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N 2 Electroreduction to NH 3 by Selenium Vacancy‐Rich ReSe 2 Catalysis at an Abrupt Interface
Author(s) -
Lai Feili,
Zong Wei,
He Guanjie,
Xu Yang,
Huang Haowei,
Weng Bo,
Rao Dewei,
Martens Johan A.,
Hofkens Johan,
Parkin Ivan P.,
Liu Tianxi
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202003129
Subject(s) - vacancy defect , chemistry , catalysis , electrocatalyst , nanotechnology , materials science , electrochemistry , crystallography , electrode , organic chemistry
Vacancy engineering has been proved repeatedly as an adoptable strategy to boost electrocatalysis, while its poor selectivity restricts the usage in nitrogen reduction reaction (NRR) as overwhelming competition from hydrogen evolution reaction (HER). Revealed by density functional theory calculations, the selenium vacancy in ReSe 2 crystal can enhance its electroactivity for both NRR and HER by shifting the d‐band from −4.42 to −4.19 eV. To restrict the HER, we report a novel method by burying selenium vacancy‐rich ReSe 2 @carbonized bacterial cellulose (V r ‐ReSe 2 @CBC) nanofibers between two CBC layers, leading to boosted Faradaic efficiency of 42.5 % and ammonia yield of 28.3 μg h −1 cm −2 at a potential of −0.25 V on an abrupt interface. As demonstrated by the nitrogen bubble adhesive force, superhydrophilic measurements, and COMSOL Multiphysics simulations, the hydrophobic and porous CBC layers can keep the internal V r ‐ReSe 2 @CBC nanofibers away from water coverage, leaving more unoccupied active sites for the N 2 reduction (especially for the potential determining step of proton‐electron coupling and transferring processes as *NN → *NNH).