Solar-driven Photoelectrochemical Water Research Articles

A ternary-structured NiCo-LDH/Ni/BiVO4 photoanode with enhanced charge dynamics for photoelectrochemical water splitting

Solar-driven photoelectrochemical (PEC) water splitting is one of the promising technologies to produce green hydrogen as the carbon-free energy carrier. However, the ideal photoanode material BiVO4 still suffers from sluggish carrier dynamic problem. Here, NiCo-LDH/Ni/BiVO4 (NC/N/BVO) composite photoanode with a three-layer structure was successfully fabricated by introducing Ni layer followed by NiCo-LDH on BiVO4 by magnetron sputtering and electrochemical deposition, respectively. The optimized structure of NC/N/BVO exhibited a photocurrent of 4.15 mA cm−2 (1.23 VREH) in neutral solution, which was 2.8 times of pristine BiVO4. Besides, the photocurrent can be well maintained at 98 % for NC/N/BVO in 1h reaction, which dramatically decreases to 60 % for BiVO4. In this composite photoanode, NiCo-LDH as excellent water oxidation catalyst can effectively enhance the kinetic process of water oxidation on the surface, while the introduction of Ni layer can not only promote the following deposition of NiCo-LDH being a finer nanostructure with high surface area, but also increase the charge conduction efficiency and promote the charge transfer process between NiCo-LDH and BiVO4 substrate. The appropriate deposition sequence of Ni and NiCo-LDH layers ultimately highly improved the charge injection efficiency of NC/N/BVO resulting in a high performance of PEC water splitting.

Enhanced solar-driven photoelectrochemical water splitting of H/N co-doped TiO2: Role of defect states in a band gap reduction and promotion of charge transfer

Photoelectrodes based on reduced TiO2 are being extensively studied in the search for photocatalytic materials that can perform solar-driven water splitting and renewable hydrogen production. To date, substantial efforts have been devoted to understanding the microscopic mechanisms that underlie their photoelectrochemical (PEC) behavior, but this is a critical missing input to the Ti 3d carriers that govern the PEC activity. In this study the single and co-doping (N, H) in anatase TiO2 are prepared for PEC hydrogen production. The codoped photocathode delivers much better PEC performance from the enhanced solar light response and a fast electron pathway. Soft x-ray spectroscopy including x-ray absorption (XAS) and photoelectron spectroscopy (XPS) has been used to investigate the location and occupation of the defect levels from doping, through which the relevant engineered electronic properties in doped TiO2 are determined. It is shown that co-doping effectively produce the substitutional nitrogen in comparison with single doping. The Ti3+ defect states promoted by doping introduces localized Ti 3d-derived states below Fermi level (EF), resulting in a large reduction (approximately 1 eV) in the band gap of co-doped TiO2. The progressive production of oxygen vacancies eventually causes a surface band upward-bending induced electron transfer mechanism critical for charge separation. The present insights into defect chemistry and its determination to the electronic structure of co-doped TiO2 provide important guidance for using TiO2 in electrocatalysis and optoelectronics.

Fabrication of Flower-Shaped Sb2S3/Fe2O3 Heterostructures for Enhanced Photoelectrochemical Performance.

Antimony sulfide (Sb2S3) has been recognized as a catalytic material for splitting water by solar energy because of its suitable narrow band gap, high absorption coefficient, and abundance of elements. However, many deep-level defects in Sb2S3 result in a significant recombination of photoexcited electron-hole pairs, weakening its photoelectrochemical performance. Here, by using a simple hydrothermal and spin-coating method, we fabricated a step-scheme heterojunction of Sb2S3/α-Fe2O3 to improve the photoelectrochemical performance of pure Sb2S3. Our Sb2S3/α-Fe2O3 photoanode has a photocurrent density of 1.18 mA/cm2 at 1.23 V vs reversible hydrogen electrode, 1.39 times higher than that of Sb2S3 (0.84 mA/cm2). In addition, our heterojunction has a lower onset potential, a higher absorbance intensity, a higher incident photon-to-current conversion efficiency, a higher applied bias photon-to-current efficiency, and a lower charge transfer resistance compared to pure Sb2S3. Based on ultraviolet photoelectron spectroscopy, we constructed a step-scheme band structure of Sb2S3/α-Fe2O3 to explain its photoelectrochemical enhancement. This work offers a promising strategy to optimize the performance of Sb2S3 photoelectrodes for solar-driven photoelectrochemical water splitting.

