Catalysts for the hydrogen evolution reaction in alkaline medium: Configuring a cooperative mechanism at the Ag-Ag$_2$S-MoS$_2$ interface

Abstract: 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 Ag@MoS$_2$ 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 MoS$_2$ 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 Ag$_2$S in the cores, and adjusting the relative fractions of Ag, Ag$_2$S, and MoS$_2$ 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 Ag$_2$S drive the water dissociation step, and the formed hydrogen subsequently recombines on the defective MoS$_2$ shell. This study demonstrates the benefits of hybrid structures as functional nanomaterials and provides a scheme to activate MoS$_2$ for HER in alkaline conditions.