Engineering Atomically Dispersed FeN4 Active Sites for CO2 Electroreduction
Abstract
Atomically dispersed FeN4 active sites have exhibited exceptional catalytic activity and selectivity for the electrochemical CO2 reduction reaction (CO2RR) to CO. However, the understanding behind the intrinsic and morphological factors contributing to the catalytic properties of FeN4 sites is still lacking. Here, using a Fe-N-C model catalyst derived from the ZIF-8, we deconvoluted three key morphological and structural elements of FeN4 sites, including particle sizes of catalysts, Fe content, and Fe-N bond structures. Their monotonous effects on the CO2RR were comprehensively elucidated. Engineering the particle size and Fe doping is critical to control extrinsic morphological factors of FeN4 sites for optimal porosity, electrochemically active surface areas, and the graphitization of the carbon support. In contrast, the intrinsic activity of FeN4 sites was only tunable by varying thermal activation temperatures during the formation of FeN4 sites, which impacted the length of the Fe-N bonds and the local strains. The structural evolution of Fe-N bonds was characterized at the atomic level. First-principles calculations further elucidated the origin of intrinsic activity improvement associated with the optimal local strain on the Fe-N bond.
- Authors:
-
[3];
[1]
- Univ. at Buffalo, NY (United States)
- Univ. of Pittsburgh, PA (United States)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Oregon State Univ., Corvallis, OR (United States)
- Univ. of South Carolina, Columbia, SC (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Publication Date:
- Research Org.:
- Brookhaven National Laboratory (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
- OSTI Identifier:
- 1737432
- Alternate Identifier(s):
- OSTI ID: 1712543
- Report Number(s):
- BNL-220728-2020-JAAM
Journal ID: ISSN 0044-8249
- Grant/Contract Number:
- SC0012704; CBET-1804326; CBET-1804534
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Angewandte Chemie
- Additional Journal Information:
- Journal Volume: 133; Journal Issue: 2; Journal ID: ISSN 0044-8249
- Publisher:
- German Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE
Citation Formats
Mohd Adli, Nadia, Shan, Weitao, Hwang, Sooyeon, Samarakoon, Widitha, Karakalos, Stavros, Li, Yi, Cullen, David A., Su, Dong, Feng, Zhenxing, Wang, Guofeng, and Wu, Gang. Engineering Atomically Dispersed FeN4 Active Sites for CO2 Electroreduction. United States: N. p., 2020.
Web. doi:10.1002/ange.202012329.
Mohd Adli, Nadia, Shan, Weitao, Hwang, Sooyeon, Samarakoon, Widitha, Karakalos, Stavros, Li, Yi, Cullen, David A., Su, Dong, Feng, Zhenxing, Wang, Guofeng, & Wu, Gang. Engineering Atomically Dispersed FeN4 Active Sites for CO2 Electroreduction. United States. https://doi.org/10.1002/ange.202012329
Mohd Adli, Nadia, Shan, Weitao, Hwang, Sooyeon, Samarakoon, Widitha, Karakalos, Stavros, Li, Yi, Cullen, David A., Su, Dong, Feng, Zhenxing, Wang, Guofeng, and Wu, Gang. Thu .
"Engineering Atomically Dispersed FeN4 Active Sites for CO2 Electroreduction". United States. https://doi.org/10.1002/ange.202012329. https://www.osti.gov/servlets/purl/1737432.
@article{osti_1737432,
title = {Engineering Atomically Dispersed FeN4 Active Sites for CO2 Electroreduction},
author = {Mohd Adli, Nadia and Shan, Weitao and Hwang, Sooyeon and Samarakoon, Widitha and Karakalos, Stavros and Li, Yi and Cullen, David A. and Su, Dong and Feng, Zhenxing and Wang, Guofeng and Wu, Gang},
abstractNote = {Atomically dispersed FeN4 active sites have exhibited exceptional catalytic activity and selectivity for the electrochemical CO2 reduction reaction (CO2RR) to CO. However, the understanding behind the intrinsic and morphological factors contributing to the catalytic properties of FeN4 sites is still lacking. Here, using a Fe-N-C model catalyst derived from the ZIF-8, we deconvoluted three key morphological and structural elements of FeN4 sites, including particle sizes of catalysts, Fe content, and Fe-N bond structures. Their monotonous effects on the CO2RR were comprehensively elucidated. Engineering the particle size and Fe doping is critical to control extrinsic morphological factors of FeN4 sites for optimal porosity, electrochemically active surface areas, and the graphitization of the carbon support. In contrast, the intrinsic activity of FeN4 sites was only tunable by varying thermal activation temperatures during the formation of FeN4 sites, which impacted the length of the Fe-N bonds and the local strains. The structural evolution of Fe-N bonds was characterized at the atomic level. First-principles calculations further elucidated the origin of intrinsic activity improvement associated with the optimal local strain on the Fe-N bond.},
doi = {10.1002/ange.202012329},
journal = {Angewandte Chemie},
number = 2,
volume = 133,
place = {United States},
year = {Thu Nov 12 00:00:00 EST 2020},
month = {Thu Nov 12 00:00:00 EST 2020}
}
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