was demonstrated under (electro)chemical and photocatalytic water oxidation conditions. In addition, testing the limits of structural diversity allowed the fabrication of self-assembled linear coordination oligomers as novel photocatalytic materials and long-range ordered covalent organic framework (COF) materials as recyclable and long-term stable solid-state materials for future applications.

Manufacturing porous BaTaO2N nanosheet via nitridation of a novel oxyhalide precursor for boosted photocatalytic water oxidation reaction

Manufacturing porous BaTaO2N nanosheet via nitridation of a novel oxyhalide precursor for boosted photocatalytic water oxidation reaction

BiVO4/CuIn5S8 heterojunction with rich sulphur vacancies for boosting visible light-driven photocatalytic water oxidation

The efficient conversion of water into clean energy using solar energy presents a sustainable solution to environmental challenges, albeit constrained by the slow kinetics of the oxygen evolution reaction. This study introduces a series of novel BiVO4/CuIn5S8 heterojunctions, developed and employed as photocatalysts for water oxidation. The photocatalytic activity of these heterojunctions was systematically enhanced by optimizing the BiVO4/CuIn5S8 ratio and hydrothermal reaction temperature. Notably, the heterojunction comprising BiVO4 coupled with 5 % CuIn5S8, synthesized at 180 °C (BiVO4/CuIn5S8/180–5), exhibited superior photocatalytic performance compared to its individual components. This enhancement was further augmented by the introduction of sulfur vacancies (VS) in VS-BiVO4/CuIn5S8/180–5, achieving approximately 3 and 1.4 times the photocatalytic activity of BiVO4 and BiVO4/CuIn5S8/180–5, respectively. Our findings demonstrate that CuIn5S8 effectively grows on decahedral BiVO4, forming n-n heterojunctions that not only improve visible light absorption but also facilitate the separation of photogenerated carriers. The incorporation of VS significantly lowers the charge carrier recombination rate and promotes the formation of additional active sites for H2O adsorption, thereby further elevating the efficiency of photocatalytic water oxidation.

Evaluation of Ce-MOFs as Photoanode Materials for the Water Oxidation Reaction: The Effect of Doping with [Ru(bpy)(dcbpy)(H2O)2]2+ Catalyst.

Artificial photosynthesis stands out as a highly effective method for harnessing sunlight to produce clean and renewable energy. The light-absorbing properties, chemical stability, and high redox activity of Ce-based metal-organic frameworks (MOFs) make them attractive materials for visible-light-driven water splitting. Currently, Ce-based MOFs remain a relatively underexplored system for photocatalytic water oxidation in acidic media. In this study, we synthesized a Ce-MOF with different linkers (1,4-benzenedicarboxylic acid, tetrafluoroterephthalic acid, 2-nitroterephthalic acid, 2,2'-bipyridine-5,5'-dicarboxylic acid, and 4,4'-biphenyldicarboxylic acid), which exhibit light-absorbing capability. Ce-based MOFs doped with [Ru(bpy)(dcbpy)(H2O)2]2+ (MOF-1 and MOF-2) water oxidation catalyst showed an enhanced photoelectrocatalytic current of ∼10-4 A·cm-2 at pH = 1, which is comparable with the [Ru(bpy)(dcbpy)(H2O)2]2+-doped MIL-126 Fe-based MOF. We also demonstrated the long-term durability of Ru-doped Ce-MOFs for photoelectrocatalytic water oxidation under acidic conditions. The as-synthesized MOFs were analyzed with powder X-ray diffraction (PXRD), Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), UV-visible diffuse reflectance spectroscopy, scanning electron microscopy (SEM), and electric conductivity measurements. This study contributes to the development of cost-effective materials for sustainable photocatalytic water splitting processes.

Regulating the Topology of Covalent Organic Frameworks for Boosting Overall H2O2 Photogeneration

