High-Performance Alkaline Seawater Electrolysis with Anomalous Chloride Promoted Oxygen Evolution Reaction

A highly selective and durable oxygen evolution reaction (OER) electrocatalyst is the bottleneck for direct seawater splitting because of side reactions primarily caused by chloride ions (Cl⁻). Most studies about OER catalysts in seawater focus on the repulsion of the Cl⁻ to reduce its negative effects. Herein, we demonstrate that the absorption of Cl⁻ on the specific site of a popular OER electrocatalyst, nickel-iron layered double hydroxide (NiFe LDH), does not have a significant negative impact; rather, it is beneficial for its activity and stability enhancement in natural seawater. A set of in situ characterization techniques reveals that the adsorption of Cl⁻ on the desired Fe site suppresses Fe leaching, and creates more OER-active Ni sites, improving the catalyst's long-term stability and activity simultaneously. Therefore, we achieve direct alkaline seawater electrolysis for the very first time on a commercial-scale alkaline electrolyser (AE, 120 cm² electrode area) using the NiFe LDH anode. The new alkaline seawater electrolyser exhibits a reduction in electricity consumption by 20.7 % compared to the alkaline purified water-based AE using commercial Ni catalyst, achieving excellent durability for 100 h at 200 mA cm⁻².     

Bifunctional Near-Neutral Electrolyte Enhances Oxygen Evolution Reaction

Performance of electrocatalytic reactions depends on not only the composition and structure of the active sites, but also their local environment, including the surrounding electrolyte. In this work, we demonstrate that BF₂(OH)₂⁻ anion is the key fluoroborate species formed in the mixed KBi/KF (KBi=potassium borate) electrolyte to enhance the rate of the oxygen evolution reaction (OER) at near-neutral pH. Through a combination of electrokinetic and in situ spectroscopic studies, we show that the mixed KBi/KF electrolyte promotes the OER via two pathways: 1) stabilizing the interfacial pH during the proton-producing reaction with its high buffering capacity; and 2) activating the interfacial water via strong hydrogen bonds with F-containing species. With the KBi/KF electrolyte, electrodeposited Co(OH)₂ is able to achieve 100 mA/cm² at 1.74 V, which is among the highest reported activities with earth-abundant electrocatalysts at near neutral conditions. These findings highlight the potential of leveraging electrolyte-engineering for improving the electrochemical performance of the OER.     

Long-Term Stability Challenges and Opportunities in Acidic Oxygen Evolution Electrocatalysis

Polymer electrolyte membrane water electrolysis (PEMWE) has been regarded as a promising technology for renewable hydrogen production. However, acidic oxygen evolution reaction (OER) catalysts with long-term stability impose a grand challenge in its large-scale industrialization. In this review, critical factors that may lead to catalyst's instability in couple with potential solutions are comprehensively discussed, including mechanical peeling, substrate corrosion, active-site over-oxidation/dissolution, reconstruction, oxide crystal structure collapse through the lattice oxygen-participated reaction pathway, etc. Last but not least, personal prospects are provided in terms of rigorous stability evaluation criteria, in situ/operando characterizations, economic feasibility and practical electrolyzer consideration, highlighting the ternary relationship of structure evolution, industrial-relevant activity and stability to serve as a roadmap towards the ultimate application of PEMWE.     

Perovskite Oxide as A New Platform for Efficient Electrocatalytic Nitrogen Oxidation

Electrocatalytic nitrogen oxidation reaction (NOR) offers an efficient and sustainable approach for conversion of widespread nitrogen (N₂) into high-value-added nitrate (NO₃⁻) under mild conditions, representing a promising alternative to the traditional approach that involves harsh Haber–Bosch and Ostwald oxidation processes. Unfortunately, due to the weak absorption/activation of N₂ and the competitive oxygen evolution reaction, the kinetics of NOR process is extremely sluggish accompanied with low Faradaic efficiencies and NO₃⁻ yield rates. In this work, an oxygen-vacancy-enriched perovskite oxide with nonstoichiometric ratio of strontium and ruthenium (denoted as Sr_0.9RuO₃) was synthesized and explored as NOR electrocatalyst, which can exhibit a high Faradaic efficiency (38.6 %) with a high NO₃⁻ yield rate (17.9 μmol mg⁻¹ h⁻¹). The experimental results show that the amount of oxygen vacancies in Sr_0.9RuO₃ is greatly higher than that of SrRuO₃, following the same trend as their NOR performance. Theoretical simulations unravel that the presence of oxygen vacancies in the Sr_0.9RuO₃ can render a decreased thermodynamic barrier toward the oxidation of *N₂ to *N₂OH at the rate-determining step, leading to its enhanced NOR performance.     

