Synergy of Ultrathin CoOx Overlayer and Nickel Single Atoms on Hematite Nanorods for Efficient Photo-Electrochemical Water Splitting

To solve surface carrier recombination and sluggish water oxidation kinetics of hematite (α-Fe₂O₃) photoanodes, herein, an attractive surface modification strategy is developed to successively deposit ultrathin CoO_x overlayer and Ni single atoms on titanium (Ti)-doped α-Fe₂O₃ (Ti:Fe₂O₃) nanorods through a two-step atomic layer deposition (ALD) and photodeposition process. The collaborative decoration of ultrathin CoO_x overlayer and Ni single atoms can trigger a big boost in photo-electrochemical (PEC) performance for water splitting over the obtained Ti:Fe₂O₃/CoO_x/Ni photoanode, with the photocurrent density reaching 1.05 mA cm⁻² at 1.23 V vs. reversible hydrogen electrode (RHE), more than three times that of Ti:Fe₂O₃ (0.326 mA cm⁻²). Electrochemical and electronic investigations reveal that the surface passivation effect of ultrathin CoO_x overlayer can reduce surface carrier recombination, while the catalysis effect of Ni single atoms can accelerate water oxidation kinetics. Moreover, theoretical calculations evidence that the synergy of ultrathin CoO_x overlayer and Ni single atoms can lower the adsorption free energy of OH* intermediates and relieve the potential-determining step (PDS) for oxygen evolution reaction (OER). This work provides an exemplary modification through rational engineering of surface electrochemical and electronic properties for the improved PEC performances, which can be applied in other metal oxide semiconductors as well.     

New BiVO4 Dual Photoanodes with Enriched Oxygen Vacancies for Efficient Solar‐Driven Water Splitting

Bismuth vanadate (BiVO₄) is a promising photoanode material for photoelectrochemical (PEC) water splitting. However, owing to the short carrier diffusion length, the trade‐off between sufficient light absorption and efficient charge separation often leads to poor PEC performance. Herein, a new electrodeposition process is developed to prepare bismuth oxide precursor films, which can be converted to transparent BiVO₄ films with well‐controlled oxygen vacancies via a mild thermal treatment process. The optimized BiVO₄ film exhibits an excellent back illumination charge separation efficiency mainly due to the presence of enriched oxygen vacancies which act as shallow donors. By loading FeOOH/NiOOH as the cocatalysts, the BiVO₄ dual photoanodes exhibit a remarkable and highly stable photocurrent density of 5.87 mA cm^?2 at 1.23 V versus the reversible hydrogen electrode under AM 1.5 G illumination. An artificial leaf composed of the BiVO₄/FeOOH/NiOOH dual photoanodes and a single sealed perovskite solar cell delivers a solar‐to‐hydrogen conversion efficiency as high as 6.5% for unbiased water splitting.     

In Situ Formation of Oxygen Vacancies Achieving Near-Complete Charge Separation in Planar BiVO4 Photoanodes

Despite a suitable bandgap of bismuth vanadate (BiVO₄) for visible light absorption, most of the photogenerated holes in BiVO₄ photoanodes are vanished before reaching the surfaces for oxygen evolution reaction due to the poor charge separation efficiency in the bulk. Herein, a new sulfur oxidation strategy is developed to prepare planar BiVO₄ photoanodes with in situ formed oxygen vacancies, which increases the majority charge carrier density and photovoltage, leading to a record charge separation efficiency of 98.2% among the reported BiVO₄ photoanodes. Upon loading NiFeO_x as an oxygen evolution cocatalyst, a stable photocurrent density of 5.54 mA cm⁻² is achieved at 1.23 V versus the reversible hydrogen electrode (RHE) under AM 1.5 G illumination. Remarkably, a dual-photoanode configuration further enhances the photocurrent density up to 6.24 mA cm⁻², achieving an excellent applied bias photon-to-current efficiency of 2.76%. This work demonstrates a simple thermal treatment approach to generate oxygen vacancies for the design of efficient planar photoanodes for solar hydrogen production.     

Surface Self-Transforming FeTi-LDH Overlayer in Fe2O3/Fe2TiO5 Photoanode for Improved Water Oxidation

Integrating hematite nanostructures with efficient layer double hydroxides (LDHs) is highly desirable to improve the photoelectrochemical (PEC) water oxidation performance. Here, an innovative and facile strategy is developed to fabricate the FeTi-LDH overlayer decorated Fe₂O₃/Fe₂TiO₅ photoanode via a surface self-transformation induced by the co-treatment of hydrazine and NaOH at room temperature. Electrochemical measurements find that this favorable structure can not only facilitate the charge transfer/separation at the electrode/electrolyte interface but also accelerate the surface water oxidation kinetics. Consequently, the as-obtained Fe₂O₃/Fe₂TiO₅/LDH photoanode exhibits a remarkably increased photocurrent density of 3.54 mA cm⁻² at 1.23 V versus reversible hydrogen electrode (RHE) accompanied by an obvious cathodic shift (≈140 mV) in the onset potential. This work opens up a new and effective pathway for the design of high-performance hematite photoanodes toward efficient PEC water oxidation.     

Enhanced Charge Separation through ALD‐Modified Fe2O3/Fe2TiO5 Nanorod Heterojunction for Photoelectrochemical Water Oxidation

Hematite suffers from poor charge transport and separation properties for solar water splitting. This paper describes the design and fabrication of a 3D Fe₂O₃/Fe₂TiO₅ heterojunction photoanode with improved charge separation, via a facile hydrothermal method followed by atomic layer deposition and air annealing. A highly crystallized Fe₂TiO₅ phase forms with a distinct interface with the underlying Fe₂O₃ core, where a 4 nm Fe₂TiO₅ overlayer leads to the best photoelectrochemical performance. The favorable band offset between Fe₂O₃ and Fe₂TiO₅ establishes a type‐II heterojunction at the Fe₂O₃/Fe₂TiO₅ interface, which drives electron–hole separation effectively. The Fe₂O₃/Fe₂TiO₅ composite electrode exhibits a dramatically improved photocurrent of 1.63 mA cm^?2 at 1.23 V versus reversible hydrogen electrode (RHE) under simulated 1 sun illumination (100 mW cm^?2), which is 3.5 times that of the bare Fe₂O₃ electrode. Decorating the Fe₂O₃/Fe₂TiO₅ heterojunction photoanode with earth‐abundant FeNiO_x cocatalyst further expedites surface reaction kinetics, leading to an onset potential of 0.8 V versus RHE with a photocurrent of 2.7 mA cm^?2 at 1.23 V and 4.6 mA cm^?2 at 1.6 V versus RHE. This sandwich photoanode shows an excellent stability for 5 h and achieves an overall Faradaic efficiency of 95% for O₂ generation. This is the best performance ever reported for Fe₂O₃/Fe₂TiO₅ photoanodes.     

FeP@C Nanotube Arrays Grown on Carbon Fabric as a Low Potential and Freestanding Anode for High‐Performance Li‐Ion Batteries

An anode of self‐supported FeP@C nanotube arrays on carbon fabric (CF) is successfully fabricated via a facile template‐based deposition and phosphorization route: first, well‐aligned FeOOH nanotube arrays are simply obtained via a solution deposition and in situ etching route with hydrothermally crystallized (Co,Ni)(CO₃)_0.5OH nanowire arrays as the template; subsequently, these uniform FeOOH nanotube arrays are transformed into robust carbon‐coated Fe₃O₄ (Fe₃O₄@C) nanotube arrays via glucose adsorption and annealing treatments; and finally FeP@C nanotube arrays on CF are achieved through the facile phosphorization of the oxide‐based arrays. As an anode for lithium‐ion batteries (LIBs), these FeP@C nanotube arrays exhibit superior rate capability (reversible capacities of 945, 871, 815, 762, 717, and 657 mA h g⁻¹ at 0.1, 0.2, 0.4, 0.8, 1.3, and 2.2 A g⁻¹, respectively, corresponding to area specific capacities of 1.73, 1.59, 1.49, 1.39, 1.31, 1.20 mA h cm⁻² at 0.18, 0.37, 0.732, 1.46, 2.38, and 4.03 mA cm⁻², respectively) and a stable long‐cycling performance (a high specific capacity of 718 mA h g⁻¹ after 670 cycles at 0.5 A g⁻¹, corresponding to an area capacity of 1.31 mA h cm⁻² at 0.92 mA cm⁻²).     

