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Title: Surface (Electro)chemistry of CO 2 on Pt Surface: An in Situ Surface-Enhanced Infrared Absorption Spectroscopy Study

Abstract

Understanding the surface (electro)chemistry of CO 2 and CO on Pt is needed to design active, selective catalysts for CO-tolerant fuel cell reactions and CO 2 reduction. In this work, the surface reactivity of Pt in a CO 2-saturated alkaline electrolyte was revealed by combining in situ surface-enhanced infrared absorption spectroscopy (SEIRAS) with density functional theory (DFT) calculations. Here, we show that during potential cycling in 1 M KHCO 3 electrolyte, CO adsorbates (CO ad), more specifically, CO ad surrounded by OH adsorbates (OH ad), with linear or bridged configuration, were produced through the reductive adsorption of HCO 3 catalyzed by H adsorbates on Pt. The CO ad coadsorbed with OH ad was oxidized to COOH ad at potentials as low as ~0.3 V RHE, which was further oxidized to CO 2 at 0.9 V RHE and higher. Further analysis suggests that the proximity between CO ad and OH ad is key to trigger the conversion reaction from CO ad to CO 2 through forming COOH ad intermediate at room temperature. The details about how Pt surface adsorbates change as a function of voltage in CO 2-saturated alkaline electrolytes can provide strategies to design CO-tolerant catalysts for fuel cellmore » applications and active and selective catalysts for the CO 2 reduction reaction.« less

Authors:
ORCiD logo [1];  [2];  [2];  [2];  [3];  [3];  [3]; ORCiD logo [2]
  1. Massachusetts Inst. of Technology, Cambridge, MA (United States); Kyoto Univ. (Japan); Yamaguchi Univ. (Japan)
  2. Massachusetts Inst. of Technology, Cambridge, MA (United States)
  3. Kyoto Univ. (Japan)
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1543648
Grant/Contract Number:  
[AC02-05CH11231]
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
[ Journal Volume: 122; Journal Issue: 23]; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; chemistry; science & technology - other topics; materials science

Citation Formats

Katayama, Yu, Giordano, Livia, Rao, Reshma R., Hwang, Jonathan, Muroyama, Hiroki, Matsui, Toshiaki, Eguchi, Koichi, and Shao-Horn, Yang. Surface (Electro)chemistry of CO2 on Pt Surface: An in Situ Surface-Enhanced Infrared Absorption Spectroscopy Study. United States: N. p., 2018. Web. doi:10.1021/acs.jpcc.8b03556.
Katayama, Yu, Giordano, Livia, Rao, Reshma R., Hwang, Jonathan, Muroyama, Hiroki, Matsui, Toshiaki, Eguchi, Koichi, & Shao-Horn, Yang. Surface (Electro)chemistry of CO2 on Pt Surface: An in Situ Surface-Enhanced Infrared Absorption Spectroscopy Study. United States. doi:10.1021/acs.jpcc.8b03556.
Katayama, Yu, Giordano, Livia, Rao, Reshma R., Hwang, Jonathan, Muroyama, Hiroki, Matsui, Toshiaki, Eguchi, Koichi, and Shao-Horn, Yang. Wed . "Surface (Electro)chemistry of CO2 on Pt Surface: An in Situ Surface-Enhanced Infrared Absorption Spectroscopy Study". United States. doi:10.1021/acs.jpcc.8b03556. https://www.osti.gov/servlets/purl/1543648.
@article{osti_1543648,
title = {Surface (Electro)chemistry of CO2 on Pt Surface: An in Situ Surface-Enhanced Infrared Absorption Spectroscopy Study},
author = {Katayama, Yu and Giordano, Livia and Rao, Reshma R. and Hwang, Jonathan and Muroyama, Hiroki and Matsui, Toshiaki and Eguchi, Koichi and Shao-Horn, Yang},
abstractNote = {Understanding the surface (electro)chemistry of CO2 and CO on Pt is needed to design active, selective catalysts for CO-tolerant fuel cell reactions and CO2 reduction. In this work, the surface reactivity of Pt in a CO2-saturated alkaline electrolyte was revealed by combining in situ surface-enhanced infrared absorption spectroscopy (SEIRAS) with density functional theory (DFT) calculations. Here, we show that during potential cycling in 1 M KHCO3 electrolyte, CO adsorbates (COad), more specifically, COad surrounded by OH adsorbates (OHad), with linear or bridged configuration, were produced through the reductive adsorption of HCO3– catalyzed by H adsorbates on Pt. The COad coadsorbed with OHad was oxidized to COOHad at potentials as low as ~0.3 VRHE, which was further oxidized to CO2 at 0.9 VRHE and higher. Further analysis suggests that the proximity between COad and OHad is key to trigger the conversion reaction from COad to CO2 through forming COOHad intermediate at room temperature. The details about how Pt surface adsorbates change as a function of voltage in CO2-saturated alkaline electrolytes can provide strategies to design CO-tolerant catalysts for fuel cell applications and active and selective catalysts for the CO2 reduction reaction.},
doi = {10.1021/acs.jpcc.8b03556},
journal = {Journal of Physical Chemistry. C},
number = [23],
volume = [122],
place = {United States},
year = {2018},
month = {5}
}

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