Toward benchmarking theoretical computations of elementary rate constants on catalytic surfaces: formate decomposition on Au and Cu
Abstract
With the emergence of methods for computing rate constants for elementary reaction steps of catalytic reactions, benchmarking their accuracy becomes important. The unimolecular dehydrogenation of adsorbed formate on metal surfaces serves as a prototype for comparing experiment and theory. Previously measured pre-exponential factors for CO2 formation from formate on metal surfaces, including Cu(110), are substantially higher than expected from the often used value of kBT/h, or ~6 × 1012 s–1, suggesting that the entropy of the transition state is higher than that of the adsorbed formate. Herein, the rate constant parameters for formate decomposition on Au(110) and Cu(110) are addressed quantitatively by both experiment and theory and compared. A pre-exponential factor of 2.3 × 1014 s–1 was obtained experimentally on Au(110). DFT calculations revealed the most stable configuration of formate on both surfaces to be bidentate and the transition states to be less rigidly bound to the surface compared to the reactant state, resulting in a higher entropy of activation and a pre-exponential factor exceeding kBT/h. Though reasonable agreement is obtained between experiment and theory for the pre-exponential factors, the activation energies determined experimentally remain consistently higher than those computed by DFT using the GGA–PBE functional. This difference was largelymore »
- Authors:
-
[1];
[3];
[4];
[5];
[1]
- John A. Paulson School of Engineering and Applied Sciences, Harvard University, Cambridge, MA 02138, USA
- Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, NY 11973, USA
- Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA 02138, USA
- John A. Paulson School of Engineering and Applied Sciences, Harvard University, Cambridge, MA 02138, USA, Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA 02138, USA
- Department of Chemical and Biomolecular Engineering, University of California, Los Angeles, Los Angeles, CA 90095, USA, Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, CA 90095, USA
- Publication Date:
- Research Org.:
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1838376
- Alternate Identifier(s):
- OSTI ID: 1854505
- Report Number(s):
- BNL-222837-2022-JAAM
Journal ID: ISSN 2041-6520; CSHCBM
- Grant/Contract Number:
- SC0012704
- Resource Type:
- Published Article
- Journal Name:
- Chemical Science
- Additional Journal Information:
- Journal Name: Chemical Science Journal Volume: 13 Journal Issue: 3; Journal ID: ISSN 2041-6520
- Publisher:
- Royal Society of Chemistry (RSC)
- Country of Publication:
- United Kingdom
- Language:
- English
- Subject:
- 77 NANOSCIENCE AND NANOTECHNOLOGY
Citation Formats
Muramoto, Eri, Chen, Wei, Jia, Xiwen, Friend, Cynthia M., Sautet, Philippe, and Madix, Robert J. Toward benchmarking theoretical computations of elementary rate constants on catalytic surfaces: formate decomposition on Au and Cu. United Kingdom: N. p., 2022.
Web. doi:10.1039/D1SC05127J.
Muramoto, Eri, Chen, Wei, Jia, Xiwen, Friend, Cynthia M., Sautet, Philippe, & Madix, Robert J. Toward benchmarking theoretical computations of elementary rate constants on catalytic surfaces: formate decomposition on Au and Cu. United Kingdom. https://doi.org/10.1039/D1SC05127J
Muramoto, Eri, Chen, Wei, Jia, Xiwen, Friend, Cynthia M., Sautet, Philippe, and Madix, Robert J. Wed .
"Toward benchmarking theoretical computations of elementary rate constants on catalytic surfaces: formate decomposition on Au and Cu". United Kingdom. https://doi.org/10.1039/D1SC05127J.
@article{osti_1838376,
title = {Toward benchmarking theoretical computations of elementary rate constants on catalytic surfaces: formate decomposition on Au and Cu},
author = {Muramoto, Eri and Chen, Wei and Jia, Xiwen and Friend, Cynthia M. and Sautet, Philippe and Madix, Robert J.},
abstractNote = {With the emergence of methods for computing rate constants for elementary reaction steps of catalytic reactions, benchmarking their accuracy becomes important. The unimolecular dehydrogenation of adsorbed formate on metal surfaces serves as a prototype for comparing experiment and theory. Previously measured pre-exponential factors for CO2 formation from formate on metal surfaces, including Cu(110), are substantially higher than expected from the often used value of kBT/h, or ~6 × 1012 s–1, suggesting that the entropy of the transition state is higher than that of the adsorbed formate. Herein, the rate constant parameters for formate decomposition on Au(110) and Cu(110) are addressed quantitatively by both experiment and theory and compared. A pre-exponential factor of 2.3 × 1014 s–1 was obtained experimentally on Au(110). DFT calculations revealed the most stable configuration of formate on both surfaces to be bidentate and the transition states to be less rigidly bound to the surface compared to the reactant state, resulting in a higher entropy of activation and a pre-exponential factor exceeding kBT/h. Though reasonable agreement is obtained between experiment and theory for the pre-exponential factors, the activation energies determined experimentally remain consistently higher than those computed by DFT using the GGA–PBE functional. This difference was largely erased when the metaGGA–SCAN functional was applied. This study provides insight into the underlying factors that result in the relatively high pre-exponential factors for unimolecular decomposition on metal surfaces generally, highlights the importance of mobility for the transition state, and offers vital information related to the direct use of DFT to predict rate constants for elementary reaction steps on metal surfaces.},
doi = {10.1039/D1SC05127J},
journal = {Chemical Science},
number = 3,
volume = 13,
place = {United Kingdom},
year = {Wed Jan 19 00:00:00 EST 2022},
month = {Wed Jan 19 00:00:00 EST 2022}
}
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