Recent strategies for activating the basal planes of transition metal dichalcogenides towards hydrogen production

Xia, Hang; Shi, Zude; Gong, Chengshi; He, Yongmin

doi:10.1039/d2ta02458f

Cited by 34 publications

(27 citation statements)

References 192 publications

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“…18 This empirical trend has led to the optimization of HBE as a primary design principle for HER catalysts. Beyond metal surfaces, this concept of finding an optimal HBE has been extended to the development of phosphide 14 and chalcogenide-based 19 catalysts.…”

Section: Hbe Theory and The Role Of Hadmentioning

confidence: 99%

The Role of Hydrogen Adsorption Site Diversity in Catalysis on Transition Metal Phosphide Surfaces

Kuo

Nishiwaki

Rivera-Maldonado

et al. 2022

Preprint

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Hydrogen production via clean technologies such as water electrolysis, and its use in the synthesis of value-added chemicals (e.g., ammonia production), play a critical role in the pursuit of decarbonization. This realization requires effective earth-abundant catalysts that facilitate making and breaking H—H and H—X bonds. Transition metal phosphides (TMPs), such as nickel phosphide, cobalt phosphide, and molybdenum phosphide, have been historically used as hydro-processing catalysts in the petroleum industry, enabling critical hydrodenitrogenation (HDN) and hydrodesulfurization (HDS) reactions. Over the past two decades, TMPs have been attracting extensive attention for applications in energy conversion due to their exceptional activity towards the hydrogen evolution reaction (HER). The exceptional HER activity of certain TMPs has been attributed to their nearly ideal H binding energy (HBE), similar to Pt, as deduced by first-principles calculations. In contrast to Pt and other noble metals, where HER and the hydrogen oxidation reaction (HOR) activities are usually correlated, TMPs are usually inactive for HOR. This challenges the applicability of HBE theory to describe activity trends for H2 electrocatalysis on TMPs. In this viewpoint, we discuss the structural complexity of TMPs and its impact on the formation of adsorbed H (Had) and catalysis. In light of this we discuss the validity of HBE theory on TMPs and whether a single value of HBE is sufficient to describe TMP activity trends. Lastly, we propose that the presence of diverse adsorption sites on TMP surfaces can be leveraged to design selective and efficient hydrogenation and electrochemical reduction reactions beyond HER.

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Section: Hbe Theory and The Role Of Hadmentioning

confidence: 99%

The Role of Hydrogen Adsorption Site Diversity in Catalysis on Transition Metal Phosphide Surfaces

Kuo

Nishiwaki

Rivera-Maldonado

et al. 2022

Preprint

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“…Recently, layered transition metal dichalcogenides (TMDCs) with the formula MX 2 (M = group IV-VII transition metal, X = S, Se, and Te) have attracted considerable attention because of their distinct thickness-dependent electronic structures and outstanding catalytic properties. [24,25] MoS 2 , as the most renowned TMDC, exhibits significant HER potential, [26] but, HER activity of unmodified MoS 2 is unsatisfactory over a wide pH range because of inefficient H 2 O cleavage and sluggish H desorption. For all MX 2 2D electrocatalysts, the limited edge atom with unsaturated coordination is the HER active site, whereas the entire inert basal plane is considered to be the origin of the restricted HER activity.…”

Section: Introductionmentioning

confidence: 99%

Spatial Relation Controllable Di‐Defects Synergy Boosts Electrocatalytic Hydrogen Evolution Reaction over VSe₂ Nanoflakes in All pH Electrolytes

Zhang

Huang

et al. 2022

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the Chinese government. However, the electro catalytic HER suffers from sluggish kinetics, high cost of catalysts and technologies, and instability at certain pH electrolytes due to the scarcity of highperformance earth-abundant catalysts. Although the HER performance of catalysts can optimize by adjusting the acidity of the electrolyte, designing the pseudo-pH-independent electrocatalysts may make the water electrolyzers more affordable and safer for the commercial development of hydrogen energy applications. [2] As a water electrolysis benchmark, precious metal electrocatalyst (Pt) possesses excellent activity overall pH values toward HER, but difficulty in industrialization for its scarcity and high cost. [3][4][5] To date, many nonprecious metal-based HER catalysts with high performance in certain electrolytes have been reported, including transition metal sulfides, [6] selenides, [7][8][9][10][11][12][13][14][15][16][17][18] carbides, [19,20] phosphides, [21,22] and thiopho sphates. [23] However, most developed catalysts deliver attractive HER performance only under acidic conditions, limiting their practical applications. Accordingly, the exploration of pH-universal HER electrocatalysts with competitive Defect engineering of transition metal dichalcogenides (TMDCs) is important for improving electrocatalytic hydrogen evolution reaction (HER) performance. Herein, a facile and scalable atomic-level di-defect strategy over thermodynamically stable VSe 2 nanoflakes, yielding attractive improvements in the electrocatalytic HER performance over a wide electrolyte pH range is reported. The di-defect configuration with controllable spatial relation between single-atom (SA) V defects and single Se vacancy defects effectively triggers the electrocatalytic HER activity of the inert VSe 2 basal plane. When employed as a cathode, this di-defects decorated VSe 2 electrocatalyst requires overpotentials of 67.2, 72.3, and 122.3 mV to reach a HER current density of 10 mA cm −2 under acidic, alkaline, and neutral conditions, respectively, which are superior to most previously reported non-noble metal HER electrocatalysts. Theoretical calculations reveal that the reactive microenvironment consists of two adjacent SA Mo atoms with two surrounding symmetric Se vacancies, yielding optimal water dissociation and hydrogen desorption kinetics. This study provides a scalable strategy for improving the electrocatalytic activity of other TMDCs with inert atoms in the basal plane.

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“…Therefore, a lot of effort has recently been devoted to making the basal planes of TMDCs and other 2D materials active, or to enhance their activity by other means. [21][22][23][24][25][26] The strategies to make basal planes active included 'internal regulation' such as doping metal or non-metal atoms, creating vacancies, changing the structural phase of the material and creating superlattices, for example. 'External regulation' has included applying electric eld, strain, tuning the electronic property of the 2D material by using different substrates and creating hetero-structures of different 2D materials.…”

Section: Introductionmentioning

confidence: 99%

Complementary effects of functionalization, vacancy defects and strain engineering in activating the basal plane of monolayer FePS₃ for HER

Das

Chakraborty

Sen

2022

Sustainable Energy Fuels

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Recent strategies for activating the basal planes of transition metal dichalcogenides towards hydrogen production

Abstract: The currently strategies for activating the TMDC basal planes toward hydrogen evolution reaction were summarized, which are divided into internal and external regulation, depending on whether the pristine structure is altered or not.

Cited by 34 publications

References 192 publications

The Role of Hydrogen Adsorption Site Diversity in Catalysis on Transition Metal Phosphide Surfaces

The Role of Hydrogen Adsorption Site Diversity in Catalysis on Transition Metal Phosphide Surfaces

Spatial Relation Controllable Di‐Defects Synergy Boosts Electrocatalytic Hydrogen Evolution Reaction over VSe₂ Nanoflakes in All pH Electrolytes

Complementary effects of functionalization, vacancy defects and strain engineering in activating the basal plane of monolayer FePS₃ for HER

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Recent strategies for activating the basal planes of transition metal dichalcogenides towards hydrogen production

Abstract: The currently strategies for activating the TMDC basal planes toward hydrogen evolution reaction were summarized, which are divided into internal and external regulation, depending on whether the pristine structure is altered or not.

Cited by 34 publications

References 192 publications

The Role of Hydrogen Adsorption Site Diversity in Catalysis on Transition Metal Phosphide Surfaces

The Role of Hydrogen Adsorption Site Diversity in Catalysis on Transition Metal Phosphide Surfaces

Spatial Relation Controllable Di‐Defects Synergy Boosts Electrocatalytic Hydrogen Evolution Reaction over VSe2 Nanoflakes in All pH Electrolytes

Complementary effects of functionalization, vacancy defects and strain engineering in activating the basal plane of monolayer FePS3 for HER

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Spatial Relation Controllable Di‐Defects Synergy Boosts Electrocatalytic Hydrogen Evolution Reaction over VSe₂ Nanoflakes in All pH Electrolytes

Complementary effects of functionalization, vacancy defects and strain engineering in activating the basal plane of monolayer FePS₃ for HER