Discrepancy of alkaline/neutral hydrogen evolution activity from NiCoSe2/NC and Co–NiSe/NC derived from in-situ thermal and solution processing selenizations of ZIF-67

Constructing cobalt-based selenide catalyst with accessible active site and superior charge transfer capability by simultaneous tailoring chemical component and structure through the feasible strategy is the key to display improved hydrogen evolution reaction (HER) activity. Herein, the bimetal NiCoSe2/nitrogen-doped carbon (NC) with novel flake structure (NiCoSe2/NC/NF) and particle-like cobalt-doped NiSe/NC (Co–NiSe/NC/NF) were synthesized by the in-situ thermal and solution processing selenizations of ZIF-67/NF, respectively. The intrinsic catalytic activity of NiCoSe2, the further accelerated charge-transfer capability originated from the fresh NC and two-dimensional layer structure, and mutually reinforcing kinetics from the closely integrated NiCoSe2 nanoparticles and NC plate endow NiCoSe2/NC/NF with 141 and 284 mV to reach 10 mA cm−2 under alkaline and neutral electrolytes, respectively, accompanying with Tafel slope of 109 and 206 mV dec−1, which were obviously higher than that of the HER properties of Co–NiSe/NC/NF (η10 = 179 mV and Tafel slope of 127 mV dec−1 at alkaline condition, η10 = 301 mV and Tafel slope of 235 mV dec−1 at neutral condition). Meanwhile, the NiCoSe2/NC/NF and Co–NiSe/NC/NF were exhibited well electrochemical stability under alkaline/neutral conditions. This study offers practicable strategy for intuitive comparing the influence of selenization procedures on the whole alkaline/neutral HER activity of cobalt-based catalysts.