GaP/GaNP Heterojunctions for Efficient Solar‐Driven Water Oxidation

The growth and characterization of an n‐GaP/i‐GaNP/p⁺‐GaP thin film heterojunction synthesized using a gas‐source molecular beam epitaxy (MBE) method, and its application for efficient solar‐driven water oxidation is reported. The TiO₂/Ni passivated n‐GaP/i‐GaNP/p⁺‐GaP thin film heterojunction provides much higher photoanodic performance in 1 m KOH solution than the TiO₂/Ni‐coated n‐GaP substrate, leading to much lower onset potential and much higher photocurrent. There is a significant photoanodic potential shift of 764 mV at a photocurrent of 0.34 mA cm^?2, leading to an onset potential of ≈0.4 V versus reversible hydrogen electrode (RHE) at 0.34 mA cm^?2 for the heterojunction. The photocurrent at the water oxidation potential (1.23 V vs RHE) is 1.46 and 7.26 mA cm^?2 for the coated n‐GaP and n‐GaP/i‐GaNP/p⁺‐GaP photoanodes, respectively. The passivated heterojunction offers a maximum applied bias photon‐to‐current efficiency (ABPE) of 1.9% while the ABPE of the coated n‐GaP sample is almost zero. Furthermore, the coated n‐GaP/i‐GaNP/p⁺‐GaP heterojunction photoanode provides a broad absorption spectrum up to ≈620 nm with incident photon‐to‐current efficiencies (IPCEs) of over 40% from ≈400 to ≈560 nm. The high low‐bias performance and broad absorption of the wide‐bandgap GaP/GaNP heterojunctions render them as a promising photoanode material for tandem photoelectrochemical (PEC) cells to carry out overall solar water splitting.     

3D Brochosomes‐Like TiO2/WO3/BiVO4 Arrays as Photoanode for Photoelectrochemical Hydrogen Production

An ideal photoelectrochemical (PEC) anode should process effective light absorption, charge transport, and separation efficiency. Here, a novel 3D brochosomes‐like TiO₂/WO₃/BiVO₄ array as an efficient photoanode by combining a colloid polystyrene sphere template and electrochemical deposition routes for PEC hydrogen generation is reported. The as‐fabricated 3D TiO₂/WO₃/BiVO₄ brochosomes photoanode yields excellent PEC performance with photocurrent densities of ≈3.13 and ≈4.27 mA cm^?2 with FeOOH/NiOOH catalyst, respectively, measured in 0.5 m Na₂SO₄ solution with 0.1 m Na₂SO₃ at 1.23 V versus reversible hydrogen electrode (RHE) under simulated AM1.5 light illumination, which is ≈6 times the reference sample of a planar WO₃/BiVO₄ film electrode. The significantly improved performance could be benefited from the ordered hollow porous structure that provides enhanced light absorption and efficient charge transport as well as improved charge separation efficiency by WO₃/BiVO₄ “host–guest” heterojunctions.     

Spinel Structural Disorder Influences Solar‐Water‐Splitting Performance of ZnFe2O4 Nanorod Photoanodes

Zinc spinel ferrite, ZnFe₂O₄ (ZFO), is an emerging photoanode material for photoelectrochemical (PEC) solar fuel production. However, a lack of fundamental insight into the factors limiting the photocurrent has prevented substantial advance in its performance. Herein, it is found that ZFO nanorod array photoelectrodes with varying crystallinity exhibit vastly different PEC properties. Using a sacrificial hole scavenger (H₂O₂), spatially defined carrier generation, and electrochemical impedance spectroscopy, it is shown that ZFO with a relatively poor crystallinity but a higher spinel inversion degree (due to cation disorder) exhibits superior photogenerated charge separation efficiency and improved majority charge carrier transport compared to ZFO with higher crystallinity and a lower inversion degree. Conversely, the latter condition leads to better charge injection efficiency. Optimization of these factors, and the addition of a nickel–iron oxide cocatalyst overlayer, leads to a new benchmark solar photocurrent for ZFO of 1.0 mA cm^?2 at 1.23 V versus reversible hydrogen electrode (RHE) and 1.7 mA cm^?2 at 1.6 V versus RHE. Importantly, the observed correlation between the cation disorder and the PEC performance represents a new insight into the factors important to the PEC performance of the spinel ferrites and suggests a path to further improvement.     

Plasmonic Enhancement in BiVO4 Photonic Crystals for Efficient Water Splitting

Photo‐electrochemical water splitting is a very promising and environmentally friendly route for the conversion of solar energy into hydrogen. However, the solar‐to‐H₂ conversion efficiency is still very low due to rapid bulk recombination of charge carriers. Here, a photonic nano‐architecture is developed to improve charge carrier generation and separation by manipulating and confining light absorption in a visible‐light‐active photoanode constructed from BiVO₄ photonic crystal and plasmonic nanostructures. Synergistic effects of photonic crystal stop bands and plasmonic absorption are observed to operate in this photonic nanostructure. Within the scaffold of an inverse opal photonic crystal, the surface plasmon resonance is significantly enhanced by the photonic Bragg resonance. Nanophotonic photoanodes show AM 1.5 photocurrent densities of 3.1 ± 0.1 mA cm^?2 at 1.23 V versus RHE, which is among the highest for oxide‐based photoanodes and over 4 times higher than the unstructured planar photoanode.     

MOF-Derived In2O3/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 In₂O₃/CuO p-n heterojunction composite. After incorporation of small amounts of graphene nanoribbons (GNRs), the optimized PEC devices exhibited a maximum current density of 1.51 mA cm⁻² (at 1.6 V vs RHE) under one sun illumination (AM 1.5G, 100 mW cm⁻²), which is approximately four times higher than that of the reference device based on only In₂O₃ 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 In₂O₃/CuO p-n heterojunction composite is used to demonstrate a high-performance PEC device for hydrogen generation.     

Cobalt–Nickel Layered Double Hydroxides Modified on TiO2 Nanotube Arrays for Highly Efficient and Stable PEC Water Splitting

TiO₂‐based photoanodes have attracted extensive attention worldwide for photoelectrochemical (PEC) water splitting, but these materials still suffer from poor electron–hole separation and low photoconversion efficiency. Here, the high PEC water splitting activity and long‐term stability against photocorrosion of well‐aligned hierarchical TiO₂@CoNi‐layered double hydroxides nanotube arrays (TiO₂@CoNi‐LDHs NTAs) are reported. The typical TiO₂@CoNi‐LDHs NTAs exhibits enhancing photocurrent density of 4.4 mA cm^?2 at a potential of 1.23 V (vs reversible hydrogen electrode) under AM 1.5G simulated sunlight (100 mW cm^?2), 3.3 times higher than that of the pristine TiO₂ sample. Moreover, this hierarchical electrode displays excellent stability against photocorrosion with initial activity loss no more than 1.0% even after 10 h irradiation in Na₂SO₄ electrolyte solution (pH 6.8), much competitive to those reported TiO₂‐based photoelectrodes. This work may offer a combinatorial synthesis strategy for the preparation of hierarchical architectures with high PEC performances.     

Fe2O3–TiO2 Nano‐heterostructure Photoanodes for Highly Efficient Solar Water Oxidation

Harnessing solar energy for the production of clean hydrogen by photo­electrochemical water splitting represents a very attractive, but challenging approach for sustainable energy generation. In this regard, the fabrication of Fe₂O₃–TiO₂ photoanodes is reported, showing attractive performances [≈2.0 mA cm⁻² at 1.23 V vs. the reversible hydrogen electrode in 1 M NaOH] under simulated one‐sun illumination. This goal, corresponding to a tenfold photoactivity enhancement with respect to bare Fe₂O₃, is achieved by atomic layer deposition of TiO₂ over hematite (α‐Fe₂O₃) nanostructures fabricated by plasma enhanced‐chemical vapor deposition and final annealing at 650 °C. The adopted approach enables an intimate Fe₂O₃–TiO₂ coupling, resulting in an electronic interplay at the Fe₂O₃/TiO₂ interface. The reasons for the photocurrent enhancement determined by TiO₂ overlayers with increasing thickness are unraveled by a detailed chemico‐physical investigation, as well as by the study of photo­generated charge carrier dynamics. Transient absorption spectroscopy shows that the increased photoelectrochemical response of heterostructured photoanodes compared to bare hematite is due to an enhanced separation of photogenerated charge carriers and more favorable hole dynamics for water oxidation. The stable responses obtained even in simulated seawater provides a feasible route in view of the eventual large‐scale generation of renewable energy.     

Rugged Forest Morphology of Magnetoplasmonic Nanorods that Collect Maximum Light for Photoelectrochemical Water Splitting

A feasible nanoscale framework of heterogeneous plasmonic materials and proper surface engineering can enhance photoelectrochemical (PEC) water-splitting performance owing to increased light absorbance, efficient bulk carrier transport, and interfacial charge transfer. This article introduces a new magnetoplasmonic (MagPlas) Ni-doped Au@Fe_xO_y nanorods (NRs) based material as a novel photoanode for PEC water-splitting. A two stage procedure produces core–shell Ni/Au@Fe_xO_y MagPlas NRs. The first-step is a one-pot solvothermal synthesis of Au@Fe_xO_y. The hollow Fe_xO_y nanotubes (NTs) are a hybrid of Fe₂O₃ and Fe₃O₄, and the second-step is a sequential hydrothermal treatment for Ni doping. Then, a transverse magnetic field-induced assembly is adopted to decorate Ni/Au@Fe_xO_y on FTO glass to be an artificially roughened morphologic surface called a rugged forest, allowing more light absorption and active electrochemical sites. Then, to characterize its optical and surface properties, COMSOL Multiphysics simulations are carried out. The core–shell Ni/Au@Fe_xO_y MagPlas NRs increase photoanode interface charge transfer to 2.73 mAcm⁻² at 1.23 V RHE. This improvement is made possible by the rugged morphology of the NRs, which provide more active sites and oxygen vacancies as the hole transfer medium. The recent finding may provide light on plasmonic photocatalytic hybrids and surface morphology for effective PEC photoanodes.     

Amorphous Bimetallic Oxide–Graphene Hybrids as Bifunctional Oxygen Electrocatalysts for Rechargeable Zn–Air Batteries

Metal oxides of earth‐abundant elements are promising electrocatalysts to overcome the sluggish oxygen evolution and oxygen reduction reaction (OER/ORR) in many electrochemical energy‐conversion devices. However, it is difficult to control their catalytic activity precisely. Here, a general three‐stage synthesis strategy is described to produce a family of hybrid materials comprising amorphous bimetallic oxide nanoparticles anchored on N‐doped reduced graphene oxide with simultaneous control of nanoparticle elemental composition, size, and crystallinity. Amorphous Fe_0.5Co_0.5O_x is obtained from Prussian blue analog nanocrystals, showing excellent OER activity with a Tafel slope of 30.1 mV dec^?1 and an overpotential of 257 mV for 10 mA cm^?2 and superior ORR activity with a large limiting current density of ?5.25 mA cm^?2 at 0.6 V. A fabricated Zn–air battery delivers a specific capacity of 756 mA h g_Zn^?1 (corresponding to an energy density of 904 W h kg_Zn^?1), a peak power density of 86 mW cm^?2 and can be cycled over 120 h at 10 mA cm^?2. Other two amorphous bimetallic, Ni_0.4Fe_0.6O_x and Ni_0.33Co_0.67O_x , are also produced to demonstrate the general applicability of this method for synthesizing binary metal oxides with controllable structures as electrocatalysts for energy conversion.     

