Ultrathin FeOOH Nanolayers with Abundant Oxygen Vacancies on BiVO4 Photoanodes for Efficient Water Oxidation

Photoelectrochemical (PEC) water splitting is a promising method for storing solar energy in the form of hydrogen fuel, but it is greatly hindered by the sluggish kinetics of the oxygen evolution reaction (OER). Herein, a facile solution impregnation method is developed for growing ultrathin (2 nm) highly crystalline β‐FeOOH nanolayers with abundant oxygen vacancies on BiVO₄ photoanodes. These exhibited a remarkable photocurrent density of 4.3 mA cm^?2 at 1.23 V (vs. reversible hydrogen electrode (RHE), AM 1.5 G), which is approximately two times higher than that of amorphous FeOOH fabricated by electrodeposition. Systematic studies reveal that the excellent PEC activity should be attributed to their ultrathin crystalline structure and abundant oxygen vacancies, which could effectively facilitate the hole transport/trapping and provide more active sites for water oxidation.     

Morphology Engineering of BiVO4 with CoOx Derived from Cobalt-containing Polyoxometalate as Co-catalyst for Oxygen Evolution

Bismuth vanadate (BiVO₄) as a metal oxidation semiconductor has stimulated extensive attention in the photocatalytic water splitting field. However, the poor transport ability and easy recombination of charge carriers limit photocatalytic water oxidation activity of pure BiVO₄. Herein, the photocatalytic activity of BiVO₄ is enhanced via adjusting its morphology and combination co-catalyst. First, the Cu-BiVO₄ was synthesized by copper doping to control the growth of {110} facet of BiVO₄, which is regarded for the separation of photo-generated charge carriers. Then the CoO_x in-situ generated from K₆[SiCo^II(H₂O)W₁₁O₃₉] ⋅ 16H₂O was photo-deposited on Cu-BiVO₄ surface as co-catalyst to speed up reaction kinetics. Cu-BiVO₄@CoO_x hybrid catalyst shows highest photocatalytic activity and best stability among all the prepared catalysts. Oxygen evolution is about 34.6 μmol in pH 4 acetic acid buffer under 420 nm LED irradiation, which is nearly 20 times higher than that of pure BiVO₄. Apparent quantum efficiency (AQE) in 1 h and O₂ yield are 1.83% and 23.1%, respectively. O₂ evolution amount nearly maintains the original value even after 5 cycles.     

Boosting the Photoactivity of BiVO4 Photoanodes by a ZnCoFe-LDH Thin Layer for Water Oxidation

Monoclinic bismuth vanadate (BiVO₄) has been used as an efficient photoanode material for photoelectrochemical water oxidation owing to its suitable band gap and nontoxicity. Nevertheless, the practical application of BiVO₄ photoanode has been severely limited by the surface charge recombination and sluggish kinetic, which leads to the obtained photoactivity of BiVO₄ is much lower than its theoretical value. In this case, ZnCoFe-LDH thin layer is conformally decorated on the porous BiVO₄ photoanode through a simple electrodeposition process. The results show that a boosted photoactivity and a remarkably enhanced photocurrent density (3.43 mA cm⁻² at 1.23 V_RHE) are attained for BiVO₄/ZnCoFe-LDH. In addition, the optimized BiVO₄/ZnCoFe-LDH photoanode exhibits significant negative shift in the onset potential (0.51 V_RHE to 0.21 V_RHE), promotes charge separation efficiency (49.3% to 60.4% in the bulk, 29.6% to 61.9% on the surface at 1.23 V_RHE) and enhanced IPCE efficiency (25.5% to 54.7% at 425 nm) compared with that of bare BiVO₄ photoanode. It is demonstrated that the boosted photoactivity of BiVO₄/ZnCoFe-LDH photoanode is mainly ascribed to the synergy effects of the formation of p-n heterojunction between ZnCoFe-LDH and BiVO₄ to accelerate the photogenerated charge transfer and separation, broaden light absorption, as well as promote the surface water oxidation kinetics.     

