Interfacial Engineering of SeO Ligands on Tellurium Featuring Synergistic Functionalities of Bond Activation and Chemical States Buffering toward Electrocatalytic Conversion of Nitrogen to Ammonia

Abstract Ammonia (NH3) production from electrochemical nitrogen (N2) reduction reaction (NRR) under ambient conditions represents a sustainable alternative to the traditional Haber–Bosch process. However, the conventional electrocatalytic NRR process often suffers from low selectivity (competition with the hydrogen evolution reaction (HER)) and electron transfer bottleneck for efficient activation and dissociation. Herein, a strategy to simultaneously promote selectivity and activity through dual‐incorporation of Se and O elements onto the shell of HER‐inactive Te nanorods is reported. It is theoretically and experimentally verified that the exposure of lone‐pair electrons in the TeO2 shell of Se, O dual‐doped Te nanorods can maximize orbits overlap between N2 and Te for N‐N bond activation via π‐backdonation interactions. Further, the Gibbs free energy change indicates that the Lewis‐basic anchor ‐SeO ligand with strong electron‐donating characteristics serves as an electron reservoir and is capable of buffering the oxidation state variation of Te, thereby improving the thermodynamics of desorption of the intermediates in the N2‐to‐NH3 conversion process. As expected, a high faradaic efficiency of 24.56% and NH3 yield rate of ≈21.54 µg h−1 mg−1 are obtained under a low overpotential of ≈0.30 V versus reversible hydrogen electrode in an aqueous electrolyte under ambient conditions.