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Transition metal nitride/carbide (TMN/C) have been actively explored as low-cost hydrogen evolution reaction (HER) electrocatalysts owing to their Pt-like physical and chemical properties. Unfortunately, pure TMN/C suffers from strong hydrogen adsorption and lacks active centers for water dissociation. Herein, we developed a switchable WO3-based in situ gas–solid reaction for preparing sophisticated Fe-N doped WC and Fe-C doped WN nanoarrays. Interestingly, the switch of codoping and phase can be effectively manipulated by regulating the amount of ferrocene. Resultant Fe-C-WN and Fe-N-WC exhibit robust electrocatalytic performance for HER in alkaline and acid electrolytes, respectively. The collective collaboration of morphological, phase and electronic effects are suggested to be responsible for the superior HER activity. The smallest |ΔGH*| value of Fe-N-WC indicates preferable hydrogen-evolving kinetics on the Fe-N-WC surface for HER under acid condition, while Fe-C-WN is suggested to be beneficial to the adsorption and dissociation of H2O for HER in alkaline electrolyte.
This work was supported by Shandong Provincial Natural Science Foundation (No. ZR2019BB025), the National Natural Science Foundation of China (Nos. 21976014 and U1930402), The Fundamental Research Funds for the Central Universities (FRF-TP-20-11B and FRF-BR-20-02B), and the generous computer time from TianHe2-JK Supercomputer Center.