Open AccessInterfacial Engineering of SeO Ligands on Tellurium Featuring Synergistic Functionalities of Bond Activation and Chemical States Buffering toward Electrocatalytic Conversion of Nitrogen to Ammonia
Author(s) -
Zhang Gong,
Xu Hang,
Li Yang,
Xiang Chao,
Ji Qinghua,
Liu Huijuan,
Qu Jiuhui,
Li Jinghong
Publication year - 2019
Publication title -
advanced science
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.388
H-Index - 100
ISSN - 2198-3844
DOI - 10.1002/advs.201901627
Subject(s) - overpotential , chemistry , lone pair , electron transfer , faraday efficiency , electrochemistry , dissociation (chemistry) , nanorod , redox , inorganic chemistry , electrocatalyst , ammonia , ammonia production , aqueous solution , reversible hydrogen electrode , photochemistry , electrode , materials science , nanotechnology , organic chemistry , molecule , reference electrode
Ammonia (NH 3 ) production from electrochemical nitrogen (N 2 ) 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 TeO 2 shell of Se, O dual‐doped Te nanorods can maximize orbits overlap between N 2 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 N 2 ‐to‐NH 3 conversion process. As expected, a high faradaic efficiency of 24.56% and NH 3 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.