Towards Long‐Term Photostability of Nickel Hydroxide/BiVO4 Photoanodes for Oxygen Evolution Catalysts via In Situ Catalyst Tuning

Increasing long‐term photostability of BiVO₄ photoelectrode is an important issue for solar water splitting. The NiOOH oxygen evolution catalyst (OEC) has fast water oxidation kinetics compared to the FeOOH OEC. However, it generally shows a lower photoresponse and poor stability because of the more substantial interface recombination at the NiOOH/BiVO₄ junction. Herein, we utilize a plasma etching approach to reduce both interface/surface recombination at NiOOH/BiVO₄ and NiOOH/electrolyte junctions. Further, adding Fe²⁺ into the borate buffer electrolyte alleviates the active but unstable character of etched‐NiOOH/BiVO₄, leading to an outstanding oxygen evolution over 200 h. The improved charge transfer and photostability can be attributed to the active defects and a mixture of NiOOH/NiO/Ni in OEC induced by plasma etching. Metallic Ni acts as the ion source for the in situ generation of the NiFe OEC over long‐term durability.     

Insight into the Key Restriction of BiVO4 Photoanodes Prepared by Pyrolysis Method for Scalable Preparation

Bismuth Vanadate (BiVO₄) photoanode has been popularly investigated for promising solar water oxidation, but its intrinsic performance has been greatly retarded by the direct pyrolysis method. Here we insight the key restriction of BiVO₄ prepared by metal–organic decomposition (MOD) method. It is found that the evaporation of vanadium during the pyrolysis tends to cause a substantial phase impurity, and the unexpected few tetragonal phase inhibits the charge separation evidently. Consequently, suitably excessive vanadium precursor was adopted to eliminate the phase impurity, based on which the obtained intrinsic BiVO₄ photoanode could exhibit photocurrent density of 4.2 mA cm⁻² at 1.23 V_RHE under AM 1.5 G irradiation, as comparable to the one fabricated by the currently popular two-step electrodeposition method. Furthermore, the excellent performance can be maintained on the enlarged photoanode (25 cm²), demonstrating the advantage of MOD method in scalable preparation. Our work provides new insight and highlights the glorious future of MOD method for the design of scale-up efficient BiVO₄ photoanode.     

Unveiling the Activity and Stability Origin of BiVO4 Photoanodes with FeNi Oxyhydroxides for Oxygen Evolution

Understanding the origin of formation and active sites of oxygen evolution reaction (OER) cocatalysts is highly required for solar photoelectrochemical (PEC) devices that generate hydrogen efficiently from water. Herein, we employed a simple pH-modulated method for in situ growth of FeNi oxyhydroxide ultrathin layers on BiVO₄ photoanodes, resulting in one of the highest currently known PEC activities of 5.8 mA cm⁻² (1.23 V_RHE, AM 1.5 G) accompanied with an excellent stability. More importantly, both comparative experiments and density functional theory (DFT) studies clearly reveal that the selective formation of Bi−O−Fe interfacial bonds mainly contributes the enhanced OER activities, while the construction of V−O−Ni interfacial bonds effectively restrains the dissolution of V⁵⁺ ions and promotes the OER stability. Thereby, the synergy between iron and nickel of FeNi oxyhydroxides significantly improved the PEC water oxidation properties of BiVO₄ photoanodes.     

Electrodeposited Amorphous Tungsten‐doped Cobalt Oxide as an Efficient Catalyst for the Oxygen Evolution Reaction

Thin film of amorphous tungsten‐doped cobalt oxide (W:CoO) was successfully grown on a conducting electrode via an electrochemical oxidation process employing a [Co(WS₄)₂]^2? deposition bath. The W:CoO catalyst displays an attractive performance for the oxygen evolution reaction in an alkaline solution. In an NaOH solution of pH 13, W:CoO operates with a moderate onset overpotential of 230 mV and requires 320 mV overpotential to generate a catalytic current density of 10 mA cm^?2. A low Tafel slope of 45 mV decade^?1 was determined, indicating a rapid O₂‐evolving kinetics. The as‐prepared W:CoO belongs to the best cobalt oxide‐based catalysts ever reported for the oxygen evolution (OER) reaction.     