Photocatalytic oxygen reduction reactions and water oxidation reactions are extremely promising green approaches for massive H2O2 production. Nonetheless, constructing effective photocatalysts for H2O2 generation is critical and still challenging. Since the network topology has significant impacts on the electronic properties of two dimensional (2D) polymers, herein, for the first time, we regulated the H2O2 photosynthetic activity of 2D covalent organic frameworks (COFs) by topology. Through designing the linking sites of the monomers, we synthesized a pair of novel COFs with similar chemical components on the backbones but distinct topologies. Without sacrificial agents, TBD‐COF with cpt topology exhibited superior H2O2 photoproduction performance (6085 and 5448 μmol g‐1 h‐1 in O2 and air) than TBC‐COF with hcb topology through the O2‐O2•‐‐H2O2, O2‐O2•‐‐O21‐H2O2, and H2O‐H2O2 three paths. Further experimental and theoretical investigations confirmed that during the H2O2 photosynthetic process, the charge carrier separation efficiency, O2•‐ generation and conversion, and the energy barrier of the rate determination steps in the three channels, related to the formation of *OOH, *O21, and *OH, can be well tuned by the topology of COFs. The current study enlightens the fabrication of high‐performance photocatalysts for H2O2 production by topological structure modulation.

Regulating the Topology of Covalent Organic Frameworks for Boosting Overall H2O2 Photogeneration.

Photocatalytic oxygen reduction reactions and water oxidation reactions are extremely promising green approaches for massive H2O2 production. Nonetheless, constructing effective photocatalysts for H2O2 generation is critical and still challenging. Since the network topology has significant impacts on the electronic properties of two dimensional (2D) polymers, herein, for the first time, we regulated the H2O2 photosynthetic activity of 2D covalent organic frameworks (COFs) by topology. Through designing the linking sites of the monomers, we synthesized a pair of novel COFs with similar chemical components on the backbones but distinct topologies. Without sacrificial agents, TBD-COF with cpt topology exhibited superior H2O2 photoproduction performance (6085 and 5448 μmol g-1 h-1 in O2 and air) than TBC-COF with hcb topology through the O2-O2•--H2O2, O2-O2•--O21-H2O2, and H2O-H2O2 three paths. Further experimental and theoretical investigations confirmed that during the H2O2 photosynthetic process, the charge carrier separation efficiency, O2•- generation and conversion, and the energy barrier of the rate determination steps in the three channels, related to the formation of *OOH, *O21, and *OH, can be well tuned by the topology of COFs. The current study enlightens the fabrication of high-performance photocatalysts for H2O2 production by topological structure modulation.

Fabrication of Ag-decorated La0.9Ag0.1FeO3 for efficient photocatalytic degradation of tetracycline under visible light with the assistance of water oxidation

The photocatalytic conversion of molecular O2 into reactive oxygen species, such as superoxide radicals (·O-2), has become the focus in the oxidative removal of organic pollutants. Nevertheless, the inefficient light absorption, limited adsorption of O2, and the fast recombination rate of photo-induced electron-hole pairs considerably impede the conversion efficiency of the photocatalysts. Herein, we report the synthesis of Ag@LAFO photocatalyst, which contains Ag nanoparticles (NPs)-decorated LAFO (Ag-substituted LaFeO3), to enhance the photodegradation efficiency of tetracycline (TC) with the assistance of water oxidation. Structural and spectroscopic analyses confirmed the successful decoration of Ag NPs on LAFO, which was prepared by substituting 10% La with Ag. The efficiency of TC photocatalytic degradation rate of Ag@LAFO is 76.25%, which is 6.1-fold higher than that of pure LFO (12.41%). The trapping experiment of active radicals verified that ·O-2 was crucial in the decomposition of TC molecules and was continuously supplied by the reduction of O2 molecules supported by photocatalytic water oxidation. Moreover, the Ag NPs in Ag@LAFO were found to be crucial for boosting the capture of photo-induced electrons and the activation of adsorbed O2. This study offers a new perspective on the conversion of O2 to ·O-2 with the assistance of photocatalytic water oxidation for photocatalytic degradation of organic pollutants.

Coupling Electron Transfer and Redox Site in Boranil Covalent Organic Framework Toward Boosting Photocatalytic Water Oxidation.

The efficient polymeric semiconducting photocatalyst for solar-driven sluggish kinetics with multielectron transfer oxygen evolution has spurred scientific interest. However, existing photocatalysts limited by π-conjugations, visible-light harvest, and charge transfer often compromise the O2 production rate. Herein, we introduced an alternative strategy involving a boranil functionalized-based fully π-conjugated ordered donor and acceptor (D-A) covalent organic frameworks (Ni-TAPP-COF-BF2 ) photocatalyst. The co-catalyst-free Ni-TAPP-COF-BF2 exhibits an excellent ~11-fold photocatalytic water oxidation rate, reaching 1404 μmol g-1  h-1 under visible light irradiation compared to pristine Ni-TAPP-COF (123 μmol g-1  h-1 ) alone and surpasses to reported organic frameworks counterpart. Both experimental and theoretical results demonstrate that the push/pull mechanism (metalloporphyrin/BF2 ) is responsible for the appropriate light-harvesting properties and extending π-conjugation through chelating BF2 moieties. This strategy benefits in narrowing band structure, improving photo-induced charge separation, and prolonged charge recombination. Further, the lower spin magnetic moment of M-TAPP-COF-BF2 and the closer d-band center of metal sites toward the Fermi level lead to a lower energy barrier for *O intermediate. Reveal the potential of the functionalization strategy and opens up an alternative approach for engineering future photocatalysts in energy conversion applications.

Coupling Electron Transfer and Redox Site in Boranil Covalent Organic Framework Toward Boosting Photocatalytic Water Oxidation

AbstractThe efficient polymeric semiconducting photocatalyst for solar‐driven sluggish kinetics with multielectron transfer oxygen evolution has spurred scientific interest. However, existing photocatalysts limited by π‐conjugations, visible‐light harvest, and charge transfer often compromise the O2 production rate. Herein, we introduced an alternative strategy involving a boranil functionalized‐based fully π‐conjugated ordered donor and acceptor (D–A) covalent organic frameworks (Ni‐TAPP‐COF‐BF2) photocatalyst. The co‐catalyst‐free Ni‐TAPP‐COF‐BF2 exhibits an excellent ~11‐fold photocatalytic water oxidation rate, reaching 1404 μmol g−1 h−1 under visible light irradiation compared to pristine Ni‐TAPP‐COF (123 μmol g−1 h−1) alone and surpasses to reported organic frameworks counterpart. Both experimental and theoretical results demonstrate that the push/pull mechanism (metalloporphyrin/BF2) is responsible for the appropriate light‐harvesting properties and extending π‐conjugation through chelating BF2 moieties. This strategy benefits in narrowing band structure, improving photo‐induced charge separation, and prolonged charge recombination. Further, the lower spin magnetic moment of M‐TAPP‐COF‐BF2 and the closer d‐band center of metal sites toward the Fermi level lead to a lower energy barrier for *O intermediate. Reveal the potential of the functionalization strategy and opens up an alternative approach for engineering future photocatalysts in energy conversion applications.

Weakened Interfacial Hydrogen Bond Connectivity Drives Selective Photocatalytic Water Oxidation toward H2O2 at Water/Brookite-TiO2 Interface.

The formation of H2O2 through the two-electron photocatalytic water oxidation reaction (WOR) is significant but encounters the competition with the four-electron O2 evolution reaction. Recent studies showed a crystal-phase dependence in H2O2 selectivity, where high purity brookite TiO2 (b-TiO2) exhibits remarkable H2O2 selectivity in contrast to the common rutile phase TiO2 (r-TiO2). However, the origin of such a structure-induced selectivity preference remains elusive, primarily due to the complexities associated with the solid-liquid interface system and excited-state chemistry. Herein, we conducted a comprehensive investigation into the selectivity mechanism of WOR at the water/b-TiO2(210) and water/r-TiO2(110) interfaces, employing first-principles molecular dynamics simulations and microkinetic analyses. Intriguingly, our results reveal that the intrinsic catalytic ability of the b-TiO2(210) itself does not enhance H2O2 selectivity compared to r-TiO2(110). Instead, it is the weakened interfacial hydrogen bond connectivity, modulated by the herringbone-like local atomic structure of the b-TiO2(210) surface, that determines the selectivity. Specifically, this weakened H-bond connectivity (i.e., local low water density) at the interface, owing to the strong water adsorption and distinct adsorption orientation, can stabilize the OH• radical and inhibit its deprotonation, leading to an improved H2O2 selectivity. By contrast, the relatively strong interface H-bond connectivity established over r-TiO2(110) accelerates the deprotonation of OH•, with the OH• coverage being 3 orders of magnitude lower than at the water/b-TiO2(210) interface. This study quantitatively demonstrates that the local H-bond structure (water density) at the liquid/solid interface significantly influences photocatalytic selectivity, and this insight may offer a rational approach to enhance the H2O2 selectivity.

Nanoparticulate TiN Loading to Promote Z-Scheme Water Splitting Using a Narrow-Bandgap Nonoxide-Based Photocatalyst Sheet.

Some oxide-based particulate photocatalyst sheets exhibit excellent activity during the water-splitting reaction. The replacement of oxide photocatalysts with narrow-bandgap photocatalysts based on nonoxides could provide the higher solar-to-hydrogen energy conversion efficiencies that are required for practical implementation. Unfortunately, the activity of nonoxide-based photocatalyst sheets is low in many cases, indicating the need for strategies to improve the quality of nonoxide photocatalysts and the charge transfer process. In this work, single-crystalline particulate SrTaO2 N is studied as an oxygen evolution photocatalyst for photocatalyst sheets applied to Z-scheme water splitting, in combination with La5 Ti2 Cu0.9 Ag0.1 O7 S5 and Au as the hydrogen evolution photocatalyst and conductive layer, respectively. The loading of SrTaO2 N with CoOx provided increases activity during photocatalytic water oxidation, giving an apparent quantum yield of 15.7% at 420nm. A photocatalyst sheet incorporating CoOx -loaded SrTaO2 N is also found to promote Z-scheme water splitting under visible light. Notably, the additional loading of nanoparticulate TiN on the CoOx -loaded SrTaO2 N improves the water splitting activity by six times because the TiN promotes electron transfer from the SrTaO2 N particles to the Au layer. This work demonstrates key concepts related to the improvement of nonoxide-based photocatalyst sheets based on facilitating the charge transfer process through appropriate surface modifications.

Ultrathin covalent organic framework nanosheets for enhanced photocatalytic water oxidation.

Photocatalytic water oxidation is a key half-reaction for various solar-to-fuel conversion systems but requires simultaneous water affinity and hole accumulation at the photocatalytic site. Here, we present the rational design and synthesis of an ionic-type covalent organic framework (COF) named tetraphenylporphyrin cobalt and cobalt bipyridine complex (CoTPP-CoBpy3) COF, combining cobalt porphyrin and cobalt bipyridine building blocks as a photocatalyst for water oxidation. The good dispersibility of porous large-size (>2 micrometers) COF nanosheets (≈1.45 nanometers) facilitates local water collection; the ultrafast triplet-state charge transfer (1.8 picoseconds) and prolonged charge separation (1.2 nanoseconds) further contribute to the efficient accumulation of holes in the CoTPP moiety, leading to a photocatalytic dioxygen production rate of 7323 micromoles per gram per hour. Moreover, we have identified an end-on superoxide radical (O2·) intermediate at the active site of the CoTPP moiety and proposed an electron-intermediate cascade mechanism that elucidates the synergistic coupling of electron relay (S1-T1-T1') and intermediate evolution during the photocatalytic process.

Accelerated Photocatalytic Carbon Dioxide Reduction and Water Oxidation under Spatial Synergy.

Photocatalytic conversion of CO2 and H2 O into fuels and oxygen is a highly promising solution for carbon-neutral recycling. Traditionally, researchers have studied CO2 reduction and H2 O oxidation separately, overlooking potential synergistic interplay between these processes. This study introduces an innovative approach, spatial synergy, which encourages synergistic progress by bringing the two half-reactions into atomic proximity. To facilitate this, we developed a defective ZnIn2 S4 -supported single-atom Cu catalyst (Cu-SA/D-ZIS), which demonstrates remarkable catalytic performance with CO2 reduction rates of 112.5 μmol g-1  h-1 and water oxidation rates of 52.3 μmol g-1  h-1 , exhibiting a six-fold enhancement over D-ZIS. The structural characterization results indicated that the trapping effect of vacancy associates on single-atom copper led to the formation of an unsaturated coordination structure, Cu-S3 , consequently giving rise to the CuZn 'VS ⋅⋅VZn " defect complexes. FT-IR studies coupled with theoretical calculations reveal the spatially synergistic CO2 reduction and water oxidation on CuZn 'VS ⋅⋅VZn ", where the breakage of O-H in water oxidation is synchronized with the formation of *COOH, significantly lowering the energy barrier. Notably, this study introduces and, for the first time, substantiates the spatial synergy effect in CO2 reduction and H2 O oxidation through a combination of experimental and theoretical analyses, providing a fresh insight in optimizing photocatalytic system.

Accelerated Photocatalytic Carbon Dioxide Reduction and Water Oxidation under Spatial Synergy

AbstractPhotocatalytic conversion of CO2 and H2O into fuels and oxygen is a highly promising solution for carbon‐neutral recycling. Traditionally, researchers have studied CO2 reduction and H2O oxidation separately, overlooking potential synergistic interplay between these processes. This study introduces an innovative approach, spatial synergy, which encourages synergistic progress by bringing the two half‐reactions into atomic proximity. To facilitate this, we developed a defective ZnIn2S4‐supported single‐atom Cu catalyst (Cu−SA/D−ZIS), which demonstrates remarkable catalytic performance with CO2 reduction rates of 112.5 μmol g−1 h−1 and water oxidation rates of 52.3 μmol g−1 h−1, exhibiting a six‐fold enhancement over D−ZIS. The structural characterization results indicated that the trapping effect of vacancy associates on single‐atom copper led to the formation of an unsaturated coordination structure, Cu‐S3, consequently giving rise to the CuZn′VS⋅⋅VZn“ defect complexes. FT‐IR studies coupled with theoretical calculations reveal the spatially synergistic CO2 reduction and water oxidation on CuZn′VS⋅⋅VZn”, where the breakage of O−H in water oxidation is synchronized with the formation of *COOH, significantly lowering the energy barrier. Notably, this study introduces and, for the first time, substantiates the spatial synergy effect in CO2 reduction and H2O oxidation through a combination of experimental and theoretical analyses, providing a fresh insight in optimizing photocatalytic system.

Oxygen evolution reaction (OER) active sites in BiVO4 studied using density functional theory and XPS experiments.

Bismuth vanadate (BiVO4/BVO) has been widely studied as a photocatalytic water splitting semiconductor material in recent years because of its many advantages, such as its ease of synthesis and suitable band gap (2.4 eV). However, BVO still has some disadvantages, one of which is the low photocatalytic water oxidation activity. It is intriguing and unexpected to note that in the current literature, Bi atoms are taken as the oxygen evolution reaction (OER) active sites, while V metal atoms are not investigated in the OER, and the underlying reason for this remains unknown. In this work, using density functional theory (DFT) calculations and ab initio molecular dynamics simulations, we found that in BVO, the VO4 tetrahedron structure is very stable and there is strong surface reconstruction that leads to the V atoms on the surface having the same coordinates as in the bulk. For some high index surfaces, there are some theoretically predicted unsaturated V sites, but it is very easy to form a VO4 tetrahedron structure again by taking oxygen atoms from water. The other intermediates of OER are difficult to adsorb or desorb on this VO4 structure, which makes the V sites in BVO unsuitable as OER active sites. This VO4 structure remained stable during the molecular dynamics simulation at 300 and 673 K. The XPS characterization of various BVO morphologies validates our primary findings from DFT and molecular dynamics simulations. It reveals the presence of unsaturated Bi sites on the BVO surface, while unsaturated V sites are not observed. This study provides novel insights into the enhancement of OER activity of BVO and offers a fundamental understanding of OER activity in other photocatalysts containing V atoms.

Tunable Photocatalytic Activity of CoFe Prussian Blue Analogue Modified SrTiO3 Core-Shell Structures for Solar-Driven Water Oxidation.

This study presents a pioneering semiconductor-catalyst core-shell architecture designed to enhance photocatalytic water oxidation activity significantly. This innovative assembly involves the in situ deposition of CoFe Prussian blue analogue (PBA) particles onto SrTiO3 (STO) and blue SrTiO3 (bSTO) nanocubes, effectively establishing a robust p-n junction, as demonstrated by Mott-Schottky analysis. Of notable significance, the STO/PB core-shell catalyst displayed remarkable photocatalytic performance, achieving an oxygen evolution rate of 129.6 μmol g-1 h-1, with stability over an extended 9-h in the presence of S2O82- as an electron scavenger. Thorough characterization unequivocally verified the precise alignment of the band energies within the STO/PB core-shell assembly. Our research underscores the critical role of tailored semiconductor-catalyst interfaces in advancing the realm of photocatalysis and its broader applications in renewable energy technologies.

A construction of core–shell dual zeolite imidazole skeleton derived composite to facilitate photocarrier separation and distribution of active sites for photocatalytic water oxidation

Limited by the severe carrier recombination and insufficient active sites of the catalyst, achieving efficient photocatalytic water oxidation remains a major challenge. Herein, a core–shell zeolite imidazole skeleton (ZIF) based material with rich active sites in its interior is obtained by in-situ growth carbonization two steps method. According to characterization, performance testing and photoelectric experiments, it is confirmed that the ZIF67@ZIF8-2-800 material has good photogenerated carrier separation efficiency and surprising O2 production. The reason for the performance improved is that ZIF8 as a shell prevents the agglomeration of active sites CoO in the carbonization process of ZIF67. Theoretical calculations reveal that the core–shell structure has a favorable influence on the separation of photogenerated carriers. The N atom acts as an electron transport mediator, transferring electrons from the CoO core to the NC shell, while the holes remain in the CoO to participate in the photocatalytic water oxidation reaction.

