Patchwork-Structured Heterointerface of 1T-WS₂/a-WO₃ with Sustained Hydrogen Spillover as a Highly Efficient Hydrogen Evolution Reaction Electrocatalyst

Abstract

Using tungsten disulfide (WS 2 ) as a hydrogen evolution reaction (HER) electrocatalyst brought on several ways to surpass its intrinsic catalytic activity. This study introduces a nanodomain tungsten oxide (WO 3 ) interface to 1T-WS 2 , opening a new route for facilitating the transfer of a proton to active sites, thereby enhancing the HER performance. After H 2 S plasma sulfurization on the W layer to realize nanocrystalline 1T-WS 2 , subsequent O 2 plasma treatment led to the formation of amorphous WO 3 (a-WO 3 ), resulting in a patchwork-structured heterointerface of 1T-WS 2 /a-WO 3 (WSO). Addition of a hydrophilic interface (WO 3 ) facilitates the hydrogen spillover effect, which represents the transfer of absorbed protons from a-WO 3 to 1T-WS 2 . Moreover, the faster response of the cathodic current peak (proton insertion) in cyclic voltammetry is confirmed by the higher degree of oxidation. The rationale behind the faster proton insertion is that the introduced a-WO 3 works as a proton channel. As a result, WSO-1.2 (the ratio of 1T-WS 2 to a-WO 3 ) exhibits a remarkable HER activity in that 1T-WS 2 consumes more protons provided by the channel, showing an overpotential of 212 mV at 10 mA/cm 2 . Density functional theory calculations also show that the WO 3 phase gives higher binding energies for initial proton adsorption, while the 1T-WS 2 phase shows reduced HER overpotential. This improved catalytic performance demonstrates a novel strategy for water splitting to actively elicit the related reaction via efficient proton transport.

Strategies for Promoting Catalytic Performance of Ru‐Based Electrocatalysts towards Oxygen/Hydrogen Evolution Reaction

“…[58][59][60][61][62][63] In general, electron transfer often occurs at the heterointerfaces of different components, which will result in the redistribution of charge and optimum adsorption of reactive intermediates. [64][65][66] Moreover, it is also reported that the strong synergistic effect between different components will further elevate the electrocatalytic performance, [67,68] which not only enhance the atomic utilization efficiency of Ru, but also substantially reduce the cost of catalyst. Inspired by this, enormous efforts have been dedicated to the rational design and fabrication of Ru-based heterostructures to boost electrocatalytic reactions.…”

“…Heterostructured materials composed of Ru and other metals are also highly active towards electrocatalytic HER, OER, and overall water splitting [58–63] . In general, electron transfer often occurs at the heterointerfaces of different components, which will result in the redistribution of charge and optimum adsorption of reactive intermediates [64–66] . Moreover, it is also reported that the strong synergistic effect between different components will further elevate the electrocatalytic performance, [67,68] which not only enhance the atomic utilization efficiency of Ru, but also substantially reduce the cost of catalyst.…”

Interfacial built-in electric-field for boosting energy conversion electrocatalysis

“…Constructing the BIEF can induce charge redistribution at the heterointerfaces to optimize the adsorption with H*, thereby contributing to the substantial improvement in electrocatalytic HER performance. [52][53][54][55] In recent years, fabricating BIEF has been widely accepted as a promising strategy for promoting the electrocatalytic HER performance of heterostructured catalysts. For example, Yan et al 56 synthesized the MXene supported MoNi 4 alloy nanocrystals catalysts with a remarkably strong BIEF at the heterointerface of two components, which benefited for the electron transfer from MXene to MoNi 4 .…”

Intensifying Hydrogen Spillover for Boosting Electrocatalytic Hydrogen Evolution Reaction

“…In addition to metal‐support binary catalysts, the hydrogen spillover phenomenon is also taking place in the transition metal compound‐based binary catalysts with different ΔG H and playing a crucial role in determining their electrocatalytic HER performance [100,101] . For example, Zhao et al [102] .…”

“…In addition to metal-support binary catalysts, the hydrogen spillover phenomenon is also taking place in the transition metal compound-based binary catalysts with different ΔG H and playing a crucial role in determining their electrocatalytic HER performance. [100,101] For example, Zhao et al [102] reported the fabrication of hybridized Ni 3 S 2 /Cr 2 S 3 sites to facilitate the hydrogen spillover for boosting electrocatalytic HER with ampere-level current density. In this contribution, they have reported the use of hydrogen spillover-bridged water dissocia-tion/hydrogen formation processes that taking place at the synergistically hybridized Ni 3 S 2 /Cr 2 S 3 sites to incapacitate the inhibition effect of high hydrogen coverage induced by high current density and simultaneously promote the Volmer/Tafel processes.…”