With the increasing demands in energy consumption and increasing environmental concerns, it is of vital significance for developing renewable and clean energy sources to substitute traditional fossil fuels. As an outstanding candidate, hydrogen is recognized as a green energy carrier due to its high gravimetric energy density, zero carbon footprints, and earth-abundance. Currently, water splitting in alkaline electrolytes represents one of the most promising methods for sustainable hydrogen production, and the key challenge lies in the development of high-performance electrocatalysts for the hydrogen evolution reaction (HER). Given the rapid advances in the design and development of efficient catalysts towards the alkaline HER, especially capable transition metal (TM)-based materials, this review aims to summarise recent progress in the theoretical understanding of the alkaline HER and TM-based electrocatalysts. TM-based catalysts classified by their different anionic compositions (metals, alloys, oxides, hydroxides, sulfides, selenides, tellurides, nitrides, phosphides, carbides, and borides) are comprehensively showcased. Special attention is given to mainstream strategies that can improve the catalytic properties of each category, as well as the underlying structure–activity regimes. Additionally, the challenges for the future development of novel catalysts are also analyzed.

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Recent advances in transition metal-based electrocatalysts for alkaline hydrogen evolution

The development of sodium-ion batteries for large-scale applications requires the synthesis of electrode materials with high capacity, high initial Coulombic efficiency (ICE), high rate performance, long cycle life, and low cost. A rational design of freestanding anode materials is reported for sodium-ion batteries, consisting of molybdenum disulfide (MoS2) nanosheets aligned vertically on carbon paper derived from paper towel. The hierarchical structure enables sufficient electrode/electrolyte interaction and fast electron transportation. Meanwhile, the unique architecture can minimize the excessive interface between carbon and electrolyte, enabling high ICE. The as-prepared MoS2@carbon paper composites as freestanding electrodes for sodium-ion batteries can liberate the traditional electrode manufacturing procedure, thereby reducing the cost of sodium-ion batteries. The freestanding MoS2@carbon paper electrode exhibits a high reversible capacity, high ICE, good cycling performance, and excellent rate capability. By exploiting in situ Raman spectroscopy, the reversibility of the phase transition from 2H-MoS2 to 1T-MoS2 is observed during the sodium-ion intercalation/deintercalation process. This work is expected to inspire the development of advanced electrode materials for high-performance sodium-ion batteries.

MoS2 Nanosheets Vertically Aligned on Carbon Paper: A Freestanding Electrode for Highly Reversible Sodium Ion Batteries

Multifunctional Transition Metal-Based Phosphides in Energy-Related Electrocatalysis

Heterogeneous Bimetallic Phosphide Ni2P-Fe2P as an Efficient Bifunctional Catalyst for Water/Seawater Splitting

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

Transition metal hydroxides (M-OH) and their heterostructures (X|M-OH, where X can be a metal, metal oxide, metal chalcogenide, metal phosphide, etc.) have recently emerged as highly active electrocatalysts for hydrogen evolution reaction (HER) of alkaline water electrolysis. Lattice hydroxide anions in metal hydroxides are primarily responsible for observing such an enhanced HER activity in alkali that facilitate water dissociation and assist the first step, the hydrogen adsorption. Unfortunately, their poor electronic conductivity had been an issue of concern that significantly lowered its activity. Interesting advancements were made when heterostructured hydroxide materials with a metallic and or a semiconducting phase were found to overcome this pitfall. However, in the midst of recently evolving metal chalcogenide and phosphide based HER catalysts, significant developments made in the field of metal hydroxides and their heterostructures catalysed alkaline HER and their superiority have unfortunately been given negligible attention. This review, unlike others, begins with the question of why alkaline HER is difficult and will take the reader through evaluation perspectives, trends in metals hydroxides and their heterostructures catalysed HER, an understanding of how alkaline HER works on different interfaces, what must be the research directions of this field in near future, and eventually summarizes why metal hydroxides and their heterostructures are inevitable for energy-efficient alkaline HER.

https://onlinelibrary.wiley.com/doi/pdf/10.1002/anie.202015738

Strategies and Perspectives to Catch the Missing Pieces in Energy-Efficient Hydrogen Evolution Reaction in Alkaline Media

Corrosion and Alloy Engineering in Rational Design of High Current Density Electrodes for Efficient Water Splitting

Harvesting Electronic Waste for the Development of Highly Efficient Eco‐Design Electrodes for Electrocatalytic Water Splitting

Numerical and experimental investigation on 25 cm2 and 100 cm2 PEMFC with novel sinuous flow field for effective water removal and enhanced performance

Electrocatalytic splitting of water is the most convincing and straight forward path to extract hydrogen, but the efficiency of this process relies heavily on the catalyst employed. Here, molybdenum sulphoselenophosphide (MoS45.1 Se11.7 P6.1 ) spheroids are reported as an active catalyst for the hydrogen evolution reaction (HER) and this is the first attempt to study on ternary anion based molybdenum chalcogenides. As-prepared MoSx Sey Pz catalyst reveals a unique morphology of microspheroids capped by stretched-out nanoflakes that exhibits excellent electrocatalytic activity (   j-10 mA cm-2 @ 93 mV, Tafel slope of 50.1 mV dec-1 , TOF-0.40 s-1 ) fairly closer to the performance of platinum (Pt) and predominant to those of the pre-existing Mo-chalcogenides and phosphides. Such an increase in performance stems from the copious amount of active edge sites, the presence of nanoflakes, and high circumferential area exposed by the spheroids. Besides, the electrode with MoS45.1 Se11.7 P6.1 displays excellent stability in acidic medium over 10 h of continuous operation. This work paves way for improving the catalytic activity of existing Mo-chalcogenide compounds by doping suitable mixed anions and also reveals the integral role of anions as well as their synergetic effects on the surface physiochemical properties and the HER catalysis.

Vasanth Rajendiran Jothi

Papers

Strategies and Perspectives to Catch the Missing Pieces in Energy-Efficient Hydrogen Evolution Reaction in Alkaline Media

Corrosion and Alloy Engineering in Rational Design of High Current Density Electrodes for Efficient Water Splitting

Harvesting Electronic Waste for the Development of Highly Efficient Eco‐Design Electrodes for Electrocatalytic Water Splitting

Numerical and experimental investigation on 25 cm2 and 100 cm2 PEMFC with novel sinuous flow field for effective water removal and enhanced performance

Molybdenum Sulphoselenophosphide Spheroids as an Effective Catalyst for Hydrogen Evolution Reaction