Reaction intermediates during operando electrocatalysis identified from full solvent quantum mechanics molecular dynamics
Abstract
Electrocatalysis provides a powerful means to selectively transform molecules, but a serious impediment in making rapid progress is the lack of a molecular-based understanding of the reactive mechanisms or intermediates at the electrode–electrolyte interface (EEI). Recent experimental techniques have been developed for operando identification of reaction intermediates using surface infrared (IR) and Raman spectroscopy. However, large noises in the experimental spectrum pose great challenges in resolving the atomistic structures of reactive intermediates. To provide an interpretation of these experimental studies and target for additional studies, we report the results from quantum mechanics molecular dynamics (QM-MD) with explicit consideration of solvent, electrode–electrolyte interface, and applied potential at 298 K, which conceptually resemble the operando experimental condition, leading to a prototype of operando QM-MD (o-QM-MD). With o-QM-MD, we characterize 22 possible reactive intermediates in carbon dioxide reduction reactions ( RRs). Furthermore, we report the vibrational density of states (v-DoSs) of these intermediates from two-phase thermodynamic (2PT) analysis. Accordingly, we identify important intermediates such as chemisorbed ( ), *HOC-COH, *C-CH, and *C-COH in our o-QM-MD likely to explain the experimental spectrum. Indeed, we assign the experimental peak at 1,191 cm −1 to the mode of C-O stretch in *HOC-COH predicted at 1,189 cm −1 and the experimental peak at 1,584 cm −1 to the mode of C-C stretch in *C-COD predicted at 1,581 cm −1 . Interestingly, we find that surface ketene (*C=C=O), arising from *HOC-COH dehydration, also shows signals at around 1,584 cm −1 , which indicates a nonelectrochemical pathway of hydrocarbon formation at low overpotential and high pH conditions.
- Authors:
- Publication Date:
- Research Org.:
- California Institute of Technology (CalTech), Pasadena, CA (United States)
- Sponsoring Org.:
- USDOE Office of Electricity (OE), Advanced Grid Research & Development. Power Systems Engineering Research; National Science Foundation (NSF)
- OSTI Identifier:
- 1499812
- Alternate Identifier(s):
- OSTI ID: 1610791
- Grant/Contract Number:
- SC0004993; ACI-1053575
- Resource Type:
- Published Article
- Journal Name:
- Proceedings of the National Academy of Sciences of the United States of America
- Additional Journal Information:
- Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 116 Journal Issue: 16; Journal ID: ISSN 0027-8424
- Publisher:
- National Academy of Sciences
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; Science & Technology - Other Topics; quantum mechanics; molecular dynamics; vibration mode; CO2 reduction reaction; reaction mechanism
Citation Formats
Cheng, Tao, Fortunelli, Alessandro, and Goddard, III, William A. Reaction intermediates during operando electrocatalysis identified from full solvent quantum mechanics molecular dynamics. United States: N. p., 2019.
Web. doi:10.1073/pnas.1821709116.
Cheng, Tao, Fortunelli, Alessandro, & Goddard, III, William A. Reaction intermediates during operando electrocatalysis identified from full solvent quantum mechanics molecular dynamics. United States. https://doi.org/10.1073/pnas.1821709116
Cheng, Tao, Fortunelli, Alessandro, and Goddard, III, William A. Wed .
"Reaction intermediates during operando electrocatalysis identified from full solvent quantum mechanics molecular dynamics". United States. https://doi.org/10.1073/pnas.1821709116.
@article{osti_1499812,
title = {Reaction intermediates during operando electrocatalysis identified from full solvent quantum mechanics molecular dynamics},
author = {Cheng, Tao and Fortunelli, Alessandro and Goddard, III, William A.},
abstractNote = {Electrocatalysis provides a powerful means to selectively transform molecules, but a serious impediment in making rapid progress is the lack of a molecular-based understanding of the reactive mechanisms or intermediates at the electrode–electrolyte interface (EEI). Recent experimental techniques have been developed for operando identification of reaction intermediates using surface infrared (IR) and Raman spectroscopy. However, large noises in the experimental spectrum pose great challenges in resolving the atomistic structures of reactive intermediates. To provide an interpretation of these experimental studies and target for additional studies, we report the results from quantum mechanics molecular dynamics (QM-MD) with explicit consideration of solvent, electrode–electrolyte interface, and applied potential at 298 K, which conceptually resemble the operando experimental condition, leading to a prototype of operando QM-MD (o-QM-MD). With o-QM-MD, we characterize 22 possible reactive intermediates in carbon dioxide reduction reactions ( C O 2 RRs). Furthermore, we report the vibrational density of states (v-DoSs) of these intermediates from two-phase thermodynamic (2PT) analysis. Accordingly, we identify important intermediates such as chemisorbed C O 2 ( b - C O 2 ), *HOC-COH, *C-CH, and *C-COH in our o-QM-MD likely to explain the experimental spectrum. Indeed, we assign the experimental peak at 1,191 cm −1 to the mode of C-O stretch in *HOC-COH predicted at 1,189 cm −1 and the experimental peak at 1,584 cm −1 to the mode of C-C stretch in *C-COD predicted at 1,581 cm −1 . Interestingly, we find that surface ketene (*C=C=O), arising from *HOC-COH dehydration, also shows signals at around 1,584 cm −1 , which indicates a nonelectrochemical pathway of hydrocarbon formation at low overpotential and high pH conditions.},
doi = {10.1073/pnas.1821709116},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 16,
volume = 116,
place = {United States},
year = {Wed Mar 13 00:00:00 EDT 2019},
month = {Wed Mar 13 00:00:00 EDT 2019}
}
https://doi.org/10.1073/pnas.1821709116
Web of Science
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