Modulating the Electronic Structure of Nickel Sulfide Electrocatalysts by Chlorine Doping toward Highly Efficient Alkaline Hydrogen Evolution

The exploration of indurative and stable low-cost catalysts for hydrogen evolution reaction (HER) is of great importance for hydrogen energy economy, but it still faces challenges. Herein, we report a Cl-doped Ni3S2 (Cl–Ni3S2) nanoplate catalyst vertically grown on Ni foam with outstanding activity and durability for HER, which only requires an overpotential of 67 mV to reach a current density of 10 mA cm–2 in alkaline media and exhibits negligible degradation after 30 h of operation. Both the advanced X-ray absorption fine structure (XAFS) and density functional theory (DFT) calculation validate that Cl doping can optimize the electronic structure and the intrinsic activity of Ni3S2. This study devoted to the revelation of the impact of ionic doping on the activity of catalysts at the atomic scale can provide the direction for the rational design of novel and advanced HER electrocatalysts.