Engineering Atomically Dispersed FeN4 Active Sites for CO2 Electroreduction

Mohd Adli, Nadia; Shan, Weitao; Hwang, Sooyeon; Samarakoon, Widitha; Karakalos, Stavros; Li, Yi; Cullen, David A.; Su, Dong; Feng, Zhenxing; Wang, Guofeng; Wu, Gang

doi:10.1002/ange.202012329

Engineering Atomically Dispersed FeN₄ Active Sites for CO₂ Electroreduction

Journal Article · Thu Nov 12 00:00:00 EST 2020 · Angewandte Chemie

DOI:https://doi.org/10.1002/ange.202012329· OSTI ID:1737432

Mohd Adli, Nadia ^[1]; Shan, Weitao ^[2]; ^[3]; Samarakoon, Widitha ^[4]; Karakalos, Stavros ^[5]; Li, Yi ^[1]; Cullen, David A. ^[6]; Su, Dong ^[3]; Feng, Zhenxing ^[4]; Wang, Guofeng ^[2]; ^[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)

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.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0012704

OSTI ID:: 1737432

Alternate ID(s):: OSTI ID: 1810879
OSTI ID: 1712543
OSTI ID: 1764261
OSTI ID: 1765230

Report Number(s):: BNL-220728-2020-JAAM

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 2 Vol. 133; ISSN 0044-8249

Publisher:: German Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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