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 ?-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.

SUBMITTER: Zhang G 

PROVIDER: S-EPMC6794632 | biostudies-literature | 2019 Oct

REPOSITORIES: biostudies-literature