Cooperativity by Multi-Metals Confined in Supertetrahedral Sulfide Nanoclusters To Enhance Electrocatalytic Hydrogen Evolution

Few multi-metal-based systems were created to probe the regulation mechanism in electrocatalytic reactions. Herein, we select supertetrahedral metal sulfide nanoclusters (MSNCs) with preconfined and precisely positioned multi-metal ions as a structure model and have successfully developed MSNC-based electrocatalysts. Unprecedentedly, those new materials based on M–Ga–Sn–S NCs (M = Mn, Co, and Zn) show the synergistic effect of multi-metal ions on hydrogen evolution reaction (HER) via experiments and density functional theory (DFT) calculations. Among various multi-metal possibilities studied here, the most efficient one is that codoped with Mn, Co, and Zn, and it achieves a low overpotential of 176 mV at 10 mA cm–2 and a small Tafel slope of 43 mV dec–1. Such unique model system allows for systematic investigation of catalytic activities of low-coordinated sulfur ions in well-defined chemical environment and could have long-lasting and fundamental impacts on creating new types of chalcogenide-based electrocatalysts.