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Modification of the Coordination Environment of Active Sites on MoC for High‐Efficiency CH 4 Production
Author(s) -
Han Lili,
Liu Xijun,
He Jia,
Liang Zhixiu,
Wang HsiaoTsu,
Bak SeongMin,
Zhang Jingmin,
Hunt Adrian,
Waluyo Iradwikanari,
Pong WayFaung,
Luo Jun,
Ding Yi,
Adzic Radoslav R.,
Xin Huolin L.
Publication year - 2021
Publication title -
advanced energy materials
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 10.08
H-Index - 220
eISSN - 1614-6840
pISSN - 1614-6832
DOI - 10.1002/aenm.202100044
Subject(s) - materials science , catalysis , active site , faraday efficiency , electrochemistry , spectroscopy , electrolyte , graphene , atom (system on chip) , synchrotron , aqueous solution , coordination sphere , nanotechnology , chemistry , electrode , organic chemistry , physics , quantum mechanics , computer science , metal , metallurgy , embedded system , nuclear physics
Modulating the coordination environment of active sites on catalyst surfaces is crucial to developing effective catalysts and controlling catalysis. However, this may be a highly challenging procedure. Guided by the first‐principles calculations, the modification of the coordination environment of active sites on MoC nanoparticle surfaces is experimentally accomplished by anchoring pyridinic N atom rings of holey graphene on Mo atoms. The rings produce electrostatic forces that enable the tuning of the Mo sites′ affinity to reaction intermediates, which passivates Mo hollow sites, activates Mo top sites, and reduces the overadsorption of OH on the Mo active sites, as predicted by calculations. The atomic‐level modification is well confirmed by atomic‐resolution imaging, high‐resolution electron tomography, synchrotron soft X‐ray spectroscopy, and operando electrochemical infrared spectroscopy. Consequently, the Faradaic efficiency for CO 2 reduction to CH 4 is enhanced from 16% to 89%, a record high efficiency so far, in aqueous electrolytes. It also exhibits a negligible activity loss over 50 h.