Hydrogen production from electrochemical water splitting represents a highly promising technology for sustainable energy storage, but its widespread implementation heavily relies on the development of high-performance and cost-effective hydrogen evolution reaction (HER) electrocatalysts. Metal oxides, an important family of functional materials with diverse compositions and structures, were traditionally believed inactive towards HER. Encouragingly, the continuous breakthroughs and significant progress in recent years (mainly from 2015 onwards) make engineered metal oxides emerge as promising candidates for HER electrocatalysis. In this article, we present a comprehensive review of recent advances in metal oxide-based electrocatalysts for HER. We start with a brief description of some key fundamental concepts of HER, such as mechanisms, computational activity descriptors, and experimental parameters used to evaluate catalytic performance. This is followed by a overview of various types of metal oxide-based HER electrocatalysts reported so far, including single transition metal oxides, spinel oxides, perovskite oxides, metal (oxy)hydroxides, specially-structured metal oxides and oxide-containing hybrids, with special emphasis on designed strategies for promoting performance and property–activity correlation. Finally, some concluding remarks and perspectives about future opportunities of this exciting field are provided.

Metal oxide-based materials as an emerging family of hydrogen evolution electrocatalysts

The proton exchange membrane (PEM) water electrolysis is one of the most promising hydrogen production techniques. The oxygen evolution reaction (OER) occurring at the anode dominates the overall efficiency. Developing active and robust electrocatalysts for OER in acid is a longstanding challenge for PEM water electrolyzers. Most catalysts show unsatisfied stability under strong acidic and oxidative conditions. Such a stability challenge also leads to difficulties for a better understanding of mechanisms. This review aims to provide the current progress on understanding of OER mechanisms in acid, analyze the promising strategies to enhance both activity and stability, and summarize the state-of-the-art catalysts for OER in acid. First, the prevailing OER mechanisms are reviewed to establish the physicochemical structure-activity relationships for guiding the design of highly efficient OER electrocatalysts in acid with stable performance. The reported approaches to improve the activity, from macroview to microview, are then discussed. To analyze the problem of instability, the key factors affecting catalyst stability are summarized and the surface reconstruction is discussed. Various noble-metal-based OER catalysts and the current progress of non-noble-metal-based catalysts are reviewed. Finally, the challenges and perspectives for the development of active and robust OER catalysts in acid are discussed.

Recent Development of Oxygen Evolution Electrocatalysts in Acidic Environment.

Herein, a novel dual single-atom catalyst comprising adjacent Fe-N4 and Mn-N4 sites on 2D ultrathin N-doped carbon nanosheets with porous structure (FeMn-DSAC) was constructed as the cathode for a flexible low-temperature Zn-air battery (ZAB). FeMn-DSAC exhibits remarkable bifunctional activities for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Control experiments and density functional theory calculations reveal that the catalytic activity arises from the cooperative effect of the Fe/Mn dual-sites aiding *OOH dissociation as well as the porous 2D nanosheet structure promoting active sits exposure and mass transfer during the reaction process. The excellent bifunctional activity of FeMn-DSAC enables the ZAB to operate efficiently at ultra-low temperature of -40 °C, delivering 30 mW cm-2 peak power density and retaining up to 86 % specific capacity from the room temperature counterpart. 

Engineering Dual Single‐Atom Sites on 2D Ultrathin N‐doped Carbon Nanosheets Attaining Ultra‐Low Temperature Zn‐Air Battery

Electrochemical water splitting has attracted significant attention as a key pathway for the development of renewable energy systems. Fabricating efficient electrocatalysts for these processes is intensely desired to reduce their overpotentials and facilitate practical applications. Recently, metal-organic framework (MOF) nanoarchitectures featuring ultrahigh surface areas, tunable nanostructures, and excellent porosities have emerged as promising materials for the development of highly active catalysts for electrochemical water splitting. Herein, the most pivotal advances in recent research on engineering MOF nanoarchitectures for efficient electrochemical water splitting are presented. First, the design of catalytic centers for MOF-based/derived electrocatalysts is summarized and compared from the aspects of chemical composition optimization and structural functionalization at the atomic and molecular levels. Subsequently, the fast-growing breakthroughs in catalytic activities, identification of highly active sites, and fundamental mechanisms are thoroughly discussed. Finally, a comprehensive commentary on the current primary challenges and future perspectives in water splitting and its commercialization for hydrogen production is provided. Hereby, new insights into the synthetic principles and electrocatalysis for designing MOF nanoarchitectures for the practical utilization of water splitting are offered, thus further promoting their future prosperity for a wide range of applications.

