Electrocatalytic nitrogen reduction reaction (NRR) presents a sustainable alternative to the Haber–Bosch process for ammonia (NH3) production. However, developing efficient catalysts for NRR and deeply elucidating their catalytic mechanism remain daunting challenges. Herein, we pioneered the successful embedding of atomically dispersed (single/dual) W atoms into V2−xCTyvia a self-capture method, and subsequently uncovered a quantifiable relationship between charge transfer and NRR performance. The prepared n-W/V2−xCTy shows an exceptional NH3 yield of 121.8 μg h−1 mg−1 and a high faradaic efficiency (FE) of 34.2% at −0.1 V (versus reversible hydrogen electrode (RHE)), creating a new record at this potential. Density functional theory (DFT) computations reveal that neighboring W atoms synergistically collaborate to significantly lower the energy barrier, achieving a remarkable limiting potential (UL) of 0.32 V. Notably, the calculated UL values for the constructed model show a well-defined linear relationship with integrated-crystal orbital Hamilton population (ICOHP) (y = 0.0934x + 1.0007, R2 = 0.9889), providing a feasible activity descriptor. Furthermore, electronic property calculations suggest that the NRR activity is rooted in d–2π* coupling, which can be explained by the “donation and back-donation” hypothesis. This work not only designs efficient atomic catalysts for NRR, but also sheds new insights into the role of neighboring single atoms in improving reaction kinetics.
This article is Open Access
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