Spatial configuration of Fe-Co dual-sites boosting catalytic intermediates coupling toward oxygen evolution reaction.

Oxygen evolution reaction (OER) is the pivotal obstacle of water splitting for hydrogen production. Dual-sites catalysts (DSCs) are considered exceeding single-site catalysts due to the preternatural synergetic effects of two metals in OER. However, appointing the specific spatial configuration of dual-sites toward more efficient catalysis still remains a challenge. Herein, we constructed two configurations of Fe-Co dual-sites: stereo Fe-Co sites (stereo-Fe-Co DSC) and planar Fe-Co sites (planar-Fe-Co DSC). Remarkably, the planar-Fe-Co DSC has excellent OER performance superior to stereo-Fe-Co DSC. DFT calculations and experiments including isotope differential electrochemical mass spectrometry, in situ infrared spectroscopy, and in situ Raman reveal the *O intermediates can be directly coupled to form *O-O* rather than *OOH by both the DSCs, which could overcome the limitation of four electron transfer steps in OER. Especially, the proper Fe-Co distance and steric direction of the planar-Fe-Co benefit the cooperation of dual sites to dehydrogenate intermediates into *O-O* than stereo-Fe-Co in the rate-determining step. This work provides valuable insights and support for further research and development of OER dual-site catalysts.

Thermal suppression of charge disproportionation accelerates interface electron transfer of water electrolysis.

The sluggish electron transfer kinetics in electrode polarization driven oxygen evolution reaction (OER) result in big energy barriers of water electrolysis. Accelerating the electron transfer at the electrolyte/catalytic layer/catalyst bulk interfaces is an efficient way to improve electricity-to-hydrogen efficiency. Herein, the electron transfer at the Sr3Fe2O7@SrFeOOH bulk/catalytic layer interface is accelerated by heating to eliminate charge disproportionation from Fe4+ to Fe3+ and Fe5+ in Sr3Fe2O7, a physical effect to thermally stabilize high-spin Fe4+ (t2g3eg1), providing available orbitals as electron transfer channels without pairing energy. As a result of thermal-induced changes in electronic states via thermal comproportionation, a sudden increase in OER performances was achieved as heating to completely suppress charge disproportionation, breaking a linear Arrhenius relationship. The strategy of regulating electronic states by thermal field opens a broad avenue to overcome the electron transfer barriers in water splitting.

Tailoring atomic chemistry to refine reaction pathway for the most enhancement by magnetization in water oxidation.

Water oxidation on magnetic catalysts has generated significant interest due to the spin-polarization effect. Recent studies have revealed that the disappearance of magnetic domain wall upon magnetization is responsible for the observed oxygen evolution reaction (OER) enhancement. However, an atomic picture of the reaction pathway remains unclear, i.e., which reaction pathway benefits most from spin-polarization, the adsorbent evolution mechanism, the intermolecular mechanism (I2M), the lattice oxygen-mediated one, or more? Here, using three model catalysts with distinguished atomic chemistries of active sites, we are able to reveal the atomic-level mechanism. We found that spin-polarized OER mainly occurs at interconnected active sites, which favors direct coupling of neighboring ligand oxygens (I2M). Furthermore, our study reveals the crucial role of lattice oxygen participation in spin-polarized OER, significantly facilitating the coupling kinetics of neighboring oxygen radicals at active sites.

Oxygen-bridging Fe, Co dual-metal dimers boost reversible oxygen electrocatalysis for rechargeable Zn-air batteries.