Designing MOF Nanoarchitectures for Electrochemical Water Splitting.

An ordered macroporous superstructure of nitrogen‐doped nanoporous carbon implanted with ultrafine Ru nanoclusters is developed via thermal pyrolysis of the ordered macroporous single crystals of ZIF‐8 accommodating Ru(III) ions, which affords unparalleled performance for the pH‐universal hydrogen evolution reaction, with order of magnitude higher mass activity compared to the benchmark Pt/C.

Ordered Macroporous Superstructure of Nitrogen-Doped Nanoporous Carbon Implanted with Ultrafine Ru Nanoclusters for Efficient pH-Universal Hydrogen Evolution Reaction

As a highly appealing technology for hydrogen generation, water electrolysis including oxygen evolution reaction (OER) at the anode and hydrogen evolution reaction (HER) at the cathode largely depends on the availability of efficient electrocatalysts. Accordingly, over the past years, much effort has been made to develop various electrocatalysts with superior performance and reduced cost. Among them, ruthenium (Ru)-based materials for OER and HER are very promising because of their prominent catalytic activity, pH-universal application, the cheapest price among the precious metal family, and so on. Herein, recent advances in this hot research field are comprehensively reviewed. A general description about water splitting is presented to understand the reaction mechanism and proposed scaling relations toward activities, and key stability issues for Ru-based materials are further given. Subsequently, various Ru-involving electrocatalysts are introduced and classified into different groups for improving or optimizing electrocatalytic properties, with a special focus on several significant bifunctional electrocatalysts along with a simulated water electrolyzer. Finally, a perspective on the existing challenges and future progress of Ru-based catalysts toward OER and HER is provided. The main aim here is to shed some light on the design and construction of emerging catalysts for energy storage and conversion technologies.

Recent advances and prospective in ruthenium-based materials for electrochemical water splitting

Multi-Functional Hydrogels for Flexible Zinc-Based Batteries Working under Extreme Conditions

A comprehensive review of solid oxide fuel cells operating on various promising alternative fuels

Optimization of gas diffusion layer in high temperature PEMFC with the focuses on thickness and porosity

Development of noble-metal-free materials with remarkable electrocatalytic water-splitting performance in acidic or neutral media has sparked considerable attention in recent years. Herein, we review the latest research on design and fabrication of precious-metal-free catalytic materials for overall water electrolysis in non-alkaline environment, especially highlighting several optimizing approaches to enhance the catalytic behavior and to realize effective bifunctional electrocatalysts. All these involved noble-metal-free electrocatalysts are classified into transition-metal oxides (TMOs), transition-metal nitrides (TMNs), transition-metal carbides (TMCs), transition-metal phosphides (TMPs), transition-metal chalcogenides, metal complexes, and metal-free carbons, as shown in the main part. Besides, the paper also offers an introduction of the fundamental electrochemistry of water splitting before entering the subject, as well as a prospective discussion on mechanism understanding, novel catalysts fabrication, and standardized performance measurements/evaluation in the last section.

Qijiao He

Papers

Recent advances and prospective in ruthenium-based materials for electrochemical water splitting

Multi-Functional Hydrogels for Flexible Zinc-Based Batteries Working under Extreme Conditions

A comprehensive review of solid oxide fuel cells operating on various promising alternative fuels

Optimization of gas diffusion layer in high temperature PEMFC with the focuses on thickness and porosity

A mini-review of noble-metal-free electrocatalysts for overall water splitting in non-alkaline electrolytes