Novel Iron Oxyhydroxide Lepidocrocite Nanosheet as Ultrahigh Power Density Anode Material for Asymmetric Supercapacitors

A simple one‐step electroplating route is proposed for the synthesis of novel iron oxyhydroxide lepidocrocite (γ‐FeOOH) nanosheet anodes with distinct layered channels, and the microstructural influence on the pseudocapacitive performance of the obtained γ‐FeOOH nanosheets is investigated via in situ X‐ray absorption spectroscopy (XAS) and electrochemical measurement. The in situ XAS results regarding charge storage mechanisms of electrodeposited γ‐FeOOH nanosheets show that a Li⁺ can reversibly insert/desert into/from the 2D channels between the [FeO₆] octahedral subunits depending on the applied potential. This process charge compensates the Fe²⁺/Fe³⁺ redox transition upon charging–discharging and thus contributes to an ideal pseudocapacitive behavior of the γ‐FeOOH electrode. Electrochemical results indicate that the γ‐FeOOH nanosheet shows the outstanding pseudocapacitive performance, which achieves the extraordinary power density of 9000 W kg^?1 with good rate performance. Most importantly, the asymmetric supercapacitors with excellent electrochemical performance are further realized by using 2D MnO₂ and γ‐FeOOH nanosheets as cathode and anode materials, respectively. The obtained device can be cycled reversibly at a maximum cell voltage of 1.85 V in a mild aqueous electrolyte, further delivering a maximum power density of 16 000 W kg^?1 at an energy density of 37.4 Wh kg^?1.     

Hierarchical CdS Nanorod@SnO2 Nanobowl Arrays for Efficient and Stable Photoelectrochemical Hydrogen Generation

An efficient photoanode based on CdS nanorod@SnO₂ nanobowl (CdS NR@SnO₂ NB) arrays is designed and fabricated by the preparation of SnO₂ nanobowl arrays via nanosphere lithography followed by hydrothermal growth of CdS nanorods on the inner surface of the SnO₂ nanobowls. A photoelectrochemical (PEC) device constructed by using this hierarchical CdS NR@SnO₂ NB photoanode presents significantly enhanced performance with a photocurrent density of 3.8 mA cm^?2 at 1.23 V versus a reversible hydrogen electrode (RHE) under AM1.5G solar light irradiation, which is about 2.5 times higher than that of CdS nanorod arrays. After coating with a thin layer of SiO₂, the photostability of the CdS NR@SnO₂ NB arrays is greatly enhanced, resulting in a stable photoanode with a photocurrent density of 3.0 mA cm^?2 retained at 1.23 V versus the RHE. The much improved performance of the CdS NR@SnO₂ NB arrays toward PEC hydrogen generation can be ascribed to enlarged surface area arising from the hierarchical nanostructures, improved light harvesting owing to the NR@NB architecture containing multiple scattering centers, and enhanced charge separation/collection efficiency due to the favorable CdS–SnO₂ heterojunction.     