ZrO2 modification of homogeneous nitrogen-doped oxide MgTa2O6−xNx for promoted photocatalytic water splitting

Homogeneous nitrogen-doped oxides are of wide visible light utilization for promising photocatalytic water splitting to produce hydrogen, but currently the poor charge separation severely limits their photocatalytic performances. In this work, a homogeneous nitrogen-doped tunneled oxide of MgTa2O6−xNx with an absorption edge of 570 nm was selected as a prototype to investigate the influence of ZrO2 modification on the charge separation as well as photocatalytic performance. It is interesting to observe that the formation of the reduced tantalum species, regarded as recombination centers, in the MgTa2O6−xNx sample could be effectively inhibited via the surface passivation with ZrO2 nanoparticles, based on which the photocatalytic water reduction and oxidation half-reaction activities could be remarkably promoted. Together with modification of the deposited Pt cocatalyst, the optimized H2 evolution rate over Pt-ZrO2/MgTa2O6−xNx (Zr/Ta = 0.10) photocatalyst was almost 4.5 times as high as that of the pristine Pt-MgTa2O6−xNx sample free of ZrO2 modification, whose apparent quantum yield at 420 nm (± 15 nm) achieved herein was superior to those of other reported homogeneous nitrogen-doped photocatalysts. The improved charge separation probably attributes to the introduction of Zr–O–Ta bond after ZrO2 modification, which is helpful to stabilize the tantalum species at more cationic state and inhibit the formation of the reduced tantalum species. This work extends the application territory of ZrO2 modification to the homogeneous nitrogen-doped oxide photocatalysts, and demonstrates its feasibility and effectiveness for remarkably enhanced photocatalytic water splitting performance.

Emergent CuWO4 Photoanodes for Solar Fuel Production: Recent Progress and Perspectives

Solar fuel production using a photoelectrochemical (PEC) cell is considered as an effective solution to address the climate change caused by CO2 emissions, as well as the ever-growing global demand for energy. Like all other solar energy utilization technologies, the PEC cell requires a light absorber that can efficiently convert photons into charge carriers, which are eventually converted into chemical energy. The light absorber used as a photoelectrode determines the most important factors for PEC technology—efficiency, stability, and the cost of the system. Despite intensive research in the last two decades, there is no ideal material that satisfies all these criteria to the level that makes this technology practical. Thus, further exploration and development of the photoelectode materials are necessary, especially by finding a new promising semiconductor material with a suitable band gap and photoelectronic properties. CuWO4 (n-type, Eg = 2.3 eV) is one of those emerging materials that has favorable intrinsic properties for photo(electro)catalytic water oxidation, yet it has been receiving less attention than it deserves. Nonetheless, valuable pioneering studies have been reported for this material, proving its potential to become a significant option as a photoanode material for PEC cells. Herein, we review recent progress of CuWO4-based photoelectrodes; discuss the material’s optoelectronic properties, synthesis methods, and PEC characteristics; and finally provide perspective of its applications as a photoelectrode for PEC solar fuel production.

PDIP/carbon paper photocatalyst sheet for enhanced photocatalytic water oxidation

Photocatalytic water splitting is a highly promising future energy technology. In contrast to the extensive work on particulate photocatalysts, there is still a lack of sufficient investigation for regularized photocatalysts. Here, from perylene diimide polymer (PDIP) and commercial carbon paper (CP), we develop a self-assembled PDIP/CP photocatalyst sheet that is easily scalable and can be used for photocatalytic water oxidation. Driven by strong interfacial π-π interactions, the PDIP spontaneously adsorbs onto the CP, which leads to a narrowed band gap, down-shifted VB edge, and enhanced separation of the photogenerated charge carriers of the PDIP. Under visible light, the PDIP/CP photocatalyst sheet shows significantly enhanced photocatalytic water oxidation activity (4 h cumulative oxygen evolution is 1.7 times higher than that of the powder-suspended system) and considerable cycling stability. The PDIP/CP photocatalyst sheet has the potential for large-scale device applications.