Scalable Synthesis of Multi-Metal Electrocatalyst Powders and Electrodes and their Application for Oxygen Evolution and Water Splitting

Multi-metal electrocatalysts provide nearly unlimited catalytic possibilities arising from synergistic element interactions. We propose a polymer/metal precursor spraying technique that can easily be adapted to produce a large variety of compositional different multi-metal catalyst materials. To demonstrate this, 11 catalysts were synthesized, characterized, and investigated for the oxygen evolution reaction (OER). Further investigation of the most active OER catalyst, namely CoNiFeMoCr, revealed a polycrystalline structure, and operando Raman measurements indicate that multiple active sites are participating in the reaction. Moreover, Ni foam-supported CoNiFeMoCr electrodes were developed and applied for water splitting in flow-through electrolysis cells with electrolyte gaps and in zero-gap membrane electrode assembly (MEA) configurations. The proposed alkaline MEA-type electrolyzers reached up to 3 A cm⁻², and 24 h measurements demonstrated no loss of current density of 1 A cm⁻².     

Accelerated Surface Reconstruction through Regulating the Solid-Liquid Interface by Oxyanions in Perovskite Electrocatalysts for Enhanced Oxygen Evolution

A comprehensive understanding of surface reconstruction was critical to developing high performance lattice oxygen oxidation mechanism (LOM) based perovskite electrocatalysts. Traditionally, the primary determining factor of the surface reconstruction process was believed to be the oxygen vacancy formation energy. Hence, most previous studies focused on optimizing composition to reduce the oxygen vacancy formation energy, which in turn facilitated the surface reconstruction process. Here, for the first time, we found that adding oxyanions (SO₄²⁻, CO₃²⁻, NO₃⁻) into the electrolyte could effectively regulate the solid–liquid interface, significantly accelerating the surface reconstruction process and enhancing oxygen evolution reaction (OER) activities. Further studies indicated that the added oxyanions would adsorb onto the solid–liquid interface layer, disrupting the dynamic equilibrium between the adsorbed OH⁻ ions and the OH⁻ ions generated during surface reconstruction process. As such, the OH⁻ ions generated during surface reconstruction process could be more readily released into the electrolyte, thereby leading to an acceleration of the surface reconstruction. Thus, it was expected that our finding would provide a new layer of understanding to the surface reconstruction process in LOM-based perovskite electrocatalysts.     

Electrocatalytic Water Oxidation Activity-Stability Maps for Perovskite Oxides Containing 3d, 4d and 5d Transition Metals

Improving catalytic activity without loss of catalytic stability is one of the core goals in search of low-iridium-content oxygen evolution electrocatalysts under acidic conditions. Here, we synthesize a family of 66 SrBO₃ perovskite oxides (B=Ti, Ru, Ir) with different Ti : Ru : Ir atomic ratios and construct catalytic activity-stability maps over composition variation. The maps classify the multicomponent perovskites into chemical groups with distinct catalytic activity and stability for acidic oxygen evolution reaction, and highlights a chemical region where high catalytic activity and stability are achieved simultaneously at a relatively low iridium level. By quantifying the extent of hybridization of mixed transition metal 3d-4d-5d and oxygen 2p orbitals for multicomponent perovskites, we demonstrate this complex interplay between 3d-4d-5d metals and oxygen atoms in governing the trends in both activity and stability as well as in determining the catalytic mechanism involving lattice oxygen or not.     

Unveiling the Electrolyte Cations Dependent Kinetics on CoOOH-Catalyzed Oxygen Evolution Reaction

The electrolyte cations-dependent kinetics have been widely observed in many fields of electrocatalysis, however, the exact mechanism of the influence on catalytic performance is still a controversial topic of considerable discussion. Herein, combined with operando X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM), we verify that the electrolyte cations could intercalate into the layer of pristine CoOOH catalyst during the oxygen evolution reaction (OER) process, while the bigger cations lead to enlarged interlayer spacing and increased OER activity, following the order Cs⁺>K⁺>Na⁺>Li⁺. X-ray absorption spectroscopy (XAS), in situ Raman, in situ Ultraviolet-visible (UV/Vis) spectroscopy, in situ XAS spectroscopy, cyclic voltammetry (CV), and theoretical calculations reveal that the intercalation of electrolyte cations efficiently modify the oxidation states of Co by enlarging the Co−O bonds, which in turn enhance the d-band center of Co, optimize the adsorption strength of oxygen intermediates, facilitate the formation of OER active Co(IV) species, and reduce the energy barrier of the rate-determing step (RDS), thereby enhancing the OER activity. This work not only provides an informative picture to understand the complicated dependence of OER kinetics on electrolyte cations, but also sheds light on understanding the mechanism of other electrolyte cation-targeted electrocatalysis.     

Water-Assisted Chemical Route Towards the Oxygen Evolution Reaction at the Hydrated (110) Ruthenium Oxide Surface: Heterogeneous Catalysis via DFT-MD and Metadynamics Simulations

Notwithstanding that RuO₂ is a promising catalyst for the oxygen evolution reaction (OER), a plethora of fundamental details on its catalytic properties are still elusive, severely limiting its large-scale deployment. It is also established experimentally that corrosion and wettability of metal oxides can, in fact, enhance the catalytic activity for OER owing to the formation of a hydrated surface layer. However, the mechanistic interplay between surface wettability, interfacial water dynamics and OER across RuO₂, and what degree these processes are correlated are still debated. Herein, spin-polarized Density Functional Theory Molecular Dynamics (DFT-MD) simulations, coupled with advanced enhanced sampling methods in the well-tempered metadynamics framework, are applied to gain a global understanding of RuO₂ aqueous interface (explicit water solvent) in catalyzing the OER, and hence possibly help in the design of novel catalysts in the context of photochemical water oxidation. The present study quantitatively assesses the free-energy barriers behind the OER at the (110)-RuO₂ catalyst surface revealing plausible pathways composing the reaction network of the O₂ evolution. In particular, OER is investigated at room temperature when such a surface is exposed to both gas-phase and liquid-phase water. Albeit a unique efficient pathway has been identified in the gas-phase OER, a surprisingly lowest-free-energy-requiring reaction route is possible when (110)-RuO₂ is in contact with explicit liquid water. By estimating the free-energy surfaces associated to these processes, we reveal a noticeable water-assisted OER mechanism which involves a crucial proton-transfer-step assisted by the local water environment. These findings pave the way toward the systematic usage of DFT-MD coupled with metadynamics techniques for the fine assessment of the activity of catalysts, considering finite-temperature and explicit-solvent effects.     

钙钛矿型复合氧化物CaVO3的制备及对氧还原反应的电催化性能

以五氧化二钒、硝酸钙、柠檬酸和草酸为原料,采用溶胶-凝胶法制备出CaVO₃的前驱体,在氩气保护下1000 ℃煅烧2 h,成功制备出目标产物CaVO₃.对前驱体和目标产物分别进行了傅里叶变换红外(FTIR)光谱、热重(TG)分析、X射线衍射(XRD)和电导率等表征.在1 mol·L^-1的KOH电解质溶液中测试了样品的氧还原反应(ORR)催化性能.结果表明,修饰电极上(ORR)的电子转移数是1.5-1.7,发生的是2电子还原.     

微波热冲快速制备二维多孔La0.2Sr0.8CoO3钙钛矿用于高效电催化析氧反应

析氧反应(OER)被认为是电解水的关键限制步骤,已被广泛作为清洁能源方式用于解决能源和环境问题。钙钛矿氧化物(ABO₃)具有可调的电子结构、高灵活性的元素组成,能在OER中表现出良好的催化活性。然而,钙钛矿氧化物的合成通常需要经历长时间的高温,极易导致金属的聚集和影响材料的本征活性。气相微波技术可以显著缩短热处理时间,从而减少相关的碳排放。这项技术不仅解决了对碳中性过程日益增长的需求,而且还增加了对合成的控制,以避免产品的不良团聚。本文采用微波热冲法快速制备了二维(2D)多孔La_0.2Sr_0.8CoO₃钙钛矿。伴随微波过程的快速熵增可以有效地暴露La_0.2Sr_0.8CoO₃结构中丰富的活性位点。此外,高能微波冲击过程可以精准地将Sr²⁺引入到LaCoO₃的晶格中,通过增加Co的氧化态来增加氧空位量。这种锶元素取代镧引入的氧空位能极大提高催化剂的本征催化活性。对于碱性电解液中的OER应用,制备的La_0.2Sr_0.8CoO₃在10 mA∙cm⁻²下展现出了360 mV的过电位,Tafel斜率为76.6 mV∙dec⁻¹。且在经历30000秒的长时间循环测试后仍能维持初始电流密度的97%。这项研究为高活性二维钙钛矿的合成提供了一种简便、快速的策略。     

Non-Kinetic Effects Convolute Activity and Tafel Analysis for the Alkaline Oxygen Evolution Reaction on NiFeOOH Electrocatalysts

A large variety of nickel-based catalysts has been investigated for the oxygen evolution reaction (OER) in alkaline media. However, their reported activity, as well as Tafel slope values, vary greatly. To understand this variation, we studied electrodeposited Ni₈₀Fe₂₀OOH catalysts with different loadings at varying rotation rates, hydroxide concentrations, with or without sonication. We show that, at low current density (<5 mA cm⁻²), the Tafel slope value is ≈30 mV dec⁻¹ for Ni₈₀Fe₂₀OOH. At higher polarization, the Tafel slope continuously increases and is dependent on rotation rate, loading, hydroxide concentration and sonication. These Tafel slope values are convoluted by non-kinetic effects, such as bubbles, potential-dependent changes in ohmic resistance and (internal) OH⁻ gradients. As best practise, we suggest that Tafel slopes should be plotted vs. current or potential. In such a plot, it can be appreciated if there is a kinetic Tafel slope or if the observed Tafel slope is influenced by non-kinetic effects.     

Reversely Trapping Isolated Atoms in High Oxidation State for Accelerating the Oxygen Evolution Reaction Kinetics

Developing efficient electrocatalysts for the oxygen evolution reaction (OER) is paramount to the energy conversion and storage devices. However, the structural complexity of heterogeneous electrocatalysts makes it a great challenge to elucidate the dynamic structural evolution and OER mechanisms. Here, we develop a controllable atom-trapping strategy to extract isolated Mo atom from the amorphous MoO_x-decorated CoSe₂ (a-MoO_x@CoSe₂) pre-catalyst into Co-based oxyhydroxide (Mo-CoOOH) through an ultra-fast self-reconstruction process during the OER process. This conceptual advance has been validated by operando characterizations, which reveals that the initially rapid Mo leaching can expedite the dynamic reconstruction of pre-catalyst, and simultaneously trap Mo species in high oxidation state into the lattice of in situ generated CoOOH support. Impressively, the OER kinetics of CoOOH has been greatly accelerated after the reverse decoration of Mo species, in which the Mo-CoOOH affords a markedly decreased overpotential of 297 mV at the current density of 100 mA cm⁻². Density functional theory (DFT) calculations demonstrate that the Co species have been greatly activated via the effective electron coupling with Mo species in high oxidation state. These findings open new avenues toward directly synthesizing atomically dispersed electrocatalysts for high-efficiency water splitting.     

Low Ruthenium Content Confined on Boron Carbon Nitride as an Efficient and Stable Electrocatalyst for Acidic Oxygen Evolution Reaction

To date, only a few noble metal oxides exhibit the required efficiency and stability as oxygen evolution reaction (OER) catalysts under the acidic, high-voltage conditions that exist during proton exchange membrane water electrolysis (PEMWE). The high cost and scarcity of these catalysts hinder the large-scale application of PEMWE. Here, we report a novel OER electrocatalyst for OER comprised of uniformly dispersed Ru clusters confined on boron carbon nitride (BCN) support. Compared to RuO₂, our BCN-supported catalyst shows enhanced charge transfer. It displays a low overpotential of 164 mV at a current density of 10 mA cm⁻², suggesting its excellent OER catalytic activity. This catalyst was able to operate continuously for over 12 h under acidic conditions, whereas RuO₂ without any support fails in 1 h. Density functional theory (DFT) calculations confirm that the interaction between the N on BCN support and Ru clusters changes the adsorption capacity and reduces the OER energy barrier, which increases the electrocatalytic activity of Ru.     

