Catalysts for the hydrogen evolution reaction in alkaline medium: Configuring a cooperative mechanism at the Ag-Ag2S-MoS2 interface

Designing electrocatalysts for HER in alkaline conditions to overcome the sluggish kinetics associated with the additional water dissociation step is a recognized challenge in promoting the hydrogen economy. To this end, delicately tuning the atomic-scale structure and surface composition of nanoparticles is a common strategy and, specifically, making use of hybrid structures, can produce synergistic effects that lead to highly active catalysts. Here, we present a core-shell catalyst of [email protected]2 that shows promising results towards the hydrogen evolution reaction (HER) in both 0.5 M H2SO4 and 0.5 M KOH. In this hybrid structure, the MoS2 shell is strained and defective, and charge transfer occurs between the conductive core and the shell, contributing to the electrocatalytic activity. The shelling process results in a large fraction of Ag2S in the cores, and adjusting the relative fractions of Ag, Ag2S, and MoS2 leads to improved catalytic activity and fast charge-transfer kinetics. We suggest that the enhancement of alkaline HER is associated with a cooperative effect of the interfaces, where the Ag(I) sites in Ag2S drive the water dissociation step, and the formed hydrogen subsequently recombines on the defective MoS2 shell. This study demonstrates the benefits of hybrid structures as functional nanomaterials and provides a scheme to activate MoS2 for HER in alkaline conditions.