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Revealing the Origin of Activity in Nitrogen‐Doped Nanocarbons towards Electrocatalytic Reduction of Carbon Dioxide
Author(s) -
Xu Junyuan,
Kan Yuhe,
Huang Rui,
Zhang Bingsen,
Wang Bolun,
Wu KuangHsu,
Lin Yangming,
Sun Xiaoyan,
Li Qingfeng,
Centi Gabriele,
Su Dangsheng
Publication year - 2016
Publication title -
chemsuschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.412
H-Index - 157
eISSN - 1864-564X
pISSN - 1864-5631
DOI - 10.1002/cssc.201600202
Subject(s) - tafel equation , catalysis , nitrogen , chemistry , electrochemical reduction of carbon dioxide , inorganic chemistry , carbon nanotube , carbon dioxide , electron transfer , carbon fibers , density functional theory , hydrogen , photochemistry , materials science , nanotechnology , organic chemistry , electrochemistry , computational chemistry , electrode , composite material , carbon monoxide , composite number
Carbon nanotubes (CNTs) are functionalized with nitrogen atoms for reduction of carbon dioxide (CO 2 ). The investigation explores the origin of the catalyst′s activity and the role of nitrogen chemical states therein. The catalysts show excellent performances, with about 90 % current efficiency for CO formation and stability over 60 hours. The Tafel analyses and density functional theory calculations suggest that the reduction of CO 2 proceeds through an initial rate‐determining transfer of one electron to CO 2 , which leads to the formation of carbon dioxide radical anion (CO 2 .− ). The initial reduction barrier is too high on pristine CNTs, resulting in a very high overpotentials at which the hydrogen evolution reaction dominates over CO 2 reduction. The doped nitrogen atoms stabilize the radical anion, thereby lowering the initial reduction barrier and improving the intrinsic activity. The most efficient nitrogen chemical state for this reaction is quaternary nitrogen, followed by pyridinic and pyrrolic nitrogen.