Regulating the Synergistic Effect in Bimetallic Two-Dimensional Polymer Oxygen Evolution Reaction Catalysts by Adjusting the Coupling Strength Between Metal Centers

Bimetallic electrocatalysts with its superior performance has a broad application prospect in oxygen evolution reaction (OER), but the fundamental understanding of the mechanism of synergistic effect is still limited since there lacks a practical way to decouple the influence factors on the intrinsic activity of active sites from others. Herein, a series of bimetallic Co−Ni two-dimensional polymer (2DP) model OER catalysts with well-defined architecture, monolayer characteristic, were designed and synthesized to explore the influence of the coupling strength between metal centers on OER performance. The coupling strength was regulated by adjusting the spacing between metal centers or the conjugation degree of bridge skeleton. Among the examined 2DPs, CoTAPP-Ni-MF-2DP, which has the strongest coupling strength between metal centers exhibited the best OER performance. These model systems can help to explore the precise structure-performance relationships, which is important for the rational catalyst design at the atomic/molecular levels.     

Revealing the Formation Mechanism and Optimizing the Synthesis Conditions of Layered Double Hydroxides for the Oxygen Evolution Reaction

Layered double hydroxides (LDHs), whose formation is strongly related to OH⁻ concentration, have attracted significant interest in various fields. However, the effect of the real-time change of OH⁻ concentration on LDHs’ formation has not been fully explored due to the unsuitability of the existing synthesis methods for in situ characterization. Here, the deliberately designed combination of NH₃ gas diffusion and in situ pH measurement provides a solution to the above problem. The obtained results revealed the formation mechanism and also guided us to synthesize a library of LDHs with the desired attributes in water at room temperature without using any additives. After evaluating their oxygen evolution reaction performance, we found that FeNi-LDH with a Fe/Ni ratio of 25/75 exhibits one of the best performances so far reported.     

A BiVO4 Photoanode with a VOx Layer Bearing Oxygen Vacancies Offers Improved Charge Transfer and Oxygen Evolution Kinetics in Photoelectrochemical Water Splitting

Sluggish oxygen evolution kinetics are one of the key limitations of bismuth vanadate (BiVO₄) photoanodes for efficient photoelectrochemical (PEC) water splitting. To address this issue, we report a vanadium oxide (VO_x) with enriched oxygen vacancies conformally grown on BiVO₄ photoanodes by a simple photo-assisted electrodeposition process. The optimized BiVO₄/VO_x photoanode exhibits a photocurrent density of 6.29 mA cm⁻² at 1.23 V versus the reversible hydrogen electrode under AM 1.5 G illumination, which is ca. 385 % as high as that of its pristine counterpart. A high charge-transfer efficiency of 96 % is achieved and stable PEC water splitting is realized, with a photocurrent retention rate of 88.3 % upon 40 h of testing. The excellent PEC performance is attributed to the presence of oxygen vacancies in VO_x that forms undercoordinated sites, which strengthen the adsorption of water molecules onto the active sites and promote charge transfer during the oxygen evolution reaction. This work demonstrates the potential of vanadium-based catalysts for PEC water oxidation.     

Ordered Mesoporous Intermetallic Ga-Pt Nanoparticles: Phase-Controlled Synthesis and Performance in Oxygen Reduction Electrocatalysis

The intermetallic phase control is a promising strategy to optimize the physicochemical properties of ordered intermetallic compounds and engineer their performance in various (electro)catalytic reactions. However, the intermetallic phase-dependent catalytic performance is still rarely reported because of the difficulty in synthesizing ordered intermetallics with precisely controlled phase structures at atomic level, especially having ordered mesoscopic structure/morphology. Here, we successfully reported a precise synthesis of two phase-pure mesoporous intermetallic gallium-platinum (meso-i-Ga-Pt) nanoparticles, including meso-i-Ga₃Pt₅ with an orthorhombic space group and meso-i-Ga₁Pt₁ with a non-symmorphic chiral cubic space group. The intermetallic phase control of ordered meso-i-Ga-Pt nanoparticles was realized by carefully tuning the induced Ga salts with different anions that optimized the free energies during the synthesis. The intermetallic phase-dependent catalytic performance of ordered meso-i-Ga-Pt was systematically evaluated for oxygen reduction reaction (ORR) electrocatalysis, with completely opposite catalytic performance in alkaline media. Interestingly, ordered meso-i-Ga₁Pt₁ catalyst with chiral atomic arrangements disclosed unexpected high ORR activity and stability with 5.9 and 3.2 enhancement factors in mass activity compared to those of meso-i-Ga₃Pt₅ and commercial Pt/C.