DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Formation of Copper Catalysts for CO2 Reduction with High Ethylene/Methane Product Ratio Investigated with In Situ X-ray Absorption Spectroscopy

Abstract

Nanostructured copper cathodes are among the most efficient and selective catalysts to date for making multicarbon products from the electrochemical carbon dioxide reduction reaction (CO2RR). We report an in situ X-ray absorption spectroscopy investigation of the formation of a copper nanocube CO2RR catalyst with high activity that highly favors ethylene over methane production. The results show that the precursor for the copper nanocube formation is copper(I)-oxide, not copper(I)-chloride as previously assumed. A second route to an electrochemically similar material via a copper(II)–carbonate/hydroxide is also reported. In conclusion, this study highlights the importance of using oxidized copper precursors for constructing selective CO2 reduction catalysts and shows the precursor oxidation state does not affect the electrocatalyst selectivity toward ethylene formation.

Authors:
 [1];  [1];  [1];  [2]
  1. SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., CA (United States). SUNCAT Center for Interface Science and Catalysis, Dept. of Chemical Engineering
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., CA (United States). SUNCAT Center for Interface Science and Catalysis, Dept. of Chemical Engineering; Stockholm Univ. (Sweden). AlbaNova University Center, Dept. of Physics
Publication Date:
Research Org.:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Org.:
USDOE; US Air Force Office of Scientific Research (AFOSR)
OSTI Identifier:
1256341
Grant/Contract Number:  
FA9550-10-1-0572; AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 7; Journal Issue: 8; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Eilert, André, Roberts, F. Sloan, Friebel, Daniel, and Nilsson, Anders. Formation of Copper Catalysts for CO2 Reduction with High Ethylene/Methane Product Ratio Investigated with In Situ X-ray Absorption Spectroscopy. United States: N. p., 2016. Web. doi:10.1021/acs.jpclett.6b00367.
Eilert, André, Roberts, F. Sloan, Friebel, Daniel, & Nilsson, Anders. Formation of Copper Catalysts for CO2 Reduction with High Ethylene/Methane Product Ratio Investigated with In Situ X-ray Absorption Spectroscopy. United States. https://doi.org/10.1021/acs.jpclett.6b00367
Eilert, André, Roberts, F. Sloan, Friebel, Daniel, and Nilsson, Anders. Mon . "Formation of Copper Catalysts for CO2 Reduction with High Ethylene/Methane Product Ratio Investigated with In Situ X-ray Absorption Spectroscopy". United States. https://doi.org/10.1021/acs.jpclett.6b00367. https://www.osti.gov/servlets/purl/1256341.
@article{osti_1256341,
title = {Formation of Copper Catalysts for CO2 Reduction with High Ethylene/Methane Product Ratio Investigated with In Situ X-ray Absorption Spectroscopy},
author = {Eilert, André and Roberts, F. Sloan and Friebel, Daniel and Nilsson, Anders},
abstractNote = {Nanostructured copper cathodes are among the most efficient and selective catalysts to date for making multicarbon products from the electrochemical carbon dioxide reduction reaction (CO2RR). We report an in situ X-ray absorption spectroscopy investigation of the formation of a copper nanocube CO2RR catalyst with high activity that highly favors ethylene over methane production. The results show that the precursor for the copper nanocube formation is copper(I)-oxide, not copper(I)-chloride as previously assumed. A second route to an electrochemically similar material via a copper(II)–carbonate/hydroxide is also reported. In conclusion, this study highlights the importance of using oxidized copper precursors for constructing selective CO2 reduction catalysts and shows the precursor oxidation state does not affect the electrocatalyst selectivity toward ethylene formation.},
doi = {10.1021/acs.jpclett.6b00367},
journal = {Journal of Physical Chemistry Letters},
number = 8,
volume = 7,
place = {United States},
year = {Mon Apr 04 00:00:00 EDT 2016},
month = {Mon Apr 04 00:00:00 EDT 2016}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 117 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Powering the planet: Chemical challenges in solar energy utilization
journal, October 2006

  • Lewis, N. S.; Nocera, D. G.
  • Proceedings of the National Academy of Sciences, Vol. 103, Issue 43, p. 15729-15735
  • DOI: 10.1073/pnas.0603395103

Electrochemical reduction of CO2 to hydrocarbons to store renewable electrical energy and upgrade biogas
journal, April 2007


Electrochemical CO2 Reduction on Metal Electrodes
book, January 2008


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


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

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

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

Selective Electrochemical Reduction of Carbon Dioxide to Ethylene and Ethanol on Copper(I) Oxide Catalysts
journal, March 2015

