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Initial steps in forming the electrode electrolyte interface: H_2O adsorption and complex formation on the Ag(111) surface from combining Quantum Mechanics calculations and X-ray Photoelectron Spectroscopy

Qian, Jin and Ye, Yifan and Yang, Hao and Yano, Junko and Crumlin, Ethan J. and Goddard, William A., III (2019) Initial steps in forming the electrode electrolyte interface: H_2O adsorption and complex formation on the Ag(111) surface from combining Quantum Mechanics calculations and X-ray Photoelectron Spectroscopy. Journal of the American Chemical Society, 141 (17). pp. 6946-6954. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20190404-092810356

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Abstract

The interaction of water with metal surfaces is at the heart of electrocatalysis. But there remain enormous uncertainties about the atomistic interactions at the electrode–electrolyte interface (EEI). As the first step toward an understanding of the EEI, we report here the details of the initial steps of H_2O adsorption and complex formation on a Ag(111) surface, based on coupling quantum mechanics (QM) and ambient-pressure X-ray photoelectron spectroscopy (APXPS) experiments. We find a close and direct comparison between simulation and experiment, validated under various isotherm and isobar conditions. We identify five observable oxygen-containing species whose concentrations depend sensitively on temperature and pressure: chemisorbed O* and OH*, H_2O* stabilized by hydrogen bond interactions with OH* or O*, and multilayer H_2O*. We identify the species experimentally by their O 1s core-level shift that we calculate with QM along with the structures and free energies as a function of temperature and pressure. This leads to a chemical reaction network (CRN) that we use to predict the time evolution of their concentrations over a wide range of temperature (298–798 K) and pressure conditions (10^(–6)–1 Torr), which agree well with the populations determined from APXPS. This multistep simulation CRN protocol should be useful for other heterogeneous catalytic systems.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/jacs.8b13672DOIArticle
https://pubs.acs.org/doi/suppl/10.1021/jacs.8b13672PublisherSupporting Information
ORCID:
AuthorORCID
Qian, Jin0000-0002-0162-0477
Yang, Hao0000-0002-8241-6231
Yano, Junko0000-0001-6308-9071
Crumlin, Ethan J.0000-0003-3132-190X
Goddard, William A., III0000-0003-0097-5716
Alternate Title:Initial steps in forming the electrode electrolyte interface: H2O adsorption and complex formation on the Ag(111) surface from combining Quantum Mechanics calculations and X-ray Photoelectron Spectroscopy
Additional Information:© 2019 American Chemical Society. Received: December 21, 2018; Published: April 4, 2019. We thank Yufeng Huang and Samuel Clamons for helpful discussions. This project was supported by the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the U.S. Department of Energy under Award No. DE-SC0004993. W.A.G. was supported by the Computational Materials Sciences Program funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under Award No. DE-SC00014607. The calculations were carried out on the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by National Science Foundation Grant No. ACI-1548562. This research used resources of the Advanced Light Source, which is a DOE Office of Science User Facility under contract no. DE-AC02-05CH11231. In addition, Y.Y. and E.J.C. were partially supported by an Early Career Award in the Condensed Phase and Interfacial Molecular Science Program, in the Chemical Sciences Geosciences and Biosciences Division of the Office of Basic Energy Sciences of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. Author Contributions: J.Q. and Y.Y. contributed equally. The authors declare no competing financial interest.
Group:JCAP
Funders:
Funding AgencyGrant Number
Joint Center for Artificial Photosynthesis (JCAP)UNSPECIFIED
Department of Energy (DOE)DE-SC0004993
Department of Energy (DOE)DE-SC00014607
NSFACI-1548562
Department of Energy (DOE)DE-AC02-05CH11231
Subject Keywords:Density Functional Theory (DFT); PBE-D3; ambient pressure XPS; Chemical Reaction Network (CRN)
Other Numbering System:
Other Numbering System NameOther Numbering System ID
WAG1330
Issue or Number:17
Record Number:CaltechAUTHORS:20190404-092810356
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20190404-092810356
Official Citation:Initial Steps in Forming the Electrode–Electrolyte Interface: H2O Adsorption and Complex Formation on the Ag(111) Surface from Combining Quantum Mechanics Calculations and Ambient Pressure X-ray Photoelectron Spectroscopy. Jin Qian, Yifan Ye, Hao Yang, Junko Yano, Ethan J. Crumlin, and William A. Goddard III. Journal of the American Chemical Society 2019 141 (17), 6946-6954. DOI: 10.1021/jacs.8b13672
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:94450
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:04 Apr 2019 17:15
Last Modified:09 Mar 2020 13:19

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