A Low‐Temperature Molecular Precursor Approach to Copper‐Based Nano‐Sized Digenite Mineral for Efficient Electrocatalytic Oxygen Evolution Reaction

In the urge of designing noble metal‐free and sustainable electrocatalysts for oxygen evolution reaction (OER), herein, a mineral Digenite Cu₉S₅ has been prepared from a molecular copper(I) precursor, [{(PyHS)₂Cu^I(PyHS)}₂](OTf)₂ ( 1 ), and utilized as an anode material in electrocatalytic OER for the first time. A hot injection of 1 yielded a pure phase and highly crystalline Cu₉S₅, which was then electrophoretically deposited (EPD) on a highly conducting nickel foam (NF) substrate. When assessed as an electrode for OER, the Cu₉S₅/NF displayed an overpotential of merely 298±3 mV at a current density of 10 mA cm^?2 in alkaline media. The overpotential recorded here supersedes the value obtained for the best reported Cu‐based as well as the benchmark precious‐metal‐based RuO₂ and IrO₂ electrocatalysts. In addition, the choronoamperometric OER indicated the superior stability of Cu₉S₅/NF, rendering its suitability as the sustainable anode material for practical feasibility. The excellent catalytic activity of Cu₉S₅ can be attributed to the formation of a crystalline CuO overlayer on the conductive Cu₉S₅ that behaves as active species to facilitate OER. This study delivers a distinct molecular precursor approach to produce highly active copper‐based catalysts that could be used as an efficient and durable OER electro(pre)catalysts relying on non‐precious metals.     

A Stable Integrated Photoelectrochemical Reactor for H2 Production from Water Attains a Solar‐to‐Hydrogen Efficiency of 18 % at 15 Suns and 13 % at 207 Suns

The major challenge in solar water splitting to H₂ and O₂ is in making a stable and affordable system for large‐scale applications. We have designed, fabricated, and tested a photoelectrochemical reactor characterized as follows: 1) it comprises an integrated device to reduce the balance of the system cost, 2) it utilizes concentrated sunlight to reduce the photoabsorber cost, and 3) it employs and alkaline electrolyte to reduce catalyst cost and eliminate external thermal management needs. The system consists of an III‐V‐based photovoltaic cell integrated with Ni foil as an O₂ evolution catalyst that also protects the cell from corrosion. At low light concentration, without the use of optical lenses, the solar‐to‐hydrogen (STH) efficiency was 18.3 %, while at high light concentration (up to 207 suns) with the use of optical lenses, the STH efficiency was 13 %. Catalytic tests conducted for over 100 hours at 100–200 suns showed no sign of degradation nor deviation from product stoichiometry (H₂/O₂=2). Further tests projected a system stability of years.     

Preparation of BiVO4/MIL‐125(Ti) composite with enhanced visible‐light photocatalytic activity for dye degradation

Because of their desired features, including very specific surface areas and designable framework architecture together with their possibility to be functionalized, Metal Framework (MOF) is a promising platform for supporting varied materials in respect of catalytic applications in water treatment. In this work, a novel visible‐light‐responsive photocatalyst that comprised BiVO₄ together with MIL‐125(Ti), was synthesized by a two‐step hydrothermal approach. The characterization of as‐obtained samples as performed by X‐ray diffraction, scanning electron microscopy, high resolution transmission electron microscopy, Fourier transform infrared spectroscope, X‐ray photoelectron spectroscopy and ultraviolet‐visible diffuse reflection spectra. Rhodamine B was selected being a target for the evaluation of the photocatalytic function of as‐developed photocatalyst. The photocatalytic reaction parameters, for example, the content of BiVO₄ as well as initial concentration of Rhodamine B was researched. The composite photocatalyst possessing Bi:Ti molar ratio of 3:2 brought to light the fact that the greatest photocatalytic activity had the ability to degrade 92% of Rhodamine B in 180 min. In addition to that, the BiVO₄/MIL‐125(Ti) composite could keep its photocatalytic activity during the recycling test. The phenomenon of disintegration of the photo‐generated charges in the BiVO₄/MIL‐125(Ti) composite was brought to discussion as well.     

Dimension‐Matched Zinc Phthalocyanine/BiVO4 Ultrathin Nanocomposites for CO2 Reduction as Efficient Wide‐Visible‐Light‐Driven Photocatalysts via a Cascade Charge Transfer

Cascade charge transfer was realized by a H‐bond linked zinc phthalocyanine/BiVO₄ nanosheet (ZnPc/BVNS) composite, which subsequently works as an efficient wide‐visible‐light‐driven photocatalyst for converting CO₂ into CO and CH₄, as shown by product analysis and ¹³C isotopic measurement. The optimized ZnPc/BVNS nanocomposite exhibits a ca. 16‐fold enhancement in the quantum efficiency compared with the reported BiVO₄ nanoparticles at the excitation of 520 nm with an assistance of 660 nm photons. Experimental and theoretical results show the exceptional activities are attributed to the rapid charge separation by a cascade Z‐scheme charge transfer mechanism formed by the dimension‐matched ultrathin (ca. 8 nm) heterojunction nanostructure. The central Zn²⁺ in ZnPc could accept the excited electrons from the ligand and then provide a catalytic function for CO₂ reduction. This Z‐scheme is also feasible for other MPc, such as FePc and CoPc, together with BVNS.     

Fabricating Dual‐Atom Iron Catalysts for Efficient Oxygen Evolution Reaction: A Heteroatom Modulator Approach

Understanding the thermal aggregation behavior of metal atoms is important for the synthesis of supported metal clusters. Here, derived from a metal–organic framework encapsulating a trinuclear Fe^III₂Fe^II complex (denoted as Fe₃) within the channels, a well‐defined nitrogen‐doped carbon layer is fabricated as an ideal support for stabilizing the generated iron nanoclusters. Atomic replacement of Fe^II by other metal(II) ions (e.g., Zn^II/Co^II) via synthesizing isostructural trinuclear‐complex precursors (Fe₂Zn/Fe₂Co), namely the “heteroatom modulator approach”, is inhibiting the aggregation of Fe atoms toward nanoclusters with formation of a stable iron dimer in an optimal metal–nitrogen moiety, clearly identified by direct transmission electron microscopy and X‐ray absorption fine structure analysis. The supported iron dimer, serving as cooperative metal–metal site, acts as efficient oxygen evolution catalyst. Our findings offer an atomic insight to guide the future design of ultrasmall metal clusters bearing outstanding catalytic capabilities.     

A Theoretical Study on the Mechanism of Photocatalytic Oxygen Evolution on BiVO4 in Aqueous Solution

The oxygen evolution reaction (OER) is regarded as one of the key issues in achieving efficient photocatalytic water splitting. Monoclinic scheelite BiVO₄ is a visible‐light‐responsive semiconductor which has proved to be effective for oxygen evolution. Recently, the synthesis of a series of monoclinic BiVO₄ single crystals was reported, and it was found that the (010), (110), and (011) facets are highly exposed and that the photocatalytic O₂ evolution activity depends on the degree of exposure of the (010) facets. To explore the properties of and photocatalytic water oxidation reaction on different facets, DFT calculations were performed to investigate the geometric structure, optical properties, electronic structure, water adsorption, and the whole OER free‐energy profiles on BiVO₄ (010) and (011) facets. The calculated results suggest both favorable and unfavorable factors for OER on the (010) and the (011) facets. Due to the combined effects of the above‐mentioned factors, different facets exhibit quite different photocatalytic activities.     

A Novel High Efficient Catalyst AgBr/CaMoO4 for the Reduction of p‐Nitrophenol

A new composite catalyst AgBr/CaMoO₄ was successfully fabricated by loading AgBr nanoparticles on CaMoO₄ support via a convenient precipitation/deposition method, without any controlling agent and template. The microstructure, chemical composition, and morphologies of the AgBr/CaMoO₄ were characterized by X‐ray diffraction, Fourier transform infrared, X‐ray photoelectron spectroscopy, and scanning electron microscopy. A series of comparative experiments showed that the composite AgBr/CaMoO₄ exhibits higher catalytic activity than pure AgBr or CaMoO₄ for the reduction of p‐nitrophenol (4‐NP). Moreover, the AgBr content greatly impacted the catalytic activity of composite AgBr/CaMoO₄ . The conversion rate of 4‐NP with AgBr/CaMoO₄ ‐5% as catalyst could reach 100% within only 4 min, which might be attributed to more number of available active sites from the highly dispersed AgBr nanoparticles on the surface of CaMoO₄ microspheres. In addition, the composite catalyst AgBr/CaMoO₄ displayed a good structural and cycling stability. The present study might provide a new strategy to design composite materials with excellent catalytic performance.     

CoOx@Co-NC Catalyst with Dual Active Centers for Enhanced Oxygen Evolution: Breaking Trade-Off of Particle Size and Metal Loading

Increasing the metal loading and downsizing the metal particle size are two effective ways to boost the electrochemical performance of catalysts. However, it is difficult to simultaneously increase the metal loading and reduce the particle size since isolated individual atoms are easy to aggregate into nanoparticles when increasing the metal loading. To tackle this contradiction, we report a bottom-up ligand-mediated strategy to facilely prepare ultrafine CoO_x nanoclusters anchored on a Co-N-containing carbon matrix (CoO_x@Co-NC). The co-exist of N and O atoms prevent Co atoms agglomerating into large particles and allowing the formation of ultrafine dispersed Co species with large Co loading (up to 20 wt.%). Since the relationship between ultrasmall size and large metal loading is well balanced, the CoO_x nanoclusters have no inhibitory effect, but facilitate the catalytic performance of Co-N₄ sites during OER process. Consequently, due to the synergistic effect of ultrafine CoO_x nanoclusters and Co-N₄ macrocycles, the as-synthesized CoO_x@Co-NC exhibit promising OER activity (η₁₀=370 mV, Tafel plot=40 mV/dec), bettering than that of benchmark RuO₂ (η₁₀=411 mV, Tafel plot=72 mV/dec). This ligand-mediated strategy to synthesize carbonaceous materials containing dual active centers with large metal loading is promising for developing active and stable catalysts for electrocatalytic applications.     

Plasma‐Engraved Co3O4 Nanosheets with Oxygen Vacancies and High Surface Area for the Oxygen Evolution Reaction

Co₃O₄, which is of mixed valences Co²⁺ and Co³⁺, has been extensively investigated as an efficient electrocatalyst for the oxygen evolution reaction (OER). The proper control of Co²⁺/Co³⁺ ratio in Co₃O₄ could lead to modifications on its electronic and thus catalytic properties. Herein, we designed an efficient Co₃O₄‐based OER electrocatalyst by a plasma‐engraving strategy, which not only produced higher surface area, but also generated oxygen vacancies on Co₃O₄ surface with more Co²⁺ formed. The increased surface area ensures the Co₃O₄ has more sites for OER, and generated oxygen vacancies on Co₃O₄ surface improve the electronic conductivity and create more active defects for OER. Compared to pristine Co₃O₄, the engraved Co₃O₄ exhibits a much higher current density and a lower onset potential. The specific activity of the plasma‐engraved Co₃O₄ nanosheets (0.055 mA cm^?2_BET at 1.6 V) is 10 times higher than that of pristine Co₃O₄, which is contributed by the surface oxygen vacancies.