Organic-inorganic p-type PEDOT:PSS/CuO/MoS2 photocathode with in-built antipodal photogenerated holes and electrons transfer pathways for efficient solar-driven photoelectrochemical water splitting

Organic PEDOT:PSS thin film and n-type MoS2 flakes were incorporated on CuO photocathode as the underlying layer and surface co-catalysts, respectively, establishing a rationally-designed novel integrated structure of PEDOT:PSS/CuO/MoS2. The organic-inorganic interface of PEDOT:PSS/CuO effectively shuttles photogenerated holes towards the FTO/PEDOT:PSS junction. Furthermore, the surface MoS2 co-catalysts form a p-n junction with CuO, which accelerates the transport of photogenerated electrons towards the photocathode/electrolyte junction, in addition to providing more reactive sites for the H2 evolution reaction. These synergistically formed antipodal charge transfer pathways have led to improved charge separation, rapid interfacial charge transfer kinetics and impeded electron-hole recombination in the PEDOT:PSS/CuO/MoS2 photocathode, which can achieve a photocurrent density of – 2.26 mA/cm2 at −0.6 V vs Ag/AgCl (2.1 times higher than that of the bare CuO photocathode). Analytical characterisations, electrochemical impedance spectroscopy (EIS) and intensity-modulated photocurrent spectroscopy (IMPS), also provide supporting evidence for its dramatically enhanced PEC water splitting performance.

Bifunctional Lead–Iron Oxyfluorides, 3D Cubic PbFeO2f and 2D Layered Pb3Fe2O5F2, Driving Photoelectrochemical and Electrochemical Water-Oxidation

Introduction Photoelectrochemical water splitting has attracted attention as a method of generating solar fuel such as hydrogen gas to be useful as a renewable energy carrier and a clean fuel of an internal‐combustion engine. For water oxidation of the half reaction in the water splitting, mixed-anion compounds have appeared as good candidates of the catalyst. In the mixed-anion compounds, a metal center is coordinated by several kind of anionic species. This environment induces their wide variety of physical and chemical properties not to be realized in single anion counterparts. The mixed-anion compounds possess visible-light responsibility and can utilize sunlight efficiently, therefore, which have fascinated photocatalyst researchers. The reason why they absorb visible light is the narrow bandgap with less electronegative anion species than oxygen. However, they are not very stable for photoelectrochemical water-oxidation because photogenerated holes oxidize the anion species except for oxygen in the compounds and cause degradation. Recently, we have reported an oxyfluoride Pb2Ti2O5.4F1.2 as a stable photoanode material that absorbs visible light at wavelengths up to ~500 nm.1 Oxyfluoride containing O2− and F− anions in the same phase is an example of the mixed-anion compounds. The other anion F− is less oxidized than O2−. Thus, the Pb2Ti2O5.4F1.2 photoanode showed essential stability toward the degradation by photogenerated holes exceptionally. However, this is the sole example of a visible-light-responsive oxyfluoride photoanode. Development of a new oxyfluoride photoanode absorbing visible light is important to gain the insight for water oxidation using the oxyfluorides. In the present work, another type of lead-iron oxyfluorides, PbFeO2F and Pb3Fe2O5F2, are applied to water oxidation as not only a photoanode but also an electrocatalyst.2,3 The lead-iron oxyfluoride, PbFeO2F, drives photoelectrochemical water-oxidation in visible light up to ~600 nm. In addition, this oxyfluoride functions as the electrocatalyst for water oxidation.2 In the electrochemical water-oxidation, another Pb3Fe2O5F2 shows higher performance for water oxidation than PbFeO2F. It seems that the crystal structure of two-dimensional layered perovskite Pb3Fe2O5F2 influences the superior performance to three-dimensional cubic perovskite PbFeO2F.3 Results and Discussion PbFeO2F and Pb3Fe2O5F2 powder were synthesized through a solid-state reaction and that in the evacuated glass tube, respectively.2,3 They were deposited on a fluorine-doped tin oxide (FTO) glass substrate by using electrophoresis method. The PbFeO2F or Pb3Fe2O5F2/FTO electrode was subjected to post-necking treatment to deposit TiO2 layer (TiO2/PbFeO2F or Pb3Fe2O5F2/FTO electrode), followed by electrodeposition of cobalt phosphate (Co-Pi) cocatalyst (Co-Pi/TiO2/PbFeO2F or Pb3Fe2O5F2/FTO electrode). Linear-sweep voltammetry for the as-prepared electrodes was conducted under intermittent visible-light irradiation (>400 nm) in 0.1 M K3PO4 solution (Figure 1A). The PbFeO2F/FTO electrode exhibited no photocurrent response. By contrast, a slight photocurrent response was observed for the TiO2/PbFeO2F/FTO electrode because of mainly improved interparticle conductivity in the electrode. Furthermore, a clear anodic photocurrent was observed for the Co-Pi/TiO2/PbFeO2F/FTO electrode. The Co-Pi cocatalyst, known as a water-oxidation promoter, improved the charge transfer at the electrode/water interface and charge separation in the electrode. Meanwhile, the Co-Pi/TiO2/PbFeO2F/FTO electrode exhibited an anodic photocurrent in visible light with longer wavelengths than ~600 nm. These tendencies were like those of Pb3Fe2O5F2 electrodes though the photocurrent were slightly higher than the PbFeO2F electrodes (Figure 1A, right). On contrary to the photoelectrochemical water-oxidation, a clear difference was observed when using those lead-iron oxyfluorides as an electrocatalyst. Under dark conditions, controlled-potential electrolysis with non-modified PbFeO2F and Pb3Fe2O5F2/FTO electrode was performed at +1.7 V vs. RHE (Figure 1B). The evolved O2 was detected by GC analysis in the measurement. The amount of that was almost one-fourth of electrons flowed during the electrolysis, which means the water oxidation was the major path for the electrochemical reaction. Besides, Pb3Fe2O5F2/FTO electrode showed 8 times higher activity than PbFeO2F. That reason has not been revealed but the difference is likely to be attributed to two-dimensional layered perovskite Pb3Fe2O5F2 and three-dimensional cubic perovskite PbFeO2F. References Hirayama, H. Nakata, H. Wakayama, S. Nishioka, T. Kanazawa, R. Kamata, Y. Ebato, K. Kato, H. Kumagai, A. Yamakata, K. Oka and K. Maeda, Solar-Driven Photoelectrochemical Water Oxidation over an n-Type Lead-Titanium Oxyfluoride Anode, J. Am. Chem. Soc., 141, 17158 (2019).Mizuochi, K. Izumi, Y. Inaguma and K. Maeda, A bifunctional lead–iron oxyfluoride, PbFeO2F, that functions as a visible-light-responsive photoanode and an electrocatalyst for water oxidation, RSC Adv., 11, 25616 (2021).Mizuochi, K. Oka, Y. Inaguma and K. Maeda, A two-dimensional perovskite oxyfluoride Pb3Fe2O5F2 as a catalyst for electrochemical oxidation of water to oxygen, Sustain. Energy Fuels, 6, 2423 (2022). Figure 1

Impact of NiCo2O4/SrTiO3 p-n Heterojunctions on the Interface of Photoelectrochemical Water Oxidation.

Forming semiconductor heterojunctions is a promising strategy to boost the efficiency of solar-driven photoelectrochemical (PEC) water splitting by accelerating the separation and transport of photogenerated charge carriers via an interfacial electric field. However, there is limited research considering the influence of electrolytes on the band alignment of the heterojunction under PEC conditions. In this work, we use a single crystal NiCo2O4/SrTiO3 (NCO/STO) heterojunction with atomic-precision controlled thickness as a model photoelectrode to study the band structure modulations upon getting in contact with the electrolyte and the correlation with the PEC activity. It is found that the band alignment can be tuned by the control of p-n heterojunction film thickness and regulated by the water redox potential (Eredox). When the Fermi level (EF) of the heterojunction is higher/lower than the Eredox, the band bending at the NCO/STO-electrolyte interface will increase/decrease after contacting with the electrolyte. However, when the band bending width of the NCO layer is thinner than its thickness, the electrolyte will not influence the band alignment at the NCO/STO interface. In addition, PEC characterization results show that the 1 nm NCO/STO heterojunction photoanode exhibits superior water-splitting performance, owing to the optimum band structure of the p-n heterojunction and the shorter charge transfer distance.

MOF-Derived In2 O3 /CuO p-n Heterojunction Photoanode Incorporating Graphene Nanoribbons for Solar Hydrogen Generation.

