Bulk layered heterojunction as an efficient electrocatalyst for hydrogen evolution.

We describe the spontaneous formation of composite chalcogenide materials that consist of two-dimensional (2D) materials dispersed in bulk and their unusual charge transport properties for application in hydrogen evolution reactions (HERs). When MoS as a representative 2D material is deposited on transition metals (such as Cu) in a controlled manner, the sulfidation reactions also occur with the metal. This process results in remarkably unique structures, that is, bulk layered heterojunctions (BLHJs) of Cu-Mo-S that contain MoS flakes inside, which are uniformly dispersed in the CuS matrix. The resulting structures were expected to induce asymmetric charge transfer via layered frameworks and tested as electrocatalysts for HERs. Upon suitable thermal treatments, the BLHJ surfaces exhibited the efficient HER performance of approximately 10 mA/cm at a potential of -0.1 V versus a reversible hydrogen electrode. The Tafel slope was approximately 30 to 40 mV per decade. The present strategy was further generalized by demonstrating the formation of BLHJs on other transition metals, such as Ni. The resulting BLHJs of Ni-Mo-S also showed the remarkable HER performance and the stable operation over 10 days without using Pt counter electrodes by eliminating any possible issues on the Pt contamination.