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Title: Polymer-supported CuPd nanoalloy as a synergistic catalyst for electrocatalytic reduction of carbon dioxide to methane

Abstract

Developing sustainable energy strategies based on CO2 reduction is an increasingly important issue given the world’s continued reliance on hydrocarbon fuels and the rise in CO2 concentrations in the atmosphere. An important option is electrochemical or photoelectrochemical CO2 reduction to carbon fuels. We describe here an electrodeposition strategy for preparing highly dispersed, ultrafine metal nanoparticle catalysts on an electroactive polymeric film including nanoalloys of Cu and Pd. Compared with nanoCu catalysts, which are state-of-the-art catalysts for CO2 reduction to hydrocarbons, the bimetallic CuPd nanoalloy catalyst exhibits a greater than twofold enhancement in Faradaic efficiency for CO2 reduction to methane. The origin of the enhancement is suggested to arise from a synergistic reactivity interplay between Pd–H sites and Cu–CO sites during electrochemical CO2 reduction. The polymer substrate also appears to provide a basis for the local concentration of CO2 resulting in the enhancement of catalytic current densities by threefold. In conclusion, the procedure for preparation of the nanoalloy catalyst is straightforward and appears to be generally applicable to the preparation of catalytic electrodes for incorporation into electrolysis devices.

Authors:
; ; ; ; ;
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Solar Fuels (UNC EFRC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1235505
Alternate Identifier(s):
OSTI ID: 1370858
Grant/Contract Number:  
SC0001011
Resource Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 112 Journal Issue: 52; Journal ID: ISSN 0027-8424
Publisher:
Proceedings of the National Academy of Sciences
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis (homogeneous); catalysis (heterogeneous); solar (photovoltaic); solar (fuels); photosynthesis (natural and artificial); hydrogen and fuel cells; electrodes - solar; charge transport; materials and chemistry by design; synthesis (novel materials); synthesis (self-assembly); solar energy; carbon dioxide reduction; CuPd nanoalloy; electropolymerized film; hydrocarbon

Citation Formats

Zhang, Sheng, Kang, Peng, Bakir, Mohammed, Lapides, Alexander M., Dares, Christopher J., and Meyer, Thomas J. Polymer-supported CuPd nanoalloy as a synergistic catalyst for electrocatalytic reduction of carbon dioxide to methane. United States: N. p., 2015. Web. https://doi.org/10.1073/pnas.1522496112.
Zhang, Sheng, Kang, Peng, Bakir, Mohammed, Lapides, Alexander M., Dares, Christopher J., & Meyer, Thomas J. Polymer-supported CuPd nanoalloy as a synergistic catalyst for electrocatalytic reduction of carbon dioxide to methane. United States. https://doi.org/10.1073/pnas.1522496112
Zhang, Sheng, Kang, Peng, Bakir, Mohammed, Lapides, Alexander M., Dares, Christopher J., and Meyer, Thomas J. Mon . "Polymer-supported CuPd nanoalloy as a synergistic catalyst for electrocatalytic reduction of carbon dioxide to methane". United States. https://doi.org/10.1073/pnas.1522496112.
@article{osti_1235505,
title = {Polymer-supported CuPd nanoalloy as a synergistic catalyst for electrocatalytic reduction of carbon dioxide to methane},
author = {Zhang, Sheng and Kang, Peng and Bakir, Mohammed and Lapides, Alexander M. and Dares, Christopher J. and Meyer, Thomas J.},
abstractNote = {Developing sustainable energy strategies based on CO2 reduction is an increasingly important issue given the world’s continued reliance on hydrocarbon fuels and the rise in CO2 concentrations in the atmosphere. An important option is electrochemical or photoelectrochemical CO2 reduction to carbon fuels. We describe here an electrodeposition strategy for preparing highly dispersed, ultrafine metal nanoparticle catalysts on an electroactive polymeric film including nanoalloys of Cu and Pd. Compared with nanoCu catalysts, which are state-of-the-art catalysts for CO2 reduction to hydrocarbons, the bimetallic CuPd nanoalloy catalyst exhibits a greater than twofold enhancement in Faradaic efficiency for CO2 reduction to methane. The origin of the enhancement is suggested to arise from a synergistic reactivity interplay between Pd–H sites and Cu–CO sites during electrochemical CO2 reduction. The polymer substrate also appears to provide a basis for the local concentration of CO2 resulting in the enhancement of catalytic current densities by threefold. In conclusion, the procedure for preparation of the nanoalloy catalyst is straightforward and appears to be generally applicable to the preparation of catalytic electrodes for incorporation into electrolysis devices.},
doi = {10.1073/pnas.1522496112},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 52,
volume = 112,
place = {United States},
year = {2015},
month = {12}
}

