Double Perovskite LaFexNi1−xO3 Nanorods Enable Efficient Oxygen Evolution Electrocatalysis

Perovskite‐based electrocatalysts are one of the most promising materials for oxygen evolution reaction (OER), but their activity and durability are still far from desirable. Herein, we demonstrate that the double perovskite LaFe_xNi_1?xO₃ (LFNO) nanorods (NRs) can be adopted as highly active and stable OER electrocatalysts. The optimized LFNO‐II NRs with Ni/Fe ratio of 8:2 achieve a low overpotential of 302 mV at 10 mA cm^?2 and a small Tafel slope of 50 mV dec^?1, outperforming those of the commercial Ir/C. The LFNO‐II NRs also show high OER stability with slight current decrease after 20 h. The enhanced activity is explained by the improved surface area, tailored electronic structure as well as strong hybridization between O and Ni.     

Spontaneous Synthesis of Silver‐Nanoparticle‐Decorated Transition‐Metal Hydroxides for Enhanced Oxygen Evolution Reaction

The fabrication of metal‐supported hybrid structures with enhanced properties typically requires external energy input, such as pyrolysis, photolysis, and electrodeposition. In this study, silver‐nanoparticle‐decorated transition‐metal hydroxide (TMH) composites were synthesized by an approach based on a spontaneous redox reaction (SRR) at room temperature. The SRR between silver ions and TMH provides a simple and facile route to establish effective and stable heterostructures that can enhance the oxygen evolution reaction (OER) activity. Ag@Co(OH)_x grown on carbon cloth exhibits outstanding OER activity and durability, even superior to IrO₂ and many previously reported OER electrocatalysts. Experimental and theoretical analysis demonstrates that the strong electronic interaction between Ag and Co(OH)₂ activates the silver clusters as catalytically OER active sites, effectively optimizing the binding energies with reacted intermediates and facilitating the OER kinetics.     

Multifunctional Active‐Center‐Transferable Platinum/Lithium Cobalt Oxide Heterostructured Electrocatalysts towards Superior Water Splitting

Designing cost‐effective and efficient electrocatalysts plays a pivotal role in advancing the development of electrochemical water splitting for hydrogen generation. Herein, multifunctional active‐center‐transferable heterostructured electrocatalysts, platinum/lithium cobalt oxide (Pt/LiCoO₂) composites with Pt nanoparticles (Pt NPs) anchored on LiCoO₂ nanosheets, are designed towards highly efficient water splitting. In this electrocatalyst system, the active center can be alternatively switched between Pt species and LiCoO₂ for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively. Specifically, Pt species are the active centers and LiCoO₂ acts as the co‐catalyst for HER, whereas the active center transfers to LiCoO₂ and Pt turns into the co‐catalyst for OER. The unique architecture of Pt/LiCoO₂ heterostructure provides abundant interfaces with favorable electronic structure and coordination environment towards optimal adsorption behavior of reaction intermediates. The 30 % Pt/LiCoO₂ heterostructured electrocatalyst delivers low overpotentials of 61 and 285 mV to achieve 10 mA cm^?2 for HER and OER in alkaline medium, respectively.     

Coupling Magnetic Single‐Crystal Co2Mo3O8 with Ultrathin Nitrogen‐Rich Carbon Layer for Oxygen Evolution Reaction

Transition‐metal oxides as electrocatalysts for the oxygen evolution reaction (OER) provide a promising route to face the energy and environmental crisis issues. Although palmeirite oxide A₂Mo₃O₈ as OER catalyst has been explored, the correlation between its active sites (tetrahedral or octahedral) and OER performance has been elusive. Now, magnetic Co₂Mo₃O₈@NC‐800 composed of highly crystallized Co₂Mo₃O₈ nanosheets and ultrathin N‐rich carbon layer is shown to be an efficient OER catalyst. The catalyst exhibits favorable performance with an overpotential of 331 mV@10 mA cm^?2 and 422 mV@40 mA cm^?2, and a full water‐splitting electrolyzer with it as anode catalyst shows a cell voltage of 1.67 V@10 mA cm^?2 in alkaline. Combined HAADFSTEM, magnetic, and computational results show that factors influencing the OER performance can be attributed to the tetrahedral Co sites (high spin, t₂³e⁴), which improve the OER kinetics of rate‐determining step to form *OOH.     

