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Title: Electrochemical CO 2 Reduction with Atomic Iron-Dispersed on Nitrogen-Doped Graphene

Electrochemical reduction of CO 2 provides an opportunity to reach a carbon-neutral energy recycling regime, in which CO 2 emissions from fuel use are collected and converted back to fuels. The reduction of CO 2 to CO is the first step toward the synthesis of more complex carbon-based fuels and chemicals. Therefore, understanding this step is crucial for the development of high-performance electrocatalyst for CO 2 conversion to higher order products such as hydrocarbons. In this paper, atomic iron dispersed on nitrogen-doped graphene (Fe/NG) is synthesized as an efficient electrocatalyst for CO 2 reduction to CO. Fe/NG has a low reduction overpotential with high Faradic efficiency up to 80%. The existence of nitrogen-confined atomic Fe moieties on the nitrogen-doped graphene layer is confirmed by aberration-corrected high-angle annular dark-field scanning transmission electron microscopy and X-ray absorption fine structure analysis. The Fe/NG catalysts provide an ideal platform for comparative studies of the effect of the catalytic center on the electrocatalytic performance. Finally, the CO 2 reduction reaction mechanism on atomic Fe surrounded by four N atoms (Fe–N 4) embedded in nitrogen-doped graphene is further investigated through density functional theory calculations, revealing a possible promotional effect of nitrogen doping on graphene.
Authors:
 [1] ;  [2] ;  [3] ;  [4] ;  [3] ;  [1] ;  [1] ;  [5] ;  [5] ;  [1] ;  [3] ;  [6] ;  [7] ;  [8] ;  [9] ;  [10] ;  [11] ; ORCiD logo [11]
  1. Rice Univ., Houston, TX (United States). Dept. of Chemistry
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division
  3. Rice Univ., Houston, TX (United States). Dept. of Materials Science and NanoEngineering
  4. Rice Univ., Houston, TX (United States). Dept. of Materials Science and NanoEngineering; Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials
  5. Soochow Univ., Suzhou (China). Inst. of Functional Nano and Soft Materials
  6. Jiangsu Univ., Zhenjiang (China). Inst. for Energy Research
  7. Rice Univ., Houston, TX (United States). Dept. of Chemistry. Smalley-Curl Inst. The NanoCarbon Center
  8. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials
  9. Rice Univ., Houston, TX (United States). Dept. of Chemistry. Dept. of Materials Science and NanoEngineering
  10. Rice Univ., Houston, TX (United States). Dept. of Materials Science and NanoEngineering; Jiangsu Univ., Zhenjiang (China). Inst. for Energy Research
  11. Rice Univ., Houston, TX (United States). Dept. of Chemistry. Dept. of Materials Science and NanoEngineering. Smalley-Curl Inst. The NanoCarbon Center
Publication Date:
Report Number(s):
BNL-203515-2018-JAAM
Journal ID: ISSN 1614-6832
Grant/Contract Number:
SC0012704; FA9550-12-1-0035; FA9550-14-1-0111; 56256 DNI5; AC05-00OR22725
Type:
Accepted Manuscript
Journal Name:
Advanced Energy Materials
Additional Journal Information:
Journal Name: Advanced Energy Materials; Journal ID: ISSN 1614-6832
Publisher:
Wiley
Research Org:
Brookhaven National Lab. (BNL), Upton, NY (United States); Rice Univ., Houston, TX (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); US Air Force Office of Scientific Research (AFOSR); American Chemical Society Petroleum Research Fund (United States)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; atomic iron; CO2 reduction reaction; electrocatalysts; nitrogen-doped graphene
OSTI Identifier:
1433979
Alternate Identifier(s):
OSTI ID: 1429531; OSTI ID: 1435178

Zhang, Chenhao, Yang, Shize, Wu, Jingjie, Liu, Mingjie, Yazdi, Sadegh, Ren, Muqing, Sha, Junwei, Zhong, Jun, Nie, Kaiqi, Jalilov, Almaz S., Li, Zhenyuan, Li, Huaming, Yakobson, Boris I., Wu, Qin, Ringe, Emilie, Xu, Hui, Ajayan, Pulickel M., and Tour, James M.. Electrochemical CO2 Reduction with Atomic Iron-Dispersed on Nitrogen-Doped Graphene. United States: N. p., Web. doi:10.1002/aenm.201703487.
Zhang, Chenhao, Yang, Shize, Wu, Jingjie, Liu, Mingjie, Yazdi, Sadegh, Ren, Muqing, Sha, Junwei, Zhong, Jun, Nie, Kaiqi, Jalilov, Almaz S., Li, Zhenyuan, Li, Huaming, Yakobson, Boris I., Wu, Qin, Ringe, Emilie, Xu, Hui, Ajayan, Pulickel M., & Tour, James M.. Electrochemical CO2 Reduction with Atomic Iron-Dispersed on Nitrogen-Doped Graphene. United States. doi:10.1002/aenm.201703487.
Zhang, Chenhao, Yang, Shize, Wu, Jingjie, Liu, Mingjie, Yazdi, Sadegh, Ren, Muqing, Sha, Junwei, Zhong, Jun, Nie, Kaiqi, Jalilov, Almaz S., Li, Zhenyuan, Li, Huaming, Yakobson, Boris I., Wu, Qin, Ringe, Emilie, Xu, Hui, Ajayan, Pulickel M., and Tour, James M.. 2018. "Electrochemical CO2 Reduction with Atomic Iron-Dispersed on Nitrogen-Doped Graphene". United States. doi:10.1002/aenm.201703487.
@article{osti_1433979,
title = {Electrochemical CO2 Reduction with Atomic Iron-Dispersed on Nitrogen-Doped Graphene},
author = {Zhang, Chenhao and Yang, Shize and Wu, Jingjie and Liu, Mingjie and Yazdi, Sadegh and Ren, Muqing and Sha, Junwei and Zhong, Jun and Nie, Kaiqi and Jalilov, Almaz S. and Li, Zhenyuan and Li, Huaming and Yakobson, Boris I. and Wu, Qin and Ringe, Emilie and Xu, Hui and Ajayan, Pulickel M. and Tour, James M.},
abstractNote = {Electrochemical reduction of CO2 provides an opportunity to reach a carbon-neutral energy recycling regime, in which CO2 emissions from fuel use are collected and converted back to fuels. The reduction of CO2 to CO is the first step toward the synthesis of more complex carbon-based fuels and chemicals. Therefore, understanding this step is crucial for the development of high-performance electrocatalyst for CO2 conversion to higher order products such as hydrocarbons. In this paper, atomic iron dispersed on nitrogen-doped graphene (Fe/NG) is synthesized as an efficient electrocatalyst for CO2 reduction to CO. Fe/NG has a low reduction overpotential with high Faradic efficiency up to 80%. The existence of nitrogen-confined atomic Fe moieties on the nitrogen-doped graphene layer is confirmed by aberration-corrected high-angle annular dark-field scanning transmission electron microscopy and X-ray absorption fine structure analysis. The Fe/NG catalysts provide an ideal platform for comparative studies of the effect of the catalytic center on the electrocatalytic performance. Finally, the CO2 reduction reaction mechanism on atomic Fe surrounded by four N atoms (Fe–N4) embedded in nitrogen-doped graphene is further investigated through density functional theory calculations, revealing a possible promotional effect of nitrogen doping on graphene.},
doi = {10.1002/aenm.201703487},
journal = {Advanced Energy Materials},
number = ,
volume = ,
place = {United States},
year = {2018},
month = {3}
}

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