In Situ Grown Co-Based Interstitial Compounds: Non-3d Metal and Non-Metal Dual Modulation Boosts Alkaline and Acidic Hydrogen Electrocatalysis.

Interfacial engineering and elemental doping are the two parameters to enhance the catalytic behavior of cobalt nitrides for the alkaline hydrogen evolution reaction (HER). However, simultaneously combining these two parameters to improve the HER catalytic properties of cobalt nitrides in alkaline media is rarely reported and also remains challenging in acidic media. Herein, it is demonstrated that high-valence non-3d metal and non-metal integration can simultaneously achieve Co-based nitride/oxide interstitial compound phase boundaries on stainless steel mesh (denoted Mo-Co N/N-CoO) for efficient HER in alkaline and acidic media. Density functional theory (DFT) calculations show that the unique structure does not only realize multi-active sites, enhanced water dissociation kinetics, and low hydrogen adsorption free energy in alkaline media, but also enhances the positive charge density of hydrogen ions (H ) to effectively allow H to receive electrons from the catalysts surface toward promoting the HER in acidic media. As a result, the as-prepared Mo-Co N/N-CoO demands HER overpotential of -28 mV@10 mA cm in an alkaline medium, and superior to the commercial Pt/C at a current density > 44 mA cm in acidic medium. This work paves a useful strategy to design efficient cobalt-based electrocatalysts for HER and beyond.