Regulating the Electronic Structure of Bismuth Nanosheets by Titanium Doping to Boost CO2 Electroreduction and Zn–CO2 Batteries

The electrochemical carbon dioxide reduction reaction (E-CO₂RR) to formate is a promising strategy for mitigating greenhouse gas emissions and addressing the global energy crisis. Developing low-cost and environmentally friendly electrocatalysts with high selectivity and industrial current densities for formate production is an ideal but challenging goal in the field of electrocatalysis. Herein, novel titanium-doped bismuth nanosheets (Ti Bi NSs) with enhanced E-CO₂RR performance are synthesized through one-step electrochemical reduction of bismuth titanate (Bi₄Ti₃O₁₂). We comprehensively evaluated Ti Bi NSs using in situ Raman spectra, finite element method, and density functional theory. The results indicate that the ultrathin nanosheet structure of Ti Bi NSs can accelerate mass transfer, while the electron-rich properties can accelerate the production of *CO₂⁻ and enhance the adsorption strength of *OCHO intermediate. The Ti Bi NSs deliver a high formate Faradaic efficiency (FE_formate) of 96.3% and a formate production rate of 4032 µmol h⁻¹ cm⁻² at −1.01 V versus RHE. An ultra-high current density of −338.3 mA cm⁻² is achieved at −1.25 versus RHE, and simultaneously FE_formate still reaches more than 90%. Furthermore, the rechargeable Zn–CO₂ battery using Ti Bi NSs as a cathode catalyst achieves a maximum power density of 1.05 mW cm⁻² and excellent charging/discharging stability of 27 h.     

Roles of Cobalt-Coordinated Polymeric Perylene Diimide in Hematite Photoanodes for Improved Water Oxidation

Interfacial charge recombination is a permanent issue that impedes the photon energy utilization in photoelectrochemical (PEC) water splitting. Herein, a conjugated polymer, urea linked perylene diimide polymer (PDI), is introduced to the designation of hematite-based composite photoanodes. On account of its unique molecule structure with abundant electronegative atoms, the O and N atoms with lone electron pairs can bond with Fe atoms at the surface of Zr⁴⁺ doped α-Fe₂O₃ (Zr:Fe₂O₃) and thus establish charge transfer channels for expediting hole separation and migration. Meanwhile, PDI molecules can passivate the surface states in Zr:Fe₂O₃, which is in favor of suppressing carrier recombination. Particularly, Co²⁺ is used to coordinate with PDI (Co-PDI) to accelerate hole extraction as well as utilization, and the as-obtained Co-PDI form type-II heterojunction with Zr:Fe₂O₃. Such a photoanode configuration takes advantage of the unique molecule structure of PDI, and the target Co-PDI/Zr:Fe₂O₃ photoanodes eventually attain a photocurrent density of 2.17 mA cm⁻², which is inspirational for unearthing the potential use of conjugative molecules in PEC fields.     

Bimetallic Oxyhydroxide as a High-Performance Water Oxidation Electrocatalyst under Industry-Relevant Conditions

Developing high-performing oxygen evolution reaction (OER) electrocatalysts under high-current operation conditions is critical for future commercial applications of alkaline water electrolysis for clean energy generation. Herein, we prepared a three-dimensional (3D) bimetallic oxyhydroxide hybrid grown on a Ni foam (NiFeOOH/NF) prepared by immersing Ni foam (NF) into Fe(NO₃)₃ solution. In this unique 3D structure, the NiFeOOH/NF hybrid was composed of crystalline Ni(OH)₂ and amorphous FeOOH evenly grown on the NF surface. As a bimetallic oxyhydroxide electrocatalyst, the NiFeOOH/NF hybrid exhibited excellent catalytic activity, surpassing not only the other reported Ni–Fe based electrocatalysts, but also the commercial Ir/C catalyst. In situ electrochemical Raman spectroscopy demonstrated the active FeOOH and NiOOH phases involved in the OER process. Profiting from the synergy of Fe and Ni catalytic sites, the NiFeOOH/NF hybrid delivered an outstanding OER performance under challenging industrial conditions in a 10.0 mol∙L⁻¹ KOH electrolyte at 80 °C, requiring potentials as small as 1.47 and 1.51 V to achieve the super-high catalytic current densities of 100 and 500 mA∙cm⁻², respectively.