Revealing the Origin of Activity in Nitrogen-Doped Nanocarbons towards Electrocatalytic Reduction of Carbon Dioxide.
Carbon nanotubes (CNTs) are functionalized with nitrogen atoms for reduction of carbon dioxide (CO2 ). 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 CO2 proceeds through an initial rate-determining transfer of one electron to CO2 , which leads to the formation of carbon dioxide radical anion (CO2 (.-) ). The initial reduction barrier is too high on pristine CNTs, resulting in a very high overpotentials at which the hydrogen evolution reaction dominates over CO2 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.
Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, 72 Wenhua Road, Shenyang, 110016, PR China.
Junyuan
J
Xu
Jiangsu Key Laboratory for Chemistry of Low-Dimensional Materials, School of Chemistry and Chemical Engineering, Huaiyin Normal University, 111 Changjiang West Road, Huai'an, 223300, PR China.
Yuhe
Y
Kan
Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, 72 Wenhua Road, Shenyang, 110016, PR China.
Rui
R
Huang
Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, 72 Wenhua Road, Shenyang, 110016, PR China.
Bingsen
B
Zhang
Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, 72 Wenhua Road, Shenyang, 110016, PR China.
Bolun
B
Wang
Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, 72 Wenhua Road, Shenyang, 110016, PR China.
Kuang-Hsu
KH
Wu
Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, 72 Wenhua Road, Shenyang, 110016, PR China.
Yangming
Y
Lin
Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, 72 Wenhua Road, Shenyang, 110016, PR China.
Xiaoyan
X
Sun
Department of Energy Conversion and Storage, Technical University of Denmark, Kemitorvet 207, DK-2800, Kgs. Lyngby, Denmark.
Qingfeng
Q
Li
Department of Electronic Engineering, Industrial Chemistry and Engineering, Section Industrial Chemistry, University of Messina and INSTM/CASPE (Laboratory of Catalysis for Sustainable Production and Energy), V.le F. Stagno D'Alcontres 31, Messina, 98166, Italy.
Gabriele
G
Centi
Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, 72 Wenhua Road, Shenyang, 110016, PR China. dssu@imr.ac.cn.
Dangsheng
D
Su
D002245:Carbon Dioxide / Q000737:chemistry*; D002384:Catalysis; D004563:Electrochemistry; D037742:Nanotubes, Carbon / Q000737:chemistry*; D009584:Nitrogen / Q000737:chemistry*; D010084:Oxidation-Reduction
D037742:Nanotubes, Carbon; D002245:Carbon Dioxide; D009584:Nitrogen
carbon dioxide; carbon nanotubes; doping; electrochemistry; nitrogen