skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: 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 ( 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.

Authors:
ORCiD logo; ; ORCiD logo
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. doi: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. doi: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 = {2019},
month = {3}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1073/pnas.1821709116

Citation Metrics:
Cited by: 8 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Theoretical Considerations on the Electroreduction of CO to C 2 Species on Cu(100) Electrodes
journal, June 2013

  • Calle-Vallejo, Federico; Koper, Marc T. M.
  • Angewandte Chemie International Edition, Vol. 52, Issue 28
  • DOI: 10.1002/anie.201301470

A review of the aqueous electrochemical reduction of CO2 to hydrocarbons at copper
journal, August 2006


A Step Closer to the Electrochemical Production of Liquid Fuels
journal, July 2014

  • Schouten, Klaas Jan P.; Calle-Vallejo, Federico; Koper, Marc T. M.
  • Angewandte Chemie International Edition, Vol. 53, Issue 41
  • DOI: 10.1002/anie.201406174

On the origin of the elusive first intermediate of CO 2 electroreduction
journal, September 2018

  • Chernyshova, Irina V.; Somasundaran, Ponisseril; Ponnurangam, Sathish
  • Proceedings of the National Academy of Sciences, Vol. 115, Issue 40
  • DOI: 10.1073/pnas.1802256115

Selective increase in CO 2 electroreduction activity at grain-boundary surface terminations
journal, November 2017


Mechanism of CO 2 Reduction at Copper Surfaces: Pathways to C 2 Products
journal, January 2018

  • Garza, Alejandro J.; Bell, Alexis T.; Head-Gordon, Martin
  • ACS Catalysis, Vol. 8, Issue 2
  • DOI: 10.1021/acscatal.7b03477

Explanation of Dramatic pH-Dependence of Hydrogen Binding on Noble Metal Electrode: Greatly Weakened Water Adsorption at High pH
journal, May 2018

  • Cheng, Tao; Wang, Lu; Merinov, Boris V.
  • Journal of the American Chemical Society, Vol. 140, Issue 25
  • DOI: 10.1021/jacs.8b04006

Nature of the Active Sites for CO Reduction on Copper Nanoparticles; Suggestions for Optimizing Performance
journal, August 2017

  • Cheng, Tao; Xiao, Hai; Goddard, William A.
  • Journal of the American Chemical Society, Vol. 139, Issue 34
  • DOI: 10.1021/jacs.7b03300

Electroreduction of carbon monoxide to liquid fuel on oxide-derived nanocrystalline copper
journal, April 2014

  • Li, Christina W.; Ciston, Jim; Kanan, Matthew W.
  • Nature, Vol. 508, Issue 7497
  • DOI: 10.1038/nature13249

Electrochemical CO2 Reduction on Metal Electrodes
book, January 2008


Two Pathways for the Formation of Ethylene in CO Reduction on Single-Crystal Copper Electrodes
journal, June 2012

  • Schouten, Klaas Jan P.; Qin, Zisheng; Pérez Gallent, Elena
  • Journal of the American Chemical Society, Vol. 134, Issue 24
  • DOI: 10.1021/ja302668n

Selectivity of CO 2 Reduction on Copper Electrodes: The Role of the Kinetics of Elementary Steps
journal, January 2013

  • Nie, Xiaowa; Esopi, Monica R.; Janik, Michael J.
  • Angewandte Chemie International Edition, Vol. 52, Issue 9
  • DOI: 10.1002/anie.201208320

Direct Observation on Reaction Intermediates and the Role of Bicarbonate Anions in CO 2 Electrochemical Reduction Reaction on Cu Surfaces
journal, October 2017

  • Zhu, Shangqian; Jiang, Bei; Cai, Wen-Bin
  • Journal of the American Chemical Society, Vol. 139, Issue 44
  • DOI: 10.1021/jacs.7b10462

Structure- and Potential-Dependent Cation Effects on CO Reduction at Copper Single-Crystal Electrodes
journal, November 2017

  • Pérez-Gallent, Elena; Marcandalli, Giulia; Figueiredo, Marta Costa
  • Journal of the American Chemical Society, Vol. 139, Issue 45
  • DOI: 10.1021/jacs.7b10142

Catalysis for the Valorization of Exhaust Carbon: from CO 2 to Chemicals, Materials, and Fuels. Technological Use of CO 2
journal, November 2013

  • Aresta, Michele; Dibenedetto, Angela; Angelini, Antonella
  • Chemical Reviews, Vol. 114, Issue 3
  • DOI: 10.1021/cr4002758

The influence of pH on the reduction of CO and CO 2 to hydrocarbons on copper electrodes
journal, March 2014

  • Schouten, Klaas Jan P.; Pérez Gallent, Elena; Koper, Marc T. M.
  • Journal of Electroanalytical Chemistry, Vol. 716
  • DOI: 10.1016/j.jelechem.2013.08.033

In Situ Spectroscopic Study of CO 2 Electroreduction at Copper Electrodes in Acetonitrile
journal, March 2016

  • Figueiredo, Marta C.; Ledezma-Yanez, Isis; Koper, Marc T. M.
  • ACS Catalysis, Vol. 6, Issue 4
  • DOI: 10.1021/acscatal.5b02543

Status and perspectives of CO2 conversion into fuels and chemicals by catalytic, photocatalytic and electrocatalytic processes
journal, January 2013

  • Kondratenko, Evgenii V.; Mul, Guido; Baltrusaitis, Jonas
  • Energy & Environmental Science, Vol. 6, Issue 11
  • DOI: 10.1039/c3ee41272e

CO 2 electroreduction to ethylene via hydroxide-mediated copper catalysis at an abrupt interface
journal, May 2018


Full atomistic reaction mechanism with kinetics for CO reduction on Cu(100) from ab initio molecular dynamics free-energy calculations at 298 K
journal, February 2017

  • Cheng, Tao; Xiao, Hai; Goddard, William A.
  • Proceedings of the National Academy of Sciences, Vol. 114, Issue 8
  • DOI: 10.1073/pnas.1612106114

Closing the loop: captured CO 2 as a feedstock in the chemical industry
journal, January 2015

  • Otto, Alexander; Grube, Thomas; Schiebahn, Sebastian
  • Energy & Environmental Science, Vol. 8, Issue 11
  • DOI: 10.1039/C5EE02591E

Enhanced electrocatalytic CO2 reduction via field-induced reagent concentration
journal, August 2016


How copper catalyzes the electroreduction of carbon dioxide into hydrocarbon fuels
journal, January 2010

  • Peterson, Andrew A.; Abild-Pedersen, Frank; Studt, Felix
  • Energy & Environmental Science, Vol. 3, Issue 9
  • DOI: 10.1039/c0ee00071j

Reaction Mechanisms for the Electrochemical Reduction of CO 2 to CO and Formate on the Cu(100) Surface at 298 K from Quantum Mechanics Free Energy Calculations with Explicit Water
journal, October 2016

  • Cheng, Tao; Xiao, Hai; Goddard, William A.
  • Journal of the American Chemical Society, Vol. 138, Issue 42
  • DOI: 10.1021/jacs.6b08534

PRODUCTION OF CO AND CH 4 IN ELECTROCHEMICAL REDUCTION OF CO 2 AT METAL ELECTRODES IN AQUEOUS HYDROGENCARBONATE SOLUTION
journal, November 1985

  • Hori, Yoshio; Kikuchi, Katsuhei; Suzuki, Shin
  • Chemistry Letters, Vol. 14, Issue 11
  • DOI: 10.1246/cl.1985.1695

Electrochemical CO Reduction Builds Solvent Water into Oxygenate Products
journal, July 2018

  • Lum, Yanwei; Cheng, Tao; Goddard, William A.
  • Journal of the American Chemical Society, Vol. 140, Issue 30
  • DOI: 10.1021/jacs.8b03986

Existence of an Electrochemically Inert CO Population on Cu Electrodes in Alkaline pH
journal, July 2018


CO 2 Reduction on Cu at Low Overpotentials with Surface-Enhanced in Situ Spectroscopy
journal, July 2016

  • Heyes, Jeffrey; Dunwell, Marco; Xu, Bingjun
  • The Journal of Physical Chemistry C, Vol. 120, Issue 31
  • DOI: 10.1021/acs.jpcc.6b03065

New insights into the electrochemical reduction of carbon dioxide on metallic copper surfaces
journal, January 2012

  • Kuhl, Kendra P.; Cave, Etosha R.; Abram, David N.
  • Energy & Environmental Science, Vol. 5, Issue 5
  • DOI: 10.1039/c2ee21234j

Theoretical Insights into a CO Dimerization Mechanism in CO 2 Electroreduction
journal, May 2015

  • Montoya, Joseph H.; Shi, Chuan; Chan, Karen
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 11
  • DOI: 10.1021/acs.jpclett.5b00722

Spectroscopic Observation of a Hydrogenated CO Dimer Intermediate During CO Reduction on Cu(100) Electrodes
journal, February 2017

  • Pérez-Gallent, Elena; Figueiredo, Marta C.; Calle-Vallejo, Federico
  • Angewandte Chemie International Edition, Vol. 56, Issue 13
  • DOI: 10.1002/anie.201700580

Catalysts and Reaction Pathways for the Electrochemical Reduction of Carbon Dioxide
journal, September 2015

  • Kortlever, Ruud; Shen, Jing; Schouten, Klaas Jan P.
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 20
  • DOI: 10.1021/acs.jpclett.5b01559

Two-Phase Thermodynamic Model for Efficient and Accurate Absolute Entropy of Water from Molecular Dynamics Simulations
journal, June 2010

  • Lin, Shiang-Tai; Maiti, Prabal K.; Goddard, William A.
  • The Journal of Physical Chemistry B, Vol. 114, Issue 24
  • DOI: 10.1021/jp103120q

Probing the Active Surface Sites for CO Reduction on Oxide-Derived Copper Electrocatalysts
journal, July 2015

  • Verdaguer-Casadevall, Arnau; Li, Christina W.; Johansson, Tobias P.
  • Journal of the American Chemical Society, Vol. 137, Issue 31
  • DOI: 10.1021/jacs.5b06227

Spectroscopic Observation of Reversible Surface Reconstruction of Copper Electrodes under CO 2 Reduction
journal, May 2017

  • Gunathunge, Charuni M.; Li, Xiang; Li, Jingyi
  • The Journal of Physical Chemistry C, Vol. 121, Issue 22
  • DOI: 10.1021/acs.jpcc.7b03910

    Works referencing / citing this record:

    Designing materials for electrochemical carbon dioxide recycling
    journal, July 2019