Journal Article:
Free Publicly Available Full Text
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https://doi.org/10.1073/pnas.1522496112

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Cited by: 24 works
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Works referenced in this record:

Electrochemical Reduction of Carbon Dioxide at a Platinum Electrode in Acetonitrile-Water Mixtures
journal, January 2000

  • Tomita, Y.; Teruya, S.; Koga, O.
  • Journal of The Electrochemical Society, Vol. 147, Issue 11
  • DOI: 10.1149/1.1394035

Formation of hydrocarbons in the electrochemical reduction of carbon dioxide at a copper electrode in aqueous solution
journal, January 1989

  • Hori, Yoshio; Murata, Akira; Takahashi, Ryutaro
  • Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 85, Issue 8
  • DOI: 10.1039/F19898502309

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

Nanostructured Tin Catalysts for Selective Electrochemical Reduction of Carbon Dioxide to Formate
journal, January 2014

  • Zhang, Sheng; Kang, Peng; Meyer, Thomas J.
  • Journal of the American Chemical Society, Vol. 136, Issue 5
  • DOI: 10.1021/ja4113885

Chemical and electrochemical properties of 2,2'-bipyridyl complexes of ruthenium covalently bound to platinum oxide electrodes
journal, November 1979

  • Abruna, H. D.; Meyer, Thomas J.; Murray, Royce W.
  • Inorganic Chemistry, Vol. 18, Issue 11
  • DOI: 10.1021/ic50201a058

Renewable and metal-free carbon nanofibre catalysts for carbon dioxide reduction
journal, December 2013

  • Kumar, Bijandra; Asadi, Mohammad; Pisasale, Davide
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms3819

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

Electrochemistry of Aqueous Pyridinium: Exploration of a Key Aspect of Electrocatalytic Reduction of CO 2 to Methanol
journal, September 2013

  • Yan, Yong; Zeitler, Elizabeth L.; Gu, Jing
  • Journal of the American Chemical Society, Vol. 135, Issue 38
  • DOI: 10.1021/ja4064052

Electrochemical CO2 Reduction on Metal Electrodes
book, January 2008


Electrochemical Reduction of CO at a Copper Electrode
journal, September 1997

  • Hori, Yoshio; Takahashi, Ryutaro; Yoshinami, Yuzuru
  • The Journal of Physical Chemistry B, Vol. 101, Issue 36
  • DOI: 10.1021/jp970284i

Stabilization of a Ruthenium(II) Polypyridyl Dye on Nanocrystalline TiO 2 by an Electropolymerized Overlayer
journal, October 2013

  • Lapides, Alexander M.; Ashford, Dennis L.; Hanson, Kenneth
  • Journal of the American Chemical Society, Vol. 135, Issue 41
  • DOI: 10.1021/ja4055977

Adsorption of CO, intermediately formed in electrochemical reduction of CO2, at a copper electrode
journal, January 1991

  • Hori, Yoshio; Murata, Akira; Yoshinami, Yuzuru
  • Journal of the Chemical Society, Faraday Transactions, Vol. 87, Issue 1
  • DOI: 10.1039/ft9918700125

Selectivity of CO 2 Reