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

This content will become publicly available on November 22, 2020

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]
+ Show Author Affiliations
  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.
Copy to clipboard
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.
Copy to clipboard
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.
Copy to clipboard
@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}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
This content will become publicly available on November 22, 2020
Publisher's Version of Record
DOI:  10.1038/s41560-019-0490-3
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

The importance of surface morphology in controlling the selectivity of polycrystalline copper for CO2 electroreduction
journal, January 2012

  • Tang, Wei; Peterson, Andrew A.; Varela, Ana Sofia
  • Phys. Chem. Chem. Phys., Vol. 14, Issue 1
  • DOI: 10.1039/C1CP22700A

CO2 Reduction at Low Overpotential on Cu Electrodes Resulting from the Reduction of Thick Cu2O Films
journal, April 2012

  • Li, Christina W.; Kanan, Matthew W.
  • Journal of the American Chemical Society, Vol. 134, Issue 17, p. 7231-7234
  • DOI: 10.1021/ja3010978

Highly active oxide photocathode for photoelectrochemical water reduction
journal, May 2011

  • Paracchino, Adriana; Laporte, Vincent; Sivula, Kevin
  • Nature Materials, Vol. 10, Issue 6
  • DOI: 10.1038/nmat3017

New Developments in Transmission Electron Microscopy for Nanotechnology
journal, September 2003

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Cu 2 O/Reduced Graphene Oxide Composites for the Photocatalytic Conversion of CO 2
journal, February 2014

Glossary of terms used in photocatalysis and radiation catalysis (IUPAC Recommendations 2011)
journal, March 2011

  • Braslavsky, Silvia E.; Braun, André M.; Cassano, Alberto E.
  • Pure and Applied Chemistry, Vol. 83, Issue 4
  • DOI: 10.1351/PAC-REC-09-09-36

Challenges and Prospects in Solar Water Splitting and CO 2 Reduction with Inorganic and Hybrid Nanostructures
journal, March 2018

  • Stolarczyk, Jacek K.; Bhattacharyya, Santanu; Polavarapu, Lakshminarayana
  • ACS Catalysis, Vol. 8, Issue 4
  • DOI: 10.1021/acscatal.8b00791

Nanostructured transition metal dichalcogenide electrocatalysts for CO 2 reduction in ionic liquid
journal, July 2016

Conversion of CO 2 from Air into Methanol Using a Polyamine and a Homogeneous Ruthenium Catalyst
journal, January 2016

  • Kothandaraman, Jotheeswari; Goeppert, Alain; Czaun, Miklos
  • Journal of the American Chemical Society, Vol. 138, Issue 3
  • DOI: 10.1021/jacs.5b12354

Projector augmented-wave method
journal, December 1994

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

Conduction-electron g factors in the noble metals
journal, May 1989

  • Grechnev, G. E.; Savchenko, N. V.; Svechkarev, I. V.
  • Physical Review B, Vol. 39, Issue 14
  • DOI: 10.1103/PhysRevB.39.9865

Nanowire–Bacteria Hybrids for Unassisted Solar Carbon Dioxide Fixation to Value-Added Chemicals
journal, April 2015

Theory-driven design of high-valence metal sites for water oxidation confirmed using in situ soft X-ray absorption
journal, November 2017

  • Zheng, Xueli; Zhang, Bo; De Luna, Phil
  • Nature Chemistry, Vol. 10, Issue 2
  • DOI: 10.1038/nchem.2886

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999

Particle Size Effects in the Catalytic Electroreduction of CO 2 on Cu Nanoparticles
journal, May 2014

  • Reske, Rulle; Mistry, Hemma; Behafarid, Farzad
  • Journal of the American Chemical Society, Vol. 136, Issue 19
  • DOI: 10.1021/ja500328k

Electron beam damage in oxides: a review
journal, December 2015

Morphology-Dependent Interactions of ZnO with Cu Nanoparticles at the Materials’ Interface in Selective Hydrogenation of CO2 to CH3OH
journal, January 2011

  • Liao, Fenglin; Huang, Yaqun; Ge, Junwei
  • Angewandte Chemie International Edition, Vol. 50, Issue 9
  • DOI: 10.1002/anie.201007108

A hard X-ray nanoprobe beamline for nanoscale microscopy
journal, September 2012

  • Winarski, Robert P.; Holt, Martin V.; Rose, Volker
  • Journal of Synchrotron Radiation, Vol. 19, Issue 6
  • DOI: 10.1107/S0909049512036783

Visualizing Gas Molecules Interacting with Supported Nanoparticulate Catalysts at Reaction Conditions
journal, January 2012

Differential stress induced by thiol adsorption on facetted nanocrystals
journal, September 2011

  • Watari, Moyu; McKendry, Rachel A.; Vögtli, Manuel
  • Nature Materials, Vol. 10, Issue 11
  • DOI: 10.1038/nmat3124

Controlled synthesis of concave Cu 2 O microcrystals enclosed by {hhl} high-index facets and enhanced catalytic activity
journal, January 2013

  • Wang, Xue; Liu, Chang; Zheng, Binjie
  • J. Mater. Chem. A, Vol. 1, Issue 2
  • DOI: 10.1039/C2TA00241H

Chemical actinometry (IUPAC Technical Report)
journal, January 2004

  • Kuhn, H. J.; Braslavsky, S. E.; Schmidt, R.
  • Pure and Applied Chemistry, Vol. 76, Issue 12
  • DOI: 10.1351/pac200476122105

Copper in Photocatalysis
journal, July 2014

Electrodeposition of Cu[sub 2]O: An Excellent Method for Obtaining Films of Controlled Morphology and Good Performance in Li-Ion Batteries
journal, January 2005

  • Morales, J.; Sánchez, L.; Bijani, S.
  • Electrochemical and Solid-State Letters, Vol. 8, Issue 3
  • DOI: 10.1149/1.1854126

A density functional theory study of the adsorption behaviour of CO 2 on Cu 2 O surfaces
journal, July 2016

  • Mishra, Abhishek Kumar; Roldan, Alberto; de Leeuw, Nora H.
  • The Journal of Chemical Physics, Vol. 145, Issue 4
  • DOI: 10.1063/1.4958804

Partially oxidized atomic cobalt layers for carbon dioxide electroreduction to liquid fuel
journal, January 2016

A Simple Two-Step Electrodeposition of Cu 2 O/ZnO Nanopillar Solar Cells
journal, March 2010

  • Cui, Jingbiao; Gibson, Ursula J.
  • The Journal of Physical Chemistry C, Vol. 114, Issue 14
  • DOI: 10.1021/jp1004314

Artificial Photosynthesis on TiO 2 -Passivated InP Nanopillars
journal, August 2015

Metal-free efficient photocatalyst for stable visible water splitting via a two-electron pathway
journal, February 2015

Activating lattice oxygen redox reactions in metal oxides to catalyse oxygen evolution
journal, January 2017

  • Grimaud, Alexis; Diaz-Morales, Oscar; Han, Binghong
  • Nature Chemistry, Vol. 9, Issue 5
  • DOI: 10.1038/nchem.2695

High Selectivity for Ethylene from Carbon Dioxide Reduction over Copper Nanocube Electrocatalysts
journal, February 2015

  • Roberts, F. Sloan; Kuhl, Kendra P.; Nilsson, Anders
  • Angewandte Chemie International Edition, Vol. 54, Issue 17
  • DOI: 10.1002/anie.201412214

Thermodynamic and achievable efficiencies for solar-driven electrochemical reduction of carbon dioxide to transportation fuels
journal, October 2015

  • Singh, Meenesh R.; Clark, Ezra L.; Bell, Alexis T.
  • Proceedings of the National Academy of Sciences, Vol. 112, Issue 45
  • DOI: 10.1073/pnas.1519212112

Electrocatalytic CO2 Conversion to Oxalate by a Copper Complex
journal, January 2010

Controllable proton and CO2 photoreduction over Cu2O with various morphologies
journal, September 2013

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996

First-Principles Predictions of the Structure, Stability, and Photocatalytic Potential of Cu 2 O Surfaces
journal, September 2013

  • Bendavid, Leah Isseroff; Carter, Emily A.
  • The Journal of Physical Chemistry B, Vol. 117, Issue 49
  • DOI: 10.1021/jp406454c

Carbon Dioxide Fixation into Chemicals (Methyl Formate) at High Yields by Surface Coupling over a Pd/Cu/ZnO Nanocatalyst
journal, May 2007

  • Yu, K. M. Kerry; Yeung, Connie M. Y.; Tsang, Shik Chi
  • Journal of the American Chemical Society, Vol. 129, Issue 20
  • DOI: 10.1021/ja0706302

Highly active copper-ceria and copper-ceria-titania catalysts for methanol synthesis from CO2
journal, July 2014

A generalized method for high throughput in-situ experiment data analysis: An example of battery materials exploration
journal, April 2015

Pd@TiO 2 /carbon nanohorn electrocatalysts: reversible CO 2 hydrogenation to formic acid
journal, January 2018

  • Melchionna, M.; Bracamonte, M. V.; Giuliani, A.
  • Energy & Environmental Science, Vol. 11, Issue 6
  • DOI: 10.1039/C7EE03361C

Visualizing Redox Dynamics of a Single Ag/AgCl Heterogeneous Nanocatalyst at Atomic Resolution
journal, February 2016

High-Selectivity Electrochemical Conversion of CO 2 to Ethanol using a Copper Nanoparticle/N-Doped Graphene Electrode
journal, September 2016

Carbon Dioxide Conversion to Methanol over Size-Selected Cu 4 Clusters at Low Pressures
journal, July 2015

  • Liu, Cong; Yang, Bing; Tyo, Eric
  • Journal of the American Chemical Society, Vol. 137, Issue 27
  • DOI: 10.1021/jacs.5b03668

Surface Modification of Small Particle TiO 2 Colloids with Cysteine for Enhanced Photochemical Reduction:  An EPR Study †
journal, January 1996

  • Rajh, Tijana; Ostafin, Agnes E.; Micic, Olga I.
  • The Journal of Physical Chemistry, Vol. 100, Issue 11
  • DOI: 10.1021/jp952002p

Co-ordination of copper(II) ions doped in pentacyanonitrosylferrate(2–) and tetrathiocyanatometallate(II) salts: an electron spin resonance study
journal, January 1975

  • Symons, Martyn C. R.; West, Douglas X.; Wilkinson, James G.
  • Journal of the Chemical Society, Dalton Transactions, Issue 16-17
  • DOI: 10.1039/dt9750001696

Tailoring Copper Nanocrystals towards C 2 Products in Electrochemical CO 2 Reduction
journal, April 2016

  • Loiudice, Anna; Lobaccaro, Peter; Kamali, Esmail A.
  • Angewandte Chemie International Edition, Vol. 55, Issue 19
  • DOI: 10.1002/anie.201601582

Recent advances in hybrid photocatalysts for solar fuel production
journal, January 2012

  • Tran, Phong D.; Wong, Lydia H.; Barber, James
  • Energy & Environmental Science, Vol. 5, Issue 3
  • DOI: 10.1039/c2ee02849b

Photocatalytic CO2 reduction with high turnover frequency and selectivity of formic acid formation using Ru(II) multinuclear complexes
journal, August 2012

  • Tamaki, Y.; Morimoto, T.; Koike, K.
  • Proceedings of the National Academy of Sciences, Vol. 109, Issue 39
  • DOI: 10.1073/pnas.1118336109

Photocatalysis for Hydrogen Production and CO 2 Reduction: The Case of Copper‐Catalysts
journal, September 2018

  • Christoforidis, Konstantinos C.; Fornasiero, Paolo
  • ChemCatChem, Vol. 11, Issue 1
  • DOI: 10.1002/cctc.201801198

Artificial photosynthesis for solar fuels
journal, January 2012

Asymmetric copper-catalyzed C-N cross-couplings induced by visible light
journal, February 2016

Shape effects of cuprous oxide particles on stability in water and photocatalytic water splitting
journal, January 2015

  • Kwon, Yongwoo; Soon, Aloysius; Han, Haksoo
  • Journal of Materials Chemistry A, Vol. 3, Issue 1
  • DOI: 10.1039/C4TA04863F

Determination of the quantum yield of the ferrioxalate actinometer with electrically calibrated radiometers
journal, September 1981

  • Demas, J. N.; Bowman, W. D.; Zalewski, E. F.
  • The Journal of Physical Chemistry, Vol. 85, Issue 19
  • DOI: 10.1021/j150619a015

First turnover analysis of water-oxidation catalyzed by Co-oxide nanoparticles
journal, January 2015

  • Koroidov, Sergey; Anderlund, Magnus F.; Styring, Stenbjörn
  • Energy & Environmental Science, Vol. 8, Issue 8
  • DOI: 10.1039/C5EE00700C

Artificial Z-Scheme Constructed with a Supramolecular Metal Complex and Semiconductor for the Photocatalytic Reduction of CO 2
journal, March 2013

  • Sekizawa, Keita; Maeda, Kazuhiko; Domen, Kazunari
  • Journal of the American Chemical Society, Vol. 135, Issue 12
  • DOI: 10.1021/ja311541a

Water splitting–biosynthetic system with CO 2 reduction efficiencies exceeding photosynthesis
journal, June 2016

Aqueous CO 2 Reduction at Very Low Overpotential on Oxide-Derived Au Nanoparticles
journal, November 2012

  • Chen, Yihong; Li, Christina W.; Kanan, Matthew W.
  • Journal of the American Chemical Society, Vol. 134, Issue 49
  • DOI: 10.1021/ja309317u

High-Flux Solar-Driven Thermochemical Dissociation of CO2 and H2O Using Nonstoichiometric Ceria
journal, December 2010

Computational studies of electrochemical CO 2 reduction on subnanometer transition metal clusters
journal, January 2014

  • Liu, Cong; He, Haiying; Zapol, Peter
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 48
  • DOI: 10.1039/C4CP02690J

Two-dimensional detector software: From real detector to idealised image or two-theta scan
journal, January 1996

  • Hammersley, A. P.; Svensson, S. O.; Hanfland, M.
  • High Pressure Research, Vol. 14, Issue 4-6, p. 235-248
  • DOI: 10.1080/08957959608201408
    [ × clear filter / sort ]

    Similar Records in DOE PAGES and OSTI.GOV collections: