Conversion of Layered WS2 Crystals into Mixed-Domain Electrochemical Catalysts by Plasma-Assisted Surface Reconstruction

Adv Mater. 2024 Jun;36(25):e2314031. doi: 10.1002/adma.202314031. Epub 2024 Apr 3.

Abstract

Electrocatalytic water splitting is crucial to generate clean hydrogen fuel, but implementation at an industrial scale remains limited due to dependence on expensive platinum (Pt)-based electrocatalysts. Here, an all-dry process to transform electrochemically inert bulk WS2 into a multidomain electrochemical catalyst that enables scalable and cost-effective implementation of the hydrogen evolution reaction (HER) in water electrolysis is reported. Direct dry transfer of WS2 flakes to a gold thin film deposited on a silicon substrate provides a general platform to produce the working electrodes for HER with tunable charge transfer resistance. By treating the mechanically exfoliated WS2 with sequential Ar-O2 plasma, mixed domains of WS2, WO3, and tungsten oxysulfide form on the surfaces of the flakes, which gives rise to a superior HER with much greater long-term stability and steady-state activity compared to Pt. Using density functional theory, ultraefficient atomic sites formed on the constituent nanodomains are identified, and the quantification of atomic-scale reactivities and resulting HER activities fully support the experimental observations.

Keywords: catalytic materials; hydrogen evolution reaction; plasma treatment; transition metal chalcogenides; water electrolysis.