Solar-driven photoelectrochemical (PEC) water splitting is a promising approach toward sustainable hydrogen (H2 ) generation. However, the design and synthesis of efficient semiconductor photocatalysts via a facile method remains a significant challenge, especially p-n heterojunctions based on composite metal oxides. Herein, a MOF-on-MOF (metal-organic framework) template is employed as the precursor to synthesize In2 O3 /CuO p-n heterojunction composite. After incorporation of small amounts of graphene nanoribbons (GNRs), the optimized PEC devices exhibited a maximum current density of 1.51mA cm-2 (at 1.6V vs RHE) under one sun illumination (AM 1.5G, 100mW cm-2 ), which is approximately four times higher than that of the reference device based on only In2 O3 photoanodes. The improvement in the performance of these hybrid anodes is attributed to the presence of a p-n heterojunction that enhances the separation efficiency of photogenerated electron-hole pairs and suppresses charge recombination, as well as the presence of GNRs that can increase the conductivity by offering better path for electron transport, thus reducing the charge transfer resistance. The proposed MOF-derived In2 O3 /CuO p-n heterojunction composite is used to demonstrate a high-performance PEC device for hydrogen generation.

Construction of WO3 quantum dots/TiO2 nanowire arrays type II heterojunction via electrostatic self-assembly for efficient solar-driven photoelectrochemical water splitting.

Construction of a heterojunction between quantum dots and TiO2 nanowire arrays via electrostatic self-assembly is rarely reported. In this work, mercury lamp irradiation was used to change the surface potential of WO3 quantum dots and TiO2 nanowire arrays, resulting in WO3 quantum dots tightly attached on the surface of TiO2 nanowire through electrostatic self-assembly. Photoelectrochemical measurements showed that the WO3 quantum dots formed a type II heterojunction with the TiO2 nanowire arrays rather than serving as carrier-trapping sites. In the self-assembly system, the TiO2 nanowire arrays provide a charge-transfer channel for the WO3 quantum dots, greatly improving the contribution of the WO3 quantum dots to the photocurrent. Quantitative calculations showed that the improvement of the bulk carrier-separation efficiency was the reason for the enhanced photoelectrochemical performance of the self-assembled system. The photocurrent density of the optical self-assembled system at 1.23 V (vs. RHE) was ∼5.5 times as high as that of the TiO2 nanowire arrays. More importantly, the self-assembled system exhibited excellent photoelectrochemical stability.

Advanced oxygen evolution reaction catalysts for solar-driven photoelectrochemical water splitting

Herein, we summarize the recent developments in structure optimizations of oxygen evolution reaction catalysts for promoting photoelectrochemical water splitting performances.

Fe Substitutions Improve Spectral Response of Bi2WO6-Based Photoanodes

The quest for a scalable solar fuel technology has stimulated a concerted effort to develop a metal oxide semiconductor for solar-driven photoelectrochemical water oxidation (oxygen evolution reaction) in an efficient and durable manner. So far, the search for such a metal oxide photoanode has highlighted the promise of Bi-based oxides, which have also been extensively studied for other photocatalyst applications. Bi2WO6 is a durable photocatalyst whose primary shortcoming is a 2.8 eV band gap that limits utilization of the solar spectrum. Improvements in visible photoresponse upon incorporation of Fe have been reported in the photocatalysis literature, motivating our use of high-throughput synthesis and photoelectrochemistry to determine the spectral photoresponse for Bi–W–Fe oxides synthesized under nonequilibrium conditions based on thermal oxidation of metallic films. Photoactivity down to 2 eV was achieved over a broad range of compositions, with detailed characterization of optimal compositions revealing that Fe incorporation increases the valence band position by 0.75 eV. Density functional theory calculations of Fe substitutions on W sites in Bi2WO6 are consistent with this valence band shift, providing a plausible explanation for the experiments. This Fe-mediated band tuning yields a ca. 2 eV band gap while retaining a turn-on potential for photoanodic current near 0.4 V versus RHE, which combined with the operational durability motivates continuous study and development of this promising class of metal oxide photoanodes.

Interfacial engineering of 1D/2D heterostructured photoanode for efficient photoelectrochemical water splitting

Solar-driven photoelectrochemical (PEC) water splitting for hydrogen generation is regarded as a sustainable strategy to relieve fossil resource issue. However, its PEC conversion efficiency still suffers from the low light absorption and high electron–hole recombination. Herein, we report 1D/2D hierarchical heterostructured photoelectrode constructed by ordered ZnO nanorod array and intimately attached ultra-thin Hematene (thickness of monolayer: 1–2 nm) for effective PEC water oxidation with visible light irradiation. The onset potential of Hematene/ZnO NRs photoanode (0.28 V versus RHE) for PEC water oxidation has an obvious negative shift compared with that of ZnO NRs (0.32 V versus RHE) indicating the enhanced PEC kinetics. Furthermore, reduced charge transport resistance (18.82 KΩ cm−2), a high carrier density of 9.03 × 1018 cm−3 and the resulting significantly enhanced incident photon-to-current efficiency enhancement compared with ZnO NRs photoanode were obtained for Hematene/ZnO NRs photoanode. All these were ascribed to the formation of large built-in electric field which was arising from the charge redistribution at the ZnO and Hematene interface, and the band alignment engineering between the components. In summary, such interfacial engineering may inspire the future development of 1D/2D hierarchical heterostructured photoanodes in the field of PEC water splitting.

Machine Learning Guided Dopant Selection for Metal Oxide-Based Photoelectrochemical Water Splitting: The Case Study of Fe2 O3 and CuO.

Doping is an effective strategy for tuning metal oxide-based semiconductors for solar-driven photoelectrochemical (PEC) water splitting. Despite decades of extensive research effort, the dopant selection is still largely dependent on a trial-and-error approach. Machine learning (ML) is promising in providing predictable insights on the dopant selection for high-performing PEC systems because it can uncover correlations from the seemingly ambiguous linkages between vast features of dopants and the PEC performance of doped photoelectrodes. Herein, the authors successfully build ML model to predict the doping effect of 17 metal dopants into hematite (Fe2 O3 ), a prototype photoelectrode material. Their findings disclose the critical parameters from the 10 intrinsic features of each dopant. The model is further experimentally validated by the coherent prediction on Y and La dopants' behaviors. Further interpretation of the ML model suggests that the chemical state is the most significant selection criteria, meanwhile, dopants with higher metal-oxygen bond formation enthalpy and larger ionic radius are favored in improving the charge separation and transfer (CST) in the Fe2 O3 photoanodes. The generic feature of this ML guided selection criteria has been further extended to CuO-based photoelectrodes showing improved CST by alkaline metal ions doping.

Surface plasmon resonance metal-coupled biomass carbon modified TiO2 nanorods for photoelectrochemical water splitting

Exploring efficient and stable photoanode materials is a necessary link to realize the practical application of solar-driven photoelectrochemical (PEC) water splitting. Hence, we prepared rutile TiO 2 nanorods, with a width of 50 nm, which was growth in situ on carbon cloth (TiO 2 @CC) by hydrothermal reaction. And then, Ag nanoparticles (NPs) and biomass N,S-C NPs were chosen for the additional modification of the fabricated TiO 2 nanorods to produce broccoli-like Ag-N,S-C/TiO 2 @CC nanocomposites. According to the result of ultraviolet–visible diffuse reflectance spectroscopy (UV–vis) and PEC water splitting performance tests, Ag-N,S-C/TiO 2 @CC broadens the absorption region of TiO 2 @CC from the ultraviolet region to the visible region. Under AM 1.5G solar light irradiation, the photocurrent density of Ag-N,S-C/TiO 2 @CC is 89.8 μA·cm −2 , which is 11.8 times higher than TiO 2 @CC. Under visible light irradiation, the photocurrent density of Ag-N,S-C/TiO 2 @CC reaches to 12.6 μA·cm −2 , which is 21.0 times higher than TiO 2 @CC. Moreover, Ag-N,S-C/TiO 2 @CC shows a photocurrent responses in full pH range. It can be found that Ag NPs and N, S-C NPs play key roles in broaden the absorption range of TiO 2 nanorods to the visible light region and, promote the occurrence of PEC water oxidation reaction due to the surface plasmon resonance effect of Ag NPs and the synergistic effect of N,S-C NPs. The mechanism demonstrated that Ag-N,S-C/TiO 2 @CC can separate the photogenerated electron-hole pairs effectively and transfer the photogenerated electrons to the photocathode (Pt plate) in time. This research provides a new strategy for exploration surface plasma metal coupled biomass carbon materials in the field of PEC water splitting.

A Bifunctional Lead–Iron Oxyfluoride, PbFeO2F, That Drives Photoelectrochemical and Electrochemical Water Oxidation

Introduction Photoelectrochemical water splitting has attracted attention as a method of generating solar fuel, such as hydrogen that is expected to be utilize as a renewable energy carrier and clean fuel of an internal‐combustion engine.1 In the photoanode materials reported so far, ordinary metal oxides require ultraviolet light for operation because of their wide bandgaps (>3 eV), and visible-light-responsive metal oxides need an additional electrochemical bias because their conduction-band minimum is a lower position than the H+/H2 reduction potential. Mixed-anion compounds fascinating recent photocatalyst researchers possess visible-light response because of a narrow bandgap with less electronegative anion species.1,2 However, they are not very stable for water oxidation, because photogenerated holes oxidize the anion species except for oxygen in the compounds. Recently, we have reported an oxyfluoride Pb2Ti2O5.4F1.2 as a stable photoanode material that absorbs visible light at wavelengths as long as ~500 nm.3 The VBM of Pb2Ti2O5.4F1.2 is mainly composed by the O 2p orbitals. As the result, the Pb2Ti2O5.4F1.2 photoanode is essentially stable toward self-oxidation by photogenerated holes. However, this is the sole example of a visible-light-responsive oxyfluoride photoanode. Development of a new oxyfluoride photoanode absorbing visible light is important for enabling the further design of visible-light-responsive photoanode materials. In the present work, a lead–iron oxyfluoride PbFeO2F is applied to a photoanode material and electrocatalyst for water-oxidation. PbFeO2F, which can be synthesized by a high-pressure method,4 has been reported to show a yellow colour. Thus, it is expected to function as a visible-light-responsive photoanode material. Moreover, PbFeO2F containing Fe cation is possible to provide catalytic performance for water oxidation, which means that this material may also function as an electrocatalyst. Results and Discussion According to the previously reported method,4 PbFeO2F powder was synthesized. It was deposited on a fluorine-doped tin oxide (FTO) glass substrate by electrophoresis. The PbFeO2F/FTO electrode was subjected to post-necking treatment by immersing in 0.1 M Ti{OCH(CH3)2}4 –isopropanol solution to deposit TiO2 layer (TiO2/PbFeO2F/FTO electrode), followed by electrodeposition of cobalt phosphate (Co-Pi) cocatalyst (Co-Pi/TiO2/PbFeO2F/FTO electrode). Linear-sweep voltammetry of the as-prepared electrodes in 0.1 M K3PO4 solution was conducted under intermittent visible-light irradiation (Figure 1A). The PbFeO2F/FTO electrode exhibited no photocurrent response. By contrast, a slight photocurrent response was observed for the TiO2/PbFeO2F/FTO electrode because of mainly improved interparticle conductivity in the electrode. Furthermore, a clear anodic photocurrent was observed for the Co-Pi/TiO2/PbFeO2F/FTO electrode. Loading the Co-Pi cocatalyst, known as a water-oxidation promoter, improved charge transfer at the electrode/water interface and charge separation from the surface to the bulk. Besides, the Co-Pi/TiO2/PbFeO2F/FTO electrode exhibited an anodic photocurrent under visible-light irradiation with wavelengths as long as ~600 nm. It indicates that PbFeO2F can function as a photoanode material under a wide range of visible-light wavelengths. Controlled-potential electrolysis with the as-prepared PbFeO2F/FTO electrode was operated at +1.7 V vs. RHE under dark conditions (Figure 1B). The evolved O2 was observed by GC analysis in the measurement. It was almost one-fourth the amount of electrons, which flowed during the electrolysis, giving a high Faradaic efficiency of 97%. This result means that the water oxidation was the major path at the PbFeO2F/FTO electrode. In addition, α-Fe2O3/FTO electrode does not work at this potential because of the larger overpotential than the PbFeO2F/FTO electrode for water oxidation. It reveals that PbFeO2F can also function as an electrocatalyst at a relatively low overpotential for water oxidation. References Seo, H. Nishiyama, T. Yamada and K. Domen, Visible-Light-Responsive Photoanodes for Highly Active, Stable Water Oxidation, Angew. Chem. Int. Ed., 57, 8396 (2018).Miyoshi and K. Maeda, Recent Progress in Mixed‐Anion Materials for Solar Fuel Production, Solar RRL, in press.Hirayama, H. Nakata, H. Wakayama, S. Nishioka, T. Kanazawa, R. Kamata, Y. Ebato, K. Kato, H. Kumagai, A. Yamakata, K. Oka and K. Maeda, Solar-Driven Photoelectrochemical Water Oxidation over an n-Type Lead-Titanium Oxyfluoride Anode, J. Am. Chem. Soc., 141, 17158 (2019).Inaguma, J.-M. Greneche, M.-P. Crosnier-Lopez, T. Katsumata, Y. Calage and J.-L. Fourquet, Structure and Mössbauer Studies of F−O Ordering in Antiferromagnetic Perovskite PbFeO2F, Chem. Mater., 17, 1386 (2005). Figure 1

A sustainable molybdenum oxysulphide-cobalt phosphate photocatalyst for effectual solar-driven water splitting

IntroductionHydrogen is considered as a clean alternative green energy future fuel. Since the Honda-Fujishima effect for photoelectrochemical water splitting is known, there has been a substantial boost in this field. Numerous photocatalysts based on metals, semiconductors, and organic-inorganic hybrid-systems have been proposed. Several factors limit their efficiency, e.g., a stable PEC-WS setup, absorbing visible light, well-aligned band energy for charge transfer, electrons and holes, and their separation to avoid recombination and limited water redox reactions. Metallic doping and impregnation of stable and efficient co-catalysts such as Pt, Ag, and Au showed enhanced PEC-WS. We used Cobalt-based co-catalyst with molybdenum oxysulfide photocatalyst for effectual solar-driven water splitting. ObjectivesTo develop photocatalysts for efficient PEC processes capable of absorbing sufficient visible light, good band energy for effective charge transfer, inexpensive, significant solar-to-chemical energy conversion efficiencies. Above all, it is developing such PEC-WS systems that will be commercially viable for renewable energy resources. MethodsWe prepared Molybdenum oxysulphide-cobalt phosphate photocatalyst for PEC-WS through a facile hydrothermal route using ammonium heptamolybdate, thiourea, and metallic Cobalt precursors. ResultsAn effectual photocatalyst is produced for solar-driven water splitting. The conformal morphology of MoOxSy-CoPi nanoflowers is a significant feature, as observed under FE-SEM and HR-TEM. XRD confirmed the degree of purity and orthorhombic crystal structure of MoOxSy-CoPi. EDX and XPS identify the elemental compositions and corresponding oxidation states of each atom. A 2.44 eV band-gap energy is calculated for MoOxSy-CoPi from the diffused reflectance spectrum. Photo- Electrochemical Studies (PEC) under 1-SUN solar irradiation revealed 7-8 folds enhanced photocurrent (∼ 3.5 mA/cm2) generated from MoOxSy-CoPi/FTO in comparison to Co-PI/FTO (∼ 0.5 mA/cm2) and MoOxSy-/FTO respectively, within 0.5 M Na2SO4 electrolyte (@pH=7) and standard three electrodes electrochemical cell. ConclusionOur results showed MoOxSy-CoPi as promising photocatalyst material for improved solar-driven photoelectrochemical water splitting system.

Thermal Treatment of Polyvinyl Alcohol for Coupling MoS2 and TiO2 Nanotube Arrays toward Enhancing Photoelectrochemical Water Splitting Performance

Solar-driven photoelectrochemical (PEC) water splitting, using semiconductor photoelectrodes, is considered a promising renewable energy source and solution for environmental sustainability. Herein, we report polyvinyl alcohol (PVA) as a binder material for combining MoS2 and TiO2 nanotube arrays (TNAs) to improve PEC water splitting ability. By a thermal treatment process, the formation of the π conjunction in the PVA structure enhanced the PEC performance of MoS2/TNAs, exhibiting linear sweeps in an anodic direction with the current density over 65 μA/cm2 at 0 V vs. Ag/AgCl. Besides, the photoresponse ability of MoS2/TNAs is approximately 6-fold more significant than that of individual TNAs. Moreover, a Tafel slope of 140.6 mV/decade has been obtained for the oxygen evolution reaction (OER) of MoS2/TNAs materials.

Benchmarking of oxygen evolution catalysts on porous nickel supports

Summary Active and inexpensive oxygen evolution reaction (OER) electrocatalysts are needed for energy-efficient electrolysis applications. Objective comparison between OER catalysts has been blurred by the use of different supports and methods to evaluate performance. Here, we selected nine highly active transition-metal-based catalysts and described their synthesis, using a porous nickel foam and a new Ni-based dendritic material as the supports. We designed a standardized protocol to characterize and compare the catalysts in terms of structure, activity, density of active sites, and stability. NiFeSe- and CoFeSe-derived oxides showed the highest activities on our dendritic support, with low overpotentials of η100 ≈ 247 mV at 100 mA cm–2 in 1 M KOH. Stability evaluation showed no surface leaching for 8 h of electrolysis. This work highlights the most active anode materials and provides an easy way to increase the geometric current density of a catalyst by tuning the porosity of its support.

Activation of Ni2V2O7 to nonstoichiometric NiV3O8 for solar-driven photoelectrochemical water oxidation

Hydrogen treatment is an effective strategy to introduce non-stoichiometry and improve the performance of semiconductor nanomaterials for photocatalytic applications. Herein, for the first time, we report the hydrogen treatment activation of non-photoactive nickel vanadate (NV) towards photoelectrochemical (PEC) water oxidation. The NV nanostructures are synthesized by a sonication-assisted hydrothermal method. Hydrogen-treated nickel vanadate (H-NV) nanoflakes were achieved by subjecting the NV to anneal at 350 °C for 4 h in a hydrogen atmosphere. Field emission scanning electron microscopy (FESEM), and High resolution transmission electron microscopy (HRTEM) indicates irregular network morphology for the as-synthesized NV nanostructures, calcined at 500 °C (NV-500). The XRD pattern confirms monoclinic and orthorhombic crystal phases for NV-500 and hydrogen treated nickel vanadate (H-NV-500), respectively. The defects states produced on the surface of NV-500 after high dose of electrons which implies the creation of oxygen vacancies and consistent with the XPS analysis for H-NV-500. The optical properties of H-NV-500 via UV-Vis/DRS show significant absorption in the visible regime at λ = 628 nm with an indirect bandgap value of 2.15 eV from Tauc’s plot and supports by density functional theory (DFT) studies. The PEC water oxidation performance has onset potential at ~0.74 V. The photocurrent density at saturation is ~2.13 μA/cm2 for H-NV-500 photoanode. These results suggest that hydrogen treatment effectively activated NV towards PEC water oxidation process, which was initially inactive.

3D interconnected nanoporous Ta3N5 films for photoelectrochemical water splitting: thickness-controlled synthesis and insights into stability

Solar-driven photoelectrochemical (PEC) water splitting is a promising technology for sustainable hydrogen production, which relies on the development of efficient and stable photoanodes for water oxidation reaction. The thickness and microstructure of semiconductor films are generally crucial to their PEC properties. Herein, three-dimensional (3D) interconnected nanoporous Ta3N5 film photoanodes with controlled thickness were successfully fabricated via galvanostatic anodization and NH3 nitridation. The porous Ta3N5 nanoarchitectures (NAs) of 900 nm in thickness showed the highest PEC performance due to the optimal light-harvesting and charge separation. Compared with the hole-induced photocorrosion, the electrochemical oxidation at high anodic potentials resulted in severer performance degradation of Ta3N5. Although the surface oxide layer on deteriorated Ta3N5 photoanodes could be removed by NH3 re-treatment, the PEC performance was only partially recovered. As an alternative, anchoring a dual-layer Co(OH)x/CoOOH co-catalyst shell on the porous Ta3N5 NAs demonstrated substantially enhanced PEC performance and stability. Overall, this work provides reference to controllably fabricate 3D nanoporous Ta3N5-based photoanodes for efficient and stable PEC water splitting via optimizing the light absorption, hole extraction, charge separation and utilization.

Stable and efficient solar-driven photoelectrochemical water splitting into H2 and O2 based on a BaTaO2N photoanode decorated with CoO microflowers.

Stable and efficient photoelectrochemical water splitting has been achieved using a BaTaO2N photoanode decorated with CoO microflowers. The CoO microflowers effectively collect holes from BaTaO2N which kinetically protects BaTaO2N against photocorrosion. A Faraday efficiency of almost unity (99.2%) has been recorded for O2 evolution reactions. The tips of the CoO microflowers are the most active sites for water oxidation reactions.