skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Boosting CO2 reduction on Fe-N-C with sulfur incorporation: Synergistic electronic and structural engineering

Abstract

Developing earth-abundant efficient catalysts for CO2 reduction reaction (CO2RR) is of paramount importance for electrochemical conversion of CO2 into value-added products. Despite numerous studies on iron and nitrogen codoped carbon (Fe-N-C) catalysts, grand challenges exist due to limited performance and understanding of catalytic mechanisms. This study reports a general strategy to boost electrocatalytic CO2RR activity of Fe-N-C with the incorporation of S atoms to engineer carbon support structure and electronic properties of active Fe-N sites simultaneously via a copolymer-assisted synthetic approach. The employment of N,S comonomers significantly increases the numbers of micropores and surface area, enabling dense atomic Fe-N and enhanced utilization efficiency. We report the first-principles calculations reveal that S modulation upraises the Fermi energy of Fe 3d and increases charge density on Fe atoms of Fe-N4, thereby enhancing intrinsic catalytic reactivity and selectivity for CO2 reduction by strengthening the binding interaction between the Fe site and key COOH* intermediate. These integrated structural and electronic merits endow Fe-NS-C with outstanding activity (e.g., CO Faradaic efficiency of 98% at an overpotential of 490 mV) and stability (without deactivation in 30 h), ranking it one of the most active Fe-N-C reported to date. The finding offers an innovative design strategy tomore » enable the design of advanced catalysts for CO2 conversion.« less

Authors:
 [1];  [2];  [3];  [4];  [1];  [1];  [1];  [5];  [6];  [4];  [5];  [2];  [1]
  1. Texas A & M Univ., College Station, TX (United States)
  2. Univ. of Pittsburgh, PA (United States)
  3. Northern Illinois Univ., DeKalb, IL (United States)
  4. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
  5. Univ. at Buffalo, NY (United States)
  6. Northern Illinois Univ., DeKalb, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); Northern Illinois University
OSTI Identifier:
1615906
Alternate Identifier(s):
OSTI ID: 1604622; OSTI ID: 1694278
Report Number(s):
BNL-213731-2020-JAAM
Journal ID: ISSN 2211-2855; 159482
Grant/Contract Number:  
AC02-06CH11357; SC0012704; ACI-1053575
Resource Type:
Accepted Manuscript
Journal Name:
Nano Energy
Additional Journal Information:
Journal Volume: 68; Journal Issue: C; Journal ID: ISSN 2211-2855
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; CO2 reduction; Fe-N-C; density functional theory; electrocatalysis; sulfur engineering; 25 ENERGY STORAGE

Citation Formats

Pan, Fuping, Li, Boyang, Sarnello, Erik, Hwang, Sooyeon, Gang, Yang, Feng, Xuhui, Xiang, Xianmei, Adli, Nadia Mohd, Li, Tao, Su, Dong, Wu, Gang, Wang, Guofeng, and Li, Ying. Boosting CO2 reduction on Fe-N-C with sulfur incorporation: Synergistic electronic and structural engineering. United States: N. p., 2019. Web. https://doi.org/10.1016/j.nanoen.2019.104384.
Pan, Fuping, Li, Boyang, Sarnello, Erik, Hwang, Sooyeon, Gang, Yang, Feng, Xuhui, Xiang, Xianmei, Adli, Nadia Mohd, Li, Tao, Su, Dong, Wu, Gang, Wang, Guofeng, & Li, Ying. Boosting CO2 reduction on Fe-N-C with sulfur incorporation: Synergistic electronic and structural engineering. United States. https://doi.org/10.1016/j.nanoen.2019.104384
Pan, Fuping, Li, Boyang, Sarnello, Erik, Hwang, Sooyeon, Gang, Yang, Feng, Xuhui, Xiang, Xianmei, Adli, Nadia Mohd, Li, Tao, Su, Dong, Wu, Gang, Wang, Guofeng, and Li, Ying. Fri . "Boosting CO2 reduction on Fe-N-C with sulfur incorporation: Synergistic electronic and structural engineering". United States. https://doi.org/10.1016/j.nanoen.2019.104384. https://www.osti.gov/servlets/purl/1615906.
@article{osti_1615906,
title = {Boosting CO2 reduction on Fe-N-C with sulfur incorporation: Synergistic electronic and structural engineering},
author = {Pan, Fuping and Li, Boyang and Sarnello, Erik and Hwang, Sooyeon and Gang, Yang and Feng, Xuhui and Xiang, Xianmei and Adli, Nadia Mohd and Li, Tao and Su, Dong and Wu, Gang and Wang, Guofeng and Li, Ying},
abstractNote = {Developing earth-abundant efficient catalysts for CO2 reduction reaction (CO2RR) is of paramount importance for electrochemical conversion of CO2 into value-added products. Despite numerous studies on iron and nitrogen codoped carbon (Fe-N-C) catalysts, grand challenges exist due to limited performance and understanding of catalytic mechanisms. This study reports a general strategy to boost electrocatalytic CO2RR activity of Fe-N-C with the incorporation of S atoms to engineer carbon support structure and electronic properties of active Fe-N sites simultaneously via a copolymer-assisted synthetic approach. The employment of N,S comonomers significantly increases the numbers of micropores and surface area, enabling dense atomic Fe-N and enhanced utilization efficiency. We report the first-principles calculations reveal that S modulation upraises the Fermi energy of Fe 3d and increases charge density on Fe atoms of Fe-N4, thereby enhancing intrinsic catalytic reactivity and selectivity for CO2 reduction by strengthening the binding interaction between the Fe site and key COOH* intermediate. These integrated structural and electronic merits endow Fe-NS-C with outstanding activity (e.g., CO Faradaic efficiency of 98% at an overpotential of 490 mV) and stability (without deactivation in 30 h), ranking it one of the most active Fe-N-C reported to date. The finding offers an innovative design strategy to enable the design of advanced catalysts for CO2 conversion.},
doi = {10.1016/j.nanoen.2019.104384},
journal = {Nano Energy},
number = C,
volume = 68,
place = {United States},
year = {2019},
month = {12}
}

Journal Article:

Citation Metrics:
Cited by: 7 works
Citation information provided by
Web of Science

Save / Share: