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. By 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 respective impacts 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 examined at the atomic level. First-principles calculations further elucidated the origin of intrinsic activity improvement associated with the optimal local strain of the Fe−N bond.
Original language | English |
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Pages (from-to) | 1022-1032 |
Number of pages | 11 |
Journal | Angewandte Chemie - International Edition |
Volume | 60 |
Issue number | 2 |
DOIs | |
State | Published - Jan 11 2021 |
Funding
G. Wu and G. F. Wang acknowledge the support from the U.S. National Science Foundation (CBET‐1804326 and 1804534). Electron microscopy researches were conducted at Brookhaven National Laboratory (S. Hwang and D. Su, under contract No. DE‐SC0012704) and Oak Ridge National Laboratory (D. A. Cullen), which both are DOE Office of Science User Facilities. Z. Feng thanks for the startup funding from Oregon State University. XAS measurements were performed at beamline 5‐BM‐D of DND‐CAT and 9‐BM‐C at Argonne National Laboratory. G. Wu and G. F. Wang acknowledge the support from the U.S. National Science Foundation (CBET-1804326 and 1804534). Electron microscopy researches were conducted at Brookhaven National Laboratory (S. Hwang and D. Su, under contract No. DE-SC0012704) and Oak Ridge National Laboratory (D. A. Cullen), which both are DOE Office of Science User Facilities. Z. Feng thanks for the startup funding from Oregon State University. XAS measurements were performed at beamline 5-BM-D of DND-CAT and 9-BM-C at Argonne National Laboratory.
Keywords
- CO reduction
- Fe-N-C catalysts
- electrocatalysis
- local strain
- single-metal sites