Modulation of the coordination environment enhances the electrocatalytic efficiency of Mo single atoms toward water splitting
Abstract
Here, enhancing the catalytic efficiency through engineering active site environments is expected to work pronouncedly for single atom catalysts (SACs) because of intense atomic scale interactions involved between SAs and their coordination environments. Taking Mo SACs for catalyzation of the hydrogen evolution reaction (HER) as an example, three SACs of different coordination environments, namely Mo-O2N2, Mo-O2N1C1, and Mo-O2C2, were successfully created for demonstration. The HER performances are in an increasing order of Mo-O2N2, Mo-O2N1C1, and Mo-O2C2, exhibiting η10 of 98, 71, and 61 mV, η500 of 340, 248, and 200 mV, Tafel slopes of 95.8, 39.6, and 33.8 mV dec-1, and current density decays of 9, 6, and 6% after a 50 hour operation at an initial current density of 100 mA cm-2, respectively. Substituting C with N in the coordination environment results in inferior HER catalytic efficiency and stability. Density functional theory calculations reveal that replacing carbon with nitrogen for coordination with the Mo SA on a carbon substrate of a higher N-doping level shifts the d-band center of Mo more negatively from the Fermi level, thereby increasing the hydrogen adsorption energy and thus decelerating the hydrogen desorption kinetics, giving consequent inferior HER activities.
- Authors:
-
[2];
[3];
[1]
- National Tsing Hua Univ., Hsinchu (Taiwan)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- National Yang Ming Chiao Tung Univ., Tainan (Taiwan)
- Publication Date:
- Research Org.:
- Brookhaven National Laboratory (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC); Ministry of Science and Technology of Taiwan
- OSTI Identifier:
- 1868521
- Report Number(s):
- BNL-222978-2022-JAAM
Journal ID: ISSN 2050-7488
- Grant/Contract Number:
- SC0012704; MOST110-2221-E-007-012-MY3; MOST 110-2221-E-A49-017-MY3; MOST 110-2731-M-007-001
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Materials Chemistry. A
- Additional Journal Information:
- Journal Volume: 10; Journal Issue: 16; Journal ID: ISSN 2050-7488
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; aqueous battery; ion intercalation
Citation Formats
Cheng, Chih-Chieh, Yeh, Yong-Xian, Ting, Yu-Chieh, Lin, Shin-Hong, Sasaki, Kotaro, Choi, YongMan, and Lu, Shih-Yuan. Modulation of the coordination environment enhances the electrocatalytic efficiency of Mo single atoms toward water splitting. United States: N. p., 2022.
Web. doi:10.1039/d2ta01750d.
Cheng, Chih-Chieh, Yeh, Yong-Xian, Ting, Yu-Chieh, Lin, Shin-Hong, Sasaki, Kotaro, Choi, YongMan, & Lu, Shih-Yuan. Modulation of the coordination environment enhances the electrocatalytic efficiency of Mo single atoms toward water splitting. United States. https://doi.org/10.1039/d2ta01750d
Cheng, Chih-Chieh, Yeh, Yong-Xian, Ting, Yu-Chieh, Lin, Shin-Hong, Sasaki, Kotaro, Choi, YongMan, and Lu, Shih-Yuan. Mon .
"Modulation of the coordination environment enhances the electrocatalytic efficiency of Mo single atoms toward water splitting". United States. https://doi.org/10.1039/d2ta01750d. https://www.osti.gov/servlets/purl/1868521.
@article{osti_1868521,
title = {Modulation of the coordination environment enhances the electrocatalytic efficiency of Mo single atoms toward water splitting},
author = {Cheng, Chih-Chieh and Yeh, Yong-Xian and Ting, Yu-Chieh and Lin, Shin-Hong and Sasaki, Kotaro and Choi, YongMan and Lu, Shih-Yuan},
abstractNote = {Here, enhancing the catalytic efficiency through engineering active site environments is expected to work pronouncedly for single atom catalysts (SACs) because of intense atomic scale interactions involved between SAs and their coordination environments. Taking Mo SACs for catalyzation of the hydrogen evolution reaction (HER) as an example, three SACs of different coordination environments, namely Mo-O2N2, Mo-O2N1C1, and Mo-O2C2, were successfully created for demonstration. The HER performances are in an increasing order of Mo-O2N2, Mo-O2N1C1, and Mo-O2C2, exhibiting η10 of 98, 71, and 61 mV, η500 of 340, 248, and 200 mV, Tafel slopes of 95.8, 39.6, and 33.8 mV dec-1, and current density decays of 9, 6, and 6% after a 50 hour operation at an initial current density of 100 mA cm-2, respectively. Substituting C with N in the coordination environment results in inferior HER catalytic efficiency and stability. Density functional theory calculations reveal that replacing carbon with nitrogen for coordination with the Mo SA on a carbon substrate of a higher N-doping level shifts the d-band center of Mo more negatively from the Fermi level, thereby increasing the hydrogen adsorption energy and thus decelerating the hydrogen desorption kinetics, giving consequent inferior HER activities.},
doi = {10.1039/d2ta01750d},
journal = {Journal of Materials Chemistry. A},
number = 16,
volume = 10,
place = {United States},
year = {Mon Apr 11 00:00:00 EDT 2022},
month = {Mon Apr 11 00:00:00 EDT 2022}
}
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