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Title: Facet-dependent active sites of a single Cu 2O particle photocatalyst for CO 2 reduction to methanol

Abstract

Atomic level understanding of the active sites and transformation mechanisms under realistic working conditions are pre-requisites for rational design of high performance photocatalysts. By using correlated scanning fluorescence x-ray microscopy and environmental transmission electron microscopy at atmospheric pressure, in operando, we directly observed that the (110) facet of a single Cu 2O photocatalyst particle is photocatalytically active for CO 2 reduction to methanol while the (100) facet is inert. The oxidation state of the active sites changed from Cu(I) towards Cu(II) due to CO 2 and H 2O coadsorption and changed back to Cu+ after CO 2 conversion under visible light illumination. The Cu 2O photocatalyst oxidized water as it reduced CO 2. At the same time, the crystal lattice expanded due to CO 2 adsorption then reverted after CO 2 conversion. The internal quantum yield for unassisted wireless photocatalytic reduction of CO 2 to methanol using Cu 2O crystals is ~ 72% with 10% solar to fuel efficiency.

Authors:
 [1];  [2]; ORCiD logo [3];  [4];  [5];  [6];  [7];  [7];  [2];  [7];  [6];  [6]; ORCiD logo [2]; ORCiD logo [2]
  1. Argonne National Lab. (ANL), Argonne, IL (United States); Univ. of Waterloo, ON (Canada)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
  4. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division; Univ. of California, Northridge, CA (United States). Dept. of Physics and Astronomy
  5. Hong Kong Univ. (Hong Kong). Dept. of Physics
  6. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
  7. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1600936
Grant/Contract Number:  
[AC02-06CH11357]
Resource Type:
Accepted Manuscript
Journal Name:
Nature Energy
Additional Journal Information:
[ Journal Volume: 4; Journal Issue: 11]; Journal ID: ISSN 2058-7546
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; carbon dioxide reduction; methanol; active sites; cuprous oxide; X-ray nanoprobe; electron microscopy; EPR

Citation Formats

Wu, Yimin A., McNulty, Ian, Liu, Cong, Lau, Kah Chun, Liu, Qi, Paulikas, Arvydas P., Sun, Cheng-Jun, Cai, Zhonghou, Guest, Jeffrey R., Ren, Yang, Stamenkovic, Vojislav, Curtiss, Larry A., Liu, Yuzi, and Rajh, Tijana. Facet-dependent active sites of a single Cu2O particle photocatalyst for CO2 reduction to methanol. United States: N. p., 2019. Web. doi:10.1038/s41560-019-0490-3.
Wu, Yimin A., McNulty, Ian, Liu, Cong, Lau, Kah Chun, Liu, Qi, Paulikas, Arvydas P., Sun, Cheng-Jun, Cai, Zhonghou, Guest, Jeffrey R., Ren, Yang, Stamenkovic, Vojislav, Curtiss, Larry A., Liu, Yuzi, & Rajh, Tijana. Facet-dependent active sites of a single Cu2O particle photocatalyst for CO2 reduction to methanol. United States. doi:10.1038/s41560-019-0490-3.
Wu, Yimin A., McNulty, Ian, Liu, Cong, Lau, Kah Chun, Liu, Qi, Paulikas, Arvydas P., Sun, Cheng-Jun, Cai, Zhonghou, Guest, Jeffrey R., Ren, Yang, Stamenkovic, Vojislav, Curtiss, Larry A., Liu, Yuzi, and Rajh, Tijana. Fri . "Facet-dependent active sites of a single Cu2O particle photocatalyst for CO2 reduction to methanol". United States. doi:10.1038/s41560-019-0490-3.
@article{osti_1600936,
title = {Facet-dependent active sites of a single Cu2O particle photocatalyst for CO2 reduction to methanol},
author = {Wu, Yimin A. and McNulty, Ian and Liu, Cong and Lau, Kah Chun and Liu, Qi and Paulikas, Arvydas P. and Sun, Cheng-Jun and Cai, Zhonghou and Guest, Jeffrey R. and Ren, Yang and Stamenkovic, Vojislav and Curtiss, Larry A. and Liu, Yuzi and Rajh, Tijana},
abstractNote = {Atomic level understanding of the active sites and transformation mechanisms under realistic working conditions are pre-requisites for rational design of high performance photocatalysts. By using correlated scanning fluorescence x-ray microscopy and environmental transmission electron microscopy at atmospheric pressure, in operando, we directly observed that the (110) facet of a single Cu2O photocatalyst particle is photocatalytically active for CO2 reduction to methanol while the (100) facet is inert. The oxidation state of the active sites changed from Cu(I) towards Cu(II) due to CO2 and H2O coadsorption and changed back to Cu+ after CO2 conversion under visible light illumination. The Cu2O photocatalyst oxidized water as it reduced CO2. At the same time, the crystal lattice expanded due to CO2 adsorption then reverted after CO2 conversion. The internal quantum yield for unassisted wireless photocatalytic reduction of CO2 to methanol using Cu2O crystals is ~ 72% with 10% solar to fuel efficiency.},
doi = {10.1038/s41560-019-0490-3},
journal = {Nature Energy},
number = [11],
volume = [4],
place = {United States},
year = {2019},
month = {11}
}

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