  • Ren, Dan; Deng, Yilin; Handoko, Albertus Denny
  • ACS Catalysis, Vol. 5, Issue 5
  • DOI: 10.1021/cs502128q

Insights into an autonomously formed oxygen-evacuated Cu 2 O electrode for the selective production of C 2 H 4 from CO 2
journal, January 2015

  • Kim, Dahee; Lee, Seunghwa; Ocon, Joey D.
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 2
  • DOI: 10.1039/C4CP03172E

Highly Dense Cu Nanowires for Low-Overpotential CO2 Reduction
journal, September 2015


Electrocatalytic Production of C3-C4 Compounds by Conversion of CO 2 on a Chloride-Induced Bi-Phasic Cu 2 O-Cu Catalyst
journal, October 2015


Selective electrochemical reduction of CO 2 to CO on CuO-derived Cu nanowires
journal, January 2015

  • Ma, Ming; Djanashvili, Kristina; Smith, Wilson A.
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 32
  • DOI: 10.1039/C5CP03559G

Morphology-controlled CuO nanoparticles for electroreduction of CO 2 to ethanol
journal, January 2014

  • Chi, Dinghui; Yang, Hengpan; Du, Yanfang
  • RSC Adv., Vol. 4, Issue 70
  • DOI: 10.1039/C4RA05415F

Electrochemical CO 2 reduction on Cu 2 O-derived copper nanoparticles: controlling the catalytic selectivity of hydrocarbons
journal, January 2014

  • Kas, Recep; Kortlever, Ruud; Milbrat, Alexander
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 24
  • DOI: 10.1039/c4cp01520g

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

Electroreduction of Carbon Monoxide Over a Copper Nanocube Catalyst: Surface Structure and pH Dependence on Selectivity
journal, February 2016

  • Roberts, F. Sloan; Kuhl, Kendra P.; Nilsson, Anders
  • ChemCatChem, Vol. 8, Issue 6
  • DOI: 10.1002/cctc.201501189

Stable and selective electrochemical reduction of carbon dioxide to ethylene on copper mesocrystals
journal, January 2015

  • Chen, Chung Shou; Handoko, Albertus D.; Wan, Jane Hui
  • Catalysis Science & Technology, Vol. 5, Issue 1
  • DOI: 10.1039/C4CY00906A

Copper in sea-water, potential-pH diagrams
journal, January 1973


Electrochemical corrosion of unalloyed copper in chloride media––a critical review
journal, January 2004


A web-based library of XAFS data on model compounds
journal, May 1999

  • Newville, M.; Carroll, S. A.; O'Day, P. A.
  • Journal of Synchrotron Radiation, Vol. 6, Issue 3
  • DOI: 10.1107/S0909049599000795

Structure, Redox Chemistry, and Interfacial Alloy Formation in Monolayer and Multilayer Cu/Au(111) Model Catalysts for CO 2 Electroreduction
journal, April 2014

  • Friebel, Daniel; Mbuga, Felix; Rajasekaran, Srivats
  • The Journal of Physical Chemistry C, Vol. 118, Issue 15
  • DOI: 10.1021/jp412000j

Using XANES to obtain mechanistic information for the hydrolysis of CuCl2 and the decomposition of Cu2OCl2 in the thermochemical Cu–Cl cycle for H2 production
journal, November 2014

  • Ferrandon, M.; Daggupati, V.; Wang, Z.
  • Journal of Thermal Analysis and Calorimetry, Vol. 119, Issue 2
  • DOI: 10.1007/s10973-014-4240-2

X-ray absorption edge determination of the oxidation state and coordination number of copper. Application to the type 3 site in Rhus vernicifera laccase and its reaction with oxygen
journal, October 1987

  • Kau, Lung Shan; Spira-Solomon, Darlene J.; Penner-Hahn, James E.
  • Journal of the American Chemical Society, Vol. 109, Issue 21
  • DOI: 10.1021/ja00255a032

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

Grain-Boundary-Dependent CO 2 Electroreduction Activity
journal, April 2015

  • Feng, Xiaofeng; Jiang, Kaili; Fan, Shoushan
  • Journal of the American Chemical Society, Vol. 137, Issue 14
  • DOI: 10.1021/ja5130513

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

Calculation for the cathode surface concentrations in the electrochemical reduction of CO2 in KHCO3 solutions
journal, October 2005

  • Gupta, N.; Gattrell, M.; MacDougall, B.
  • Journal of Applied Electrochemistry, Vol. 36, Issue 2
  • DOI: 10.1007/s10800-005-9058-y

Selective electrochemical conversion of CO2 to C2 hydrocarbons
journal, January 2010


Works referencing / citing this record:

Effect of Annealing Treatment on Electrocatalytic Properties of Copper Electrodes toward Enhanced CO 2 Reduction
journal, August 2018


Advances and challenges in understanding the electrocatalytic conversion of carbon dioxide to fuels
journal, September 2019

  • Birdja, Yuvraj Y.; Pérez-Gallent, Elena; Figueiredo, Marta C.
  • Nature Energy, Vol. 4, Issue 9
  • DOI: 10.1038/s41560-019-0450-y

New aspects of C2 selectivity in electrochemical CO 2 reduction over oxide-derived copper
journal, January 2020

  • Shah, Aamir Hassan; Wang, Yanjie; Hussain, Sajjad
  • Physical Chemistry Chemical Physics, Vol. 22, Issue 4
  • DOI: 10.1039/c9cp06009j

Selective and Low Overpotential Electrochemical CO2 Reduction to Formate on CuS Decorated CuO Heterostructure
journal, January 2019


Electrochemical processes on solid shaped nanoparticles with defined facets
journal, January 2018

  • Strasser, Peter; Gliech, Manuel; Kuehl, Stefanie
  • Chemical Society Reviews, Vol. 47, Issue 3
  • DOI: 10.1039/c7cs00759k

Understanding three-dimensionally interconnected porous oxide-derived copper electrocatalyst for selective carbon dioxide reduction
journal, January 2019

  • Nguyen-Phan, Thuy-Duong; Wang, Congjun; Marin, Chris M.
  • Journal of Materials Chemistry A, Vol. 7, Issue 48
  • DOI: 10.1039/c9ta10135g

Solar conversion of CO2 to CO using Earth-abundant electrocatalysts prepared by atomic layer modification of CuO
journal, June 2017

  • Schreier, Marcel; Héroguel, Florent; Steier, Ludmilla
  • Nature Energy, Vol. 2, Issue 7
  • DOI: 10.1038/nenergy.2017.87

CO 2 reduction: the quest for electrocatalytic materials
journal, January 2017

  • Khezri, Bahareh; Fisher, Adrian C.; Pumera, Martin
  • Journal of Materials Chemistry A, Vol. 5, Issue 18
  • DOI: 10.1039/c6ta09875d

Understanding the Heterogeneous Electrocatalytic Reduction of Carbon Dioxide on Oxide-Derived Catalysts
journal, December 2017


Size-Dependent Activity of Palladium Nanoparticles: Efficient Conversion of CO 2 into Formate at Low Overpotentials
journal, March 2017


Catalyst electro-redeposition controls morphology and oxidation state for selective carbon dioxide reduction
journal, January 2018


Electrochemical Carbon Dioxide Reduction at Nanostructured Gold, Copper, and Alloy Materials
journal, March 2017

  • Vickers, James W.; Alfonso, Dominic; Kauffman, Douglas R.
  • Energy Technology, Vol. 5, Issue 6
  • DOI: 10.1002/ente.201600580

Controlling the nucleophilic properties of cobalt salen complexes for carbon dioxide capture
journal, January 2019

  • Chiong, Meliton R.; Paraan, Francis N. C.
  • RSC Advances, Vol. 9, Issue 40
  • DOI: 10.1039/c9ra01990a

A Disquisition on the Active Sites of Heterogeneous Catalysts for Electrochemical Reduction of CO 2 to Value‐Added Chemicals and Fuel
journal, November 2019

  • Daiyan, Rahman; Saputera, Wibawa Hendra; Masood, Hassan
  • Advanced Energy Materials, Vol. 10, Issue 11
  • DOI: 10.1002/aenm.201902106

Dopant-induced electron localization drives CO2 reduction to C2 hydrocarbons
journal, July 2018


Understanding cation effects in electrochemical CO 2 reduction
journal, January 2019

  • Ringe, Stefan; Clark, Ezra L.; Resasco, Joaquin
  • Energy & Environmental Science, Vol. 12, Issue 10
  • DOI: 10.1039/c9ee01341e

Copper sulfide derived nanoparticles supported on carbon for the electrochemical reduction of carbon dioxide
journal, October 2021

  • van Oversteeg, Christina H. M.; Tapia Rosales, Marisol; Helfferich, Kristiaan H.
  • Catalysis Today, Vol. 377
  • DOI: 10.1016/j.cattod.2020.09.020

In-situ Spectroscopic Techniques as Critical Evaluation Tools for Electrochemical Carbon dioxide Reduction: A Mini Review
journal, March 2020

  • Adarsh, K. S.; Chandrasekaran, Naveen; Chakrapani, Vidhya
  • Frontiers in Chemistry, Vol. 8
  • DOI: 10.3389/fchem.2020.00137