Rechargeable zinc-air batteries (ZABs) are regarded as a remarkably promising alternative to current lithium-ion batteries, addressing the requirements for large-scale high-energy storage. Nevertheless, the sluggish kinetics involving oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) hamper the widespread application of ZABs, necessitating the development of high-efficiency and durable bifunctional electrocatalysts. Here, we report oxygen atom-bridged Fe, Co dual-metal dimers (FeOCo-SAD), in which the active site Fe-O-Co-N6 moiety boosts exceptional reversible activity toward ORR and OER in alkaline electrolytes. Specifically, FeOCo-SAD achieves a half-wave potential (E1/2) of 0.87 V for ORR and an overpotential of 310 mV at a current density of 10 mA cm-2 for OER, with a potential gap (ΔE) of only 0.67 V. Meanwhile, FeOCo-SAD manifests high performance with a peak power density of 241.24 mW cm-2 in realistic rechargeable ZABs. Theoretical calculations demonstrate that the introduction of an oxygen bridge in the Fe, Co dimer induced charge spatial redistribution around Fe and Co atoms. This enhances the activation of oxygen and optimizes the adsorption/desorption dynamics of reaction intermediates. Consequently, energy barriers are effectively reduced, leading to a strong promotion of intrinsic activity toward ORR and OER. This work suggests that oxygen-bridging dual-metal dimers offer promising prospects for significantly enhancing the performance of reversible oxygen electrocatalysis and for creating innovative catalysts that exhibit synergistic effects and electronic states.

Triggered lattice-oxygen oxidation with active-site generation and self-termination of surface reconstruction during water oxidation.

To master the activation law and mechanism of surface lattice oxygen for the oxygen evolution reaction (OER) is critical for the development of efficient water electrolysis. Herein, we propose a strategy for triggering lattice-oxygen oxidation and enabling non-concerted proton-electron transfers during OER conditions by substituting Al in La0.3Sr0.7CoO3-δ. According to our experimental data and density functional theory calculations, the substitution of Al can have a dual effect of promoting surface reconstruction into active Co oxyhydroxides and activating deprotonation on the reconstructed oxyhydroxide, inducing negatively charged oxygen as an active site. This leads to a significant improvement in the OER activity. Additionally, Al dopants facilitate the preoxidation of active cobalt metal, which introduces great structural flexibility due to elevated O 2p levels. As OER progresses, the accumulation of oxygen vacancies and lattice-oxygen oxidation on the catalyst surface leads to the termination of Al3+ leaching, thereby preventing further reconstruction. We have demonstrated a promising approach to achieving tunable electrochemical reconstruction by optimizing the electronic structure and gained a fundamental understanding of the activation mechanism of surface oxygen sites.

Dynamic orbital hybridization triggered spin-disorder renormalization via super-exchange interaction for oxygen evolution reaction.

The oxygen evolution reaction (OER) underpins many aspects of energy storage and conversion in modern industry and technology, but which still be suffering from the dilemma of sluggish reaction kinetics and poor electrochemical performance. Different from the viewpoint of nanostructuring, this work focuses on an intriguing dynamic orbital hybridization approach to renormalize the disordering spin configuration in porous noble-metal-free metal-organic frameworks (MOFs) to accelerate the spin-dependent reaction kinetics in OER. Herein, we propose an extraordinary super-exchange interaction to reconfigure the domain direction of spin nets at porous MOFs through temporarily bonding with dynamic magnetic ions in electrolytes under alternating electromagnetic field stimulation, in which the spin renormalization from disordering low-spin state to high-spin state facilitates rapid water dissociation and optimal carrier migration, leading to a spin-dependent reaction pathway. Therefore, the spin-renormalized MOFs demonstrate a mass activity of 2,095.1 A gmetal-1 at an overpotential of 0.33 V, which is about 5.9 time of pristine ones. Our findings provide a insight into reconfiguring spin-related catalysts with ordering domain directions to accelerate the oxygen reaction kinetics.

Phenomenology of Intermediate Molecular Dynamics at Metal-Oxide Interfaces.

Reaction intermediates buried within a solid-liquid interface are difficult targets for physiochemical measurements. They are inherently molecular and locally dynamic, while their surroundings are extended by a periodic lattice on one side and the solvent dielectric on the other. Challenges compound on a metal-oxide surface of varied sites and especially so at its aqueous interface of many prominent reactions. Recently, phenomenological theory coupled with optical spectroscopy has become a more prominent tool for isolating the intermediates and their molecular dynamics. The following article reviews three examples of the SrTiO3-aqueous interface subject to the oxygen evolution from water: reaction-dependent component analyses of time-resolved intermediates, a Fano resonance of a mode at the metal-oxide-water interface, and reaction isotherms of metastable intermediates. The phenomenology uses parameters to encase what is unknown at a microscopic level to then circumscribe the clear and macroscopically tuned trends seen in the spectroscopic data.

Magnetic Field Enhanced Cobalt Iridium Alloy Catalyst for Acidic Oxygen Evolution Reaction.

Magnetic field mediated magnetic catalysts provide a powerful pathway for accelerating their sluggish kinetics toward the oxygen evolution reaction (OER) but remain great challenges in acidic media. The key obstacle comes from the production of an ordered magnetic domain catalyst in the harsh acidic OER. In this work, we form an induced local magnetic moment in the metallic Ir catalyst via the significant 3d-5d hybridization by introducing cobalt dopants. Interestingly, CoIr nanoclusters (NCs) exhibit an excellent magnetic field enhanced acidic OER activity, with the lowest overpotential of 220 mV at 10 mA cm-2 and s long-term stability of 120 h under a constant magnetic field (vs 260 mV/20 h without a magnetic field). The turnover frequency reaches 7.4 s-1 at 1.5 V (vs RHE), which is 3.0 times higher than that without magnetization. Density functional theory results show that CoIr NCs have a pronounced spin polarization intensity, which is preferable for OER enhancement.

Breaking the Bottleneck of Activity and Stability of RuO2-Based Electrocatalysts for Acidic Oxygen Evolution.

Electrochemical acidic oxygen evolution reaction (OER) is an important part for water electrolysis utilizing a proton exchange membrane (PEM) apparatus for industrial H2 production. RuO2 has garnered considerable attention as a potential acidic OER electrocatalyst. However, the overoxidation of Ru active sites under high potential conditions is usually harmful for activity and stability, thereby posing a challenge for large-scale commercialization, which needs effective strategies to circumvent the leaching of Ru and further activate Ru sites. Herein, a Mini-Review is presented to summarize the recent developments regarding the activation and stabilization of the Ru active sites and lattice oxygen through the modulation of the d-band center, coordination environment, bridged heteroatoms, and vacancy engineering, as well as structural protection strategies and reaction pathway optimization to promote the acidic OER activity and stability of RuO2-based electrocatalysts. This Mini-Review offers a profound understanding of the design of RuO2-based electrocatalysts with greatly enhanced acidic OER performances.

Surface-Diffusion-Induced Amorphization of Pt Nanoparticles over Ru Oxide Boost Acidic Oxygen Evolution.

Phase transformation offers an alternative strategy for the synthesis of nanomaterials with unconventional phases, allowing us to further explore their unique properties and promising applications. Herein, we first observed the amorphization of Pt nanoparticles on the RuO2 surface by in situ scanning transmission electron microscopy. Density functional theory calculations demonstrate the low energy barrier and thermodynamic driving force for Pt atoms transferring from the Pt cluster to the RuO2 surface to form amorphous Pt. Remarkably, the as-synthesized amorphous Pt/RuO2 exhibits 14.2 times enhanced mass activity compared to commercial RuO2 catalysts for the oxygen evolution reaction (OER). Water electrolyzer with amorphous Pt/RuO2 achieves 1.0 A cm-2 at 1.70 V and remains stable at 200 mA cm-2 for over 80 h. The amorphous Pt layer not only optimized the *O binding but also enhanced the antioxidation ability of amorphous Pt/RuO2, thereby boosting the activity and stability for the OER.

Unlocking the Potential: Atomically Thin 2D Fluoritene from Exfoliated Fluorite Ore and Its Electrochemical Activity.

Fluorite mineral holds significant importance because of its optoelectronic properties and wide range of applications. Here, we report the successful exfoliation of bulk fluorite ore (calcium fluoride, CaF2) crystals into atomically thin two-dimensional fluoritene (2D CaF2) using a highly scalable liquid-phase exfoliation method. The microscopic and spectroscopy characterizations show the formation of (111) plane-oriented 2D CaF2 sheets with exfoliation-induced material strain due to bond breaking, leading to the changes in lattice parameter. Its potential role in electrocatalysis is further explored for deeper insight, and a probable mechanism is also discussed. The 2D CaF2 with long-term stability shows overpotential values of 670 and 770 mV vs RHE for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively, at 10 mA cm-2. Computational simulations demonstrate the unique "direct-indirect" band gap switching with odd and even numbers of layers. Current work offers new avenues for exploring the structural and electrochemical properties of 2D CaF2 and its potential applicability.

Motivating Inert Strontium Manganate with Iridium Dopants as Efficient Electrocatalysts for Oxygen Evolution in Acidic Electrolyte.

The search for high-performance and low-cost electrocatalysts in acid conditions still remains a challenging target. Herein, iridium (Ir) doped strontium manganate (named as Irx -SMO) is proposed as an efficient and durable low-iridium electrocatalyst for water oxidation in acidic media. The Ir0.1 -SMO with 75% less iridium in comparison to that of iridium dioxide (IrO2 ) exhibits excellent performance for oxygen evolution reaction (OER), which is even better than most of the iridium-based oxide electrocatalysts. The theoretical outcomes confirm the activation of the inert manganese sites in strontium manganate by the incorporation of iridium dopants. This work reveals the boosted effect of the iridium dopants on the OER activity of strontium manganate, providing a strategy to tune the activity of manganese-based perovskites in electrocatalysis.

Improving the Oxygen Evolution Reaction: Exsolved Cobalt Nanoparticles on Titanate Perovskite Catalyst.

Perovskites are an important class of oxygen evolution reaction (OER) catalysts due to highly tunable compositions and adaptable characteristics. However, perovskite-based catalysts can have limited atom utilization efficiency due to large particle size, resulting in low mass activity. Herein, Cobalt nanoparticles are exsolved from La0.2+2x Ca0.7-2x Ti1-x Cox O3 perovskite and applied in OER. Upon reduction in the 5% H2 /N2 atmosphere at 800 °C for 2 h, the Co exsolved perovskite catalyst (R-LCTCo0.11) exhibits optimal OER performance. The mass activity of R-LCTCo0.11 reaches ≈1700 mA mg-1 at an overpotential of 450 mV, which is 17 times and 3 times higher than that of LCTCo0.11 (97 mA mg-1 ) and R-Mix (560 mA mg-1 ) catalysts respectively, surpassing the benchmark catalyst RuO2 (42.7 mA mg-1 of oxide at η = 470 mV). Electrochemical impedance spectroscopy (EIS) data reveals that R-LCTCo0.11 has the lowest charge transfer resistance (Rct  = 58 Ω), demonstrating the highest catalytic and kinetic activity for OER. Furthermore, this catalyst shows high stability during an accelerated durability test of 10 h electrolysis and 1000 cycles cyclic voltammetry (CV). This work demonstrates that nanoparticle exsolution from a doped perovskite is an effective strategy for improving the atom utilization efficiency in OER.

Achieving High-Performance Electrocatalytic Water Oxidation on Ni(OH)2 with Optimized Intermediate Binding Energy Enabled by S-Doping and CeO2 -Interfacing.

The adsorption energy of the reaction intermediates has a crucial influence on the electrocatalytic activity. Ni-based materials possess high oxygen evolution reaction (OER) performance in alkaline, however too strong binding of *OH and high energy barrier of the rate-determining step (RDS) severely limit their OER activity. Herein, a facile strategy is shown to fabricate novel vertical nanorod-like arrays hybrid structure with the interface contact of S-doped Ni(OH)2 and CeO2 in situ grown on Ni foam (S-Ni(OH)2 /CeO2 /NF) through a one-pot route. The alcohol molecules oxidation reaction experiments and theoretical calculations demonstrate that S-doping and CeO2 -interfacing significantly modulate the binding energies of OER intermediates toward optimal value and reduce the energy barrier of the RDS, contributing to remarkable OER activity for S-Ni(OH)2 /CeO2 /NF with an ultralow overpotential of 196 mV at 10 mA cm-2 and long-term durability over 150 h for the OER. This work offers an efficient doping and interfacing strategy to tune the binding energy of the OER intermediates for obtaining high-performance electrocatalysts.

Synchronous Surface-Interface and Crystal-Phase Engineered Multifaceted Hybrid Nanostructure of Fe-(1T)-VSe2 Nanosheet and Fe-CoSe2 Nanorods Doped with P for Rapid HER and OER, Kinetics.

Two different nanostructures of two dissimilar highly-potent active electrocatalysts, P-dopped metallic-(1T)-Fe-VSe2 (P,Fe-1T-VSe2 ) nanosheet and P-dopped Fe-CoSe2 (P,Fe-CoSe2 ) nanorods are hybridized and integrated into a single heterostructure (P,Fe-(VCo)Se2 ) on Ni-foam for high-performance water splitting (WS). The catalytic efficiency of VSe2 nanosheets is first enhanced by enriching metallic (1T)-phase, then forming bimetallic Fe-V selenide, and finally by P-doping. Similarly, the catalytic efficiency of CoSe2 nanorods is boosted by first fabricating Fe-Co bimetallic selenide and then P-doping. To develop super-efficient electrocatalysts for WS, two individual electrocatalysts P,Fe-1T-VSe2 nanosheet and P,Fe-CoSe2 are hybridized and integrated to form a heterostructure (P,Fe-(VCo)Se2 ). Metallic (1T)-phase of transition metal dichalcogenides has much higher conductivity than the 2H-phase, while bimetallization and P-doping activate basal planes, develop various active components, and form heterostructures that develop a synergistic interfacial effect, all of which, significantly boost the catalytic efficacy of the P,Fe-(VCo)Se2 . P,Fe-(VCo)Se2 shows excellent performance requiring very low overpotential (ηHER = 50 mV@10 mAcm-2 and ηOER = 230 mV@20 mAcm-2 ). P,Fe-(VCo)Se2 (+, -) device requires a cell potential of 1.48 V to reach 10 mA cm-2 for overall WS.

Advances in Stability of NiFe-Based Anodes toward Oxygen Evolution Reaction for Alkaline Water Electrolysis.

Alkaline electrolysis plays a crucial role in sustainable energy solutions by utilizing electrolytic cells to produce hydrogen gas, providing a clean and efficient method for energy storage and conversion. Efficient, stable, and low-cost electrocatalysts for the oxygen evolution reaction (OER) are essential to facilitate alkaline water electrolysis on a commercial scale. Nickel-iron-based (NiFe-based) transition metal electrocatalysts are considered the most promising non-precious metal catalysts for alkaline OER due to their low cost, abundance, and tunable catalytic properties. Nevertheless, the majority of existing NiFe-based catalysts suffer from limited activity and poor stability, posing a significant challenge in meeting industrial applications. This also highlights a common situation where the emphasis on material activity receives significant attention, while the equally critical stability aspect is often underemphasized. Initiating with a comprehensive exploration of the stability of NiFe-based OER materials, this article first summarizes the debate surrounding the determination of active sites in NiFe-based OER electrocatalysts. Subsequently, the degradation mechanisms of recently reported NiFe-based electrocatalysts are outlined, encompassing assessments of both chemical and mechanical endurance, along with essential approaches for enhancing their stability. Finally, suggestions are put forth regarding the essential considerations for the design of NiFe-based OER electrocatalysts, with a focus on heightened stability.

Recent Research on Iridium-Based Electrocatalysts for Acidic Oxygen Evolution Reaction from the Origin of Reaction Mechanism.

As the anode reaction of proton exchange membrane water electrolysis (PEMWE), the acidic oxygen evolution reaction (OER) is one of the main obstacles to the practical application of PEMWE due to its sluggish four-electron transfer process. The development of high-performance acidic OER electrocatalysts has become the key to improving the reaction kinetics. To date, although various excellent acidic OER electrocatalysts have been widely researched, Ir-based nanomaterials are still state-of-the-art electrocatalysts. Hence, a comprehensive and in-depth understanding of the reaction mechanism of Ir-based electrocatalysts is crucial for the precise optimization of catalytic performance. In this review, the origin and nature of the conventional adsorbate evolution mechanism (AEM) and the derived volcanic relationship on Ir-based electrocatalysts for acidic OER processes are summarized and some optimization strategies for Ir-based electrocatalysts based on the AEM are introduced. To further investigate the development strategy of high-performance Ir-based electrocatalysts, several unconventional OER mechanisms including dual-site mechanism and lattice oxygen mediated mechanism, and their applications are introduced in detail. Thereafter, the active species on Ir-based electrocatalysts at acidic OER are summarized and classified into surface Ir species and O species. Finally, the future development direction and prospect of Ir-based electrocatalysts for acidic OER are put forward.

Atomic Strain Wave-Featured LaRuIr Nanocrystals: Achieving Simultaneous Enhancement of Catalytic Activity and Stability toward Acidic Water Splitting.

Rare earth microalloying nanocrystals have gotten widespread attention due to their unprecedented performances with customization-defected nanostructures, divided energy bands, and ensembled surface chemistry, regarded as a class of ideal electrocatalysts for oxygen evolution reaction (OER). Herein, a lanthanide microalloying strategy is proposed to fabricate strain wave-featured LaRuIr nanocrystals with oxide skin through a rapid crystal nucleation, using thermally assisted sodium borohydride reduction in aqueous solution at 60 °C. The atomic strain waves with alternating compressive and tensile strains, resulting from La-stabilized edge dislocations in form of Cottrell atmospheres. In 0.5 m H2SO4, the LaRuIr displays an overpotential of 184 mV at 10 mA cm-2, running at a steadily cell voltage for 60 h at 50 mA cm-2, eightfold enhancement of IrO2||Pt/C assemble in PEMWE. The coupled compressive and tensile profiles boost the OER kinetics via faster AEM and LOM pathways. Moreover, the tensile facilitates surface structure stabilization through dynamic refilling of lattice oxygen vacancies by the adsorbed oxyanions on La, Ru, and Ir sites, eventually achieving a long-term stability. This work contributes to developing advanced catalysts with unique strain to realize simultaneous improvement of activity and durability by breaking the so-called seesaw relationship between them during OER for water splitting.

Recent Advancements on Spin Engineering Strategies for Highly Efficient Electrocatalytic Oxygen Evolution Reactions.

Oxygen evolution reaction (OER) is a widely employed half-electrode reaction in oxygen electrochemistry, in applications such as hydrogen evolution, carbon dioxide reduction, ammonia synthesis, and electrocatalytic hydrogenation. Unfortunately, its slow kinetics limits the commercialization of such applications. It is therefore highly imperative to develop highly robust electrocatalysts with high activity, long-term durability, and low noble-metal contents. Previously intensive efforts have been made to introduce the advancements on developing non-precious transition metal electrocatalysts and their OER mechanisms. Electronic structure tuning is one of the most effective and interesting ways to boost OER activity and spin angular momentum is an intrinsic property of the electron. Therefore, modulation on the spin states and the magnetic properties of the electrocatalyst enables the changes on energy associated with interacting electron clouds with radical absorbance, affecting the OER activity and stability. Given that few review efforts have been made on this topic, in this review, the-state-of-the-art research progress on spin-dependent effects in OER will be briefed. Spin engineering strategies, such as strain, crystal surface engineering, crystal doping, etc., will be introduced. The related mechanism for spin manipulation to boost OER activity will also be discussed. Finally, the challenges and prospects for the development of spin catalysis are presented. This review aims to highlight the significance of spin engineering in breaking the bottleneck of electrocatalysis and promoting the practical application of high-efficiency electrocatalysts.

The Role of Photo in Oxygen Evolution Reaction: A Review.

Photo enhanced oxygen evolution reaction has recently emerged as an advanced strategy with great application prospects for highly efficient energy conversion and storage. In the course of photo enhanced oxygen evolution reactions, the other works focus has predominantly centered on catalysts while inadvertently overlooking the pivotal role of photo. Consequently, this manuscript embarks upon a comprehensive review of recent advancements in photo-driven, aiming to illuminate this critical dimension. A detailed introduction to the photothermal effect, photoelectronic effect, photon-induced surface plasmon resonance, photo and heterojunction, photo-induced reversible geometric conversion, photo-induced energy barrier reduction, photo-induced chemical effect, photo-charging, and the synthesis of laser/photo-assisted catalysts, offering prospects for the development of each case is provided. A detailed introduction to the photothermal effect, photoelectronic effect, photon-induced surface plasmon resonance, photo and heterojunction, photo-induced reversible geometric conversion, photo-induced energy barrier reduction, photo-induced chemical effect, photo-charging, and the synthesis of laser/photo-assisted catalysts is provided. At the same time, the overpotential and Tafel slope of some catalysts mentioned above at 10 mA cm-2 is collected, and calculated the lifting efficiency of light on them, offering prospects for the development of each case.