Designing non-precious-metal catalysts with comparable mass activity to state-of-the-art noble-metal catalysts for the hydrogen evolution reaction (HER) in alkaline solution still remains a significant challenge. Herein a new strongly coupled nickel-cobalt nitrides/carbon complex nanocage (NiCoNzocage) is rationally designed via chemical etching of ZIF-67 nanocubes with Ni(NO3 )2 under sonication at room temperature, following nitridation. The as-prepared strongly coupled NiCoN/C nanocages exhibit a mass activity of 0.204 mA µg-1 at an overpotential of 200 mV for the HER in alkaline solution, which is comparable to that of commercial Pt/C (0.451 mA µg-1 ). The strongly coupled NiCoN/C nanocages also possess superior stability for the HER with negligible current loss under the overpotentials of 200 mV for 10 h. Density functional theory (DFT) calculations reveal that the excellent HER performance under alkaline condition arises from the robust Co2+ →Co0 transformation achieved by strong (Ni, Co)N-bonding-induced efficient d-p-d coupled electron transfer, which is a key for optimal initial water adsorption and splitting. The high degree of amorphization urges the C-sites to be an electron-pushing bath to promote the inter-layer/sites electron-transfer with loss of the orbital-selection-forbidden-rule, which uniformly boosts the surface catalytic activities up to a high level independent of the individual surface active sites.
Keywords: MOFs; carbon; electrocatalysis; metal nitride; nanocages.
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