In Situ Electrochemical Conversion of an Ultrathin Tannin Nickel Iron Complex Film as an Efficient Oxygen Evolution Reaction Electrocatalyst

The oxygen evolution reaction (OER) is an important half reaction in many energy conversion and storage techniques. However, the development of a low‐cost easy‐prepared OER electrocatalyst with high mass activity and rapid kinetics is still challenging. Herein, we report the facile deposition of tannin‐NiFe (TANF) complex film on carbon fiber paper (CP) as a highly efficient OER electrocatalyst. TANF gives rapid OER reaction kinetics with a very small Tafel slope of 28 mV dec^?1. The mass activity of TANF reaches 9.17×10³ Ag^?1 at an overpotential of 300 mV, which is nearly 200‐times larger than that of NiFe double layered hydroxide. Furthermore, tannic acid in TANF can be electrochemically extracted under anodic potential, leaving the inorganic composite Ni_xFe_1?xO_yH_z as the OER‐active species. This work may provide a guide to probing the electrochemical transformation and investigating the reactive species of other metal–organic complexes as heterogeneous electrocatalysts.     

Exploring the Influence of Halogen Coordination Effect of Stable Bimetallic MOFs on Oxygen Evolution Reaction

The energy crisis and environmental pollution have forced scientists to explore alternative energy conversion and storage devices. The anodic reactions of these devices are all oxygen evolution reactions (OER), so the development of efficient OER electrocatalysts is of great significance. At the same time, understanding the reaction mechanism of OER is conducive to the rational design of efficient OER electrocatalysts. In general, catalytic active centers play a direct role in OER performance. In this paper, a series of stable bimetallic metal–organic frameworks (MOFs, named as Fe₃-Co_n-X₂, n=2, 3 and X=F, Cl, Br) with similar structure were synthesized by changing the halogen coordinated with the cobalt metal active center, aiming to investigate the influence of halogen substitution effect on OER performance. It was found that the OER activity of Fe₃-Co₃-F₂ is much better than Fe₃-Co₂-Cl₂ and Fe₃-Co₂-Br₂, indicating that the regulation of the electronegativity change of the coordination halogen atom can regulate the coordination electron structure of the metal active center, thereby achieving effective regulation of OER performance.     

A Surface‐Oxide‐Rich Activation Layer (SOAL) on Ni2Mo3N for a Rapid and Durable Oxygen Evolution Reaction

The oxygen evolution reaction (OER) is key to renewable energy technologies such as water electrolysis and metal–air batteries. However, the multiple steps associated with proton‐coupled electron transfer result in sluggish OER kinetics and catalysts are required. Here we demonstrate that a novel nitride, Ni₂Mo₃N, is a highly active OER catalyst that outperforms the benchmark material RuO₂. Ni₂Mo₃N exhibits a current density of 10 mA cm^?2 at a nominal overpotential of 270 mV in 0.1 m KOH with outstanding catalytic cyclability and durability. Structural characterization and computational studies reveal that the excellent activity stems from the formation of a surface‐oxide‐rich activation layer (SOAL). Secondary Mo atoms on the surface act as electron pumps that stabilize oxygen‐containing species and facilitate the continuity of the reactions. This discovery will stimulate the further development of ternary nitrides with oxide surface layers as efficient OER catalysts for electrochemical energy devices.     

Identification of Key Reversible Intermediates in Self‐Reconstructed Nickel‐Based Hybrid Electrocatalysts for Oxygen Evolution

The oxygen evolution reaction (OER) has been explored extensively for reliable hydrogen supply to boost the energy conversion efficiency. The superior OER performance of newly developed non‐noble metal electrocatalysts has concealed the identification of the real active species of the catalysts. Now, the critical active phase in nickel‐based materials (represented by NiNPS) was directly identified by observing the dynamic surface reconstruction during the harsh OER process via combining in situ Raman tracking and ex situ microscopy and spectroscopy analyses. The irreversible phase transformation from NiNPS to α‐Ni(OH)₂ and reversible phase transition between α‐Ni(OH)₂ and γ‐NiOOH prior to OER demonstrate γ‐NiOOH as the key active species for OER. The hybrid catalyst exhibits 48‐fold enhanced catalytic current at 300 mV and remarkably reduced Tafel slope to 46 mV dec^?1, indicating the greatly accelerated catalytic kinetics after surface evolution.     

Heterostructures Composed of N‐Doped Carbon Nanotubes Encapsulating Cobalt and β‐Mo2C Nanoparticles as Bifunctional Electrodes for Water Splitting

Herein, we demonstrate the use of heterostructures comprised of Co/β‐Mo₂C@N‐CNT hybrids for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in an alkaline electrolyte. The Co can not only create a well‐defined heterointerface with β‐Mo₂C but also overcomes the poor OER activity of β‐Mo₂C, thus leading to enhanced electrocatalytic activity for HER and OER. DFT calculations further proved that cooperation between the N‐CNTs, Co, and β‐Mo₂C results in lower energy barriers of intermediates and thus greatly enhances the HER and OER performance. This study not only provides a simple strategy for the construction of heterostructures with nonprecious metals, but also provides in‐depth insight into the HER and OER mechanism in alkaline solution.     

Application of In Situ Techniques for the Characterization of NiFe‐Based Oxygen Evolution Reaction (OER) Electrocatalysts

Developing high‐efficiency and affordable electrocatalysts for the sluggish oxygen evolution reaction (OER) remains a crucial bottleneck on the way to the practical applications of rechargeable energy storage technologies and water splitting for producing clean fuel (H₂). In recent years, NiFe‐based materials have proven to be excellent electrocatalysts for OER. Understanding the characteristics that affect OER activity and determining the OER mechanism are of vital importance for the development of OER electrocatalysts. Therefore, in situ characterization techniques performed under OER conditions are urgently needed to monitor the key intermediates together with identifying the OER active centers and phases. In this Minireview, recent advances regarding in situ techniques for the characterization of NiFe‐based electrocatalysts are thoroughly summarized, including Raman spectroscopy, X‐ray absorption spectroscopy, ambient pressure X‐ray photoelectron spectroscopy, Mössbauer spectroscopy, Ultraviolet–visible spectroscopy, differential electrochemical mass spectrometry, and surface interrogation scanning electrochemical microscopy. The results from these in situ measurements not only reveal the structural transformation and the progressive oxidation of the catalytic species under OER conditions, but also disclose the crucial role of Ni and Fe during the OER. Finally, the need for developing new in situ techniques and theoretical investigations is discussed to better understand the OER mechanism and design promising OER electrocatalysts.     

Metallic Co4N Porous Nanowire Arrays Activated by Surface Oxidation as Electrocatalysts for the Oxygen Evolution Reaction

Designing highly efficient electrocatalysts for oxygen evolution reaction (OER) plays a key role in the development of various renewable energy storage and conversion devices. In this work, we developed metallic Co₄N porous nanowire arrays directly grown on flexible substrates as highly active OER electrocatalysts for the first time. Benefiting from the collaborative advantages of metallic character, 1D porous nanowire arrays, and unique 3D electrode configuration, surface oxidation activated Co₄N porous nanowire arrays/carbon cloth achieved an extremely small overpotential of 257 mV at a current density of 10 mA cm⁻², and a low Tafel slope of 44 mV dec⁻¹ in an alkaline medium, which is the best OER performance among reported Co‐based electrocatalysts to date. Moreover, in‐depth mechanistic investigations demonstrate the active phases are the metallic Co₄N core inside with a thin cobalt oxides/hydroxides shell during the OER process. Our finding introduces a new concept to explore the design of high‐efficiency OER electrocatalysts.     

Ultrathin Co3S4 Nanosheets that Synergistically Engineer Spin States and Exposed Polyhedra that Promote Water Oxidation under Neutral Conditions

Development of efficient and affordable electrocatalysts in neutral solutions is paramount importance for the renewable energy. Herein, we report that the oxygen evolution reaction (OER) performance of Co₃S₄ under neutral conditions can be enhanced by exposed octahedral planes and self‐adapted spin states in atomically thin nanosheets. A HAADF image clearly confirmed that the active octahedra with Jahn–Teller distortions were exposed exclusively. Most importantly, in the atomically thin nanosheets, the spin states of Co³⁺ in the octahedral self‐adapt from low‐spin to high‐spin states. As a result, the synergistic effect endow the Co₃S₄ nanosheets with superior OER performance, with exceptional low onset overpotentials of circa 0.31 V in neutral solutions, which is state‐of‐the‐art among inorganic non‐noble metal compounds.     

General π‐Electron‐Assisted Strategy for Ir,Pt, Ru,Pd, Fe,Ni Single‐Atom Electrocatalysts with Bifunctional Active Sites for Highly Efficient Water Splitting

Both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) are crucial to water splitting, but require alternative active sites. Now, a general π‐electron‐assisted strategy to anchor single‐atom sites (M=Ir, Pt, Ru, Pd, Fe, Ni) on a heterogeneous support is reported. The M atoms can simultaneously anchor on two distinct domains of the hybrid support, four‐fold N/C atoms (M@NC), and centers of Co octahedra (M@Co), which are expected to serve as bifunctional electrocatalysts towards the HER and the OER. The Ir catalyst exhibits the best water‐splitting performance, showing a low applied potential of 1.603 V to achieve 10 mA cm^?2 in 1.0 m KOH solution with cycling over 5 h. DFT calculations indicate that the Ir@Co (Ir) sites can accelerate the OER, while the Ir@NC₃ sites are responsible for the enhanced HER, clarifying the unprecedented performance of this bifunctional catalyst towards full water splitting.     

The sum is more than its parts: stability of MnFe oxide nanoparticles supported on oxygen-functionalized multi-walled carbon nanotubes at alternating oxygen reduction reaction and oxygen evolution reaction conditions

Successful design of reversible oxygen electrocatalysts does not only require to consider their activity towards the oxygen reduction (ORR) and the oxygen evolution reactions (OER), but also their electrochemical stability at alternating ORR and OER operating conditions, which is important for potential applications in reversible electrolyzers/fuel cells or metal/air batteries. We show that the combination of catalyst materials containing stable ORR active sites with those containing stable OER active sites may result in a stable ORR/OER catalyst if each of the active components can satisfy the current demand of their respective reaction. We compare the ORR/OER performances of oxides of Mn (stable ORR active sites), Fe (stable OER active sites), and bimetallic Mn_0.5Fe_0.5 (reversible ORR/OER catalyst) supported on oxidized multi-walled carbon nanotubes. Despite the instability of Mn and Fe oxide for the OER and the ORR, respectively, Mn_0.5Fe_0.5 exhibits high stability for both reactions.

     

Strong‐Coupled Cobalt Borate Nanosheets/Graphene Hybrid as Electrocatalyst for Water Oxidation Under Both Alkaline and Neutral Conditions

Developing highly active catalysts for the oxygen evolution reaction (OER) is of paramount importance for designing various renewable energy storage and conversion devices. Herein, we report the synthesis of a category of Co‐Pi analogue, namely cobalt‐based borate (Co‐B_i) ultrathin nanosheets/graphene hybrid by a room‐temperature synthesis approach. Benefiting from the high surface active sites exposure yield, enhanced electron transfer capacity, and strong synergetic coupled effect, this Co‐B_i NS/G hybrid shows high catalytic activity with current density of 10 mA cm^?2 at overpotential of 290 mV and Tafel slope of 53 mV dec^?1 in alkaline medium. Moreover, Co‐B_i NS/G electrocatalysts also exhibit promising performance under neutral conditions, with a low onset potential of 235 mV and high current density of 14.4 mA cm^?2 at 1.8 V, which is the best OER performance among well‐developed Co‐based OER electrocatalysts to date. Our finding paves a way to develop highly active OER electrocatalysts.     

NixCo3‐xO4 Nanoneedle Arrays Grown on Ni Foam as an Efficient Bifunctional Electrocatalyst for Full Water Splitting

Developing highly active, stable and robust electrocatalysts based on earth‐abundant elements for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is important for many renewable energy conversion processes. Herein, Ni_xCo_3‐xO₄ nanoneedle arrays grown on 3D porous nickel foam (NF) was synthesized as a bifunctional electrocatalyst with OER and HER activity for full water splitting. Benefiting from the advantageous structure, the composite exhibits superior OER activity with an overpotential of 320 mV achieving the current density of 10 mA cm^?2. An exceptional HER activity is also acquired with an overpotential of 170 mV at the current density of 10 mA cm^?2. Furthermore, the catalyst also shows the superior activity and stability for 20 h when used in the overall water splitting cell. Thus, the hierarchical 3D structure composed of the 1D nanoneedle structure in Ni_xCo_3‐xO₄/NF represents an avenue to design and develop highly active and bifunctional electrocatalysts for promising energy conversion.     

General π‐Electron‐Assisted Strategy for Ir,Pt, Ru,Pd, Fe,Ni Single‐Atom Electrocatalysts with Bifunctional Active Sites for Highly Efficient Water Splitting

Both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) are crucial to water splitting, but require alternative active sites. Now, a general π‐electron‐assisted strategy to anchor single‐atom sites (M=Ir, Pt, Ru, Pd, Fe, Ni) on a heterogeneous support is reported. The M atoms can simultaneously anchor on two distinct domains of the hybrid support, four‐fold N/C atoms (M@NC), and centers of Co octahedra (M@Co), which are expected to serve as bifunctional electrocatalysts towards the HER and the OER. The Ir catalyst exhibits the best water‐splitting performance, showing a low applied potential of 1.603 V to achieve 10 mA cm^?2 in 1.0 m KOH solution with cycling over 5 h. DFT calculations indicate that the Ir@Co (Ir) sites can accelerate the OER, while the Ir@NC₃ sites are responsible for the enhanced HER, clarifying the unprecedented performance of this bifunctional catalyst towards full water splitting.     

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 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.     

Molecular Mixed‐Metal Manganese Oxido Cubanes as Precursors to Heterogeneous Oxygen Evolution Catalysts

Well‐defined mixed‐metal [CoMn₃O₄] and [NiMn₃O₄] cubane complexes were synthesized and used as precursors for heterogeneous oxygen evolution reaction (OER) electrocatalysts. The discrete clusters were dropcasted onto glassy carbon (GC) and indium tin oxide (ITO) electrodes, and the OER activities of the resulting films were evaluated. The catalytic surfaces were analyzed by various techniques to gain insight into the structure‐function relationships of the electrocatalysts’ heterometallic composition. Depending on preparation conditions, the Co‐Mn oxide was found to change metal composition during catalysis, while the Ni–Mn oxides maintained the NiMn₃ ratio. XAS studies provided structural insights indicating that the electrocatalysts are different from the molecular precursors, but that the original NiMn₃O₄ cubane‐like geometry was maintained in the absence of thermal treatment ( 2‐Ni ). In contrast, the thermally generated 3‐Ni develops an oxide‐like extended structure. Both 2‐Ni and 3‐Ni undergo structural changes upon electrolysis, but they do not convert into the same material. The observed structural motifs in these heterogeneous electrocatalysts are reminiscent of the biological oxygen‐evolving complex in Photosystem II, including the MMn₃O₄ cubane moiety. The reported studies demonstrate the use of discrete heterometallic oxide clusters as precursors for heterogeneous water oxidation catalysts of novel composition and the distinct behavior of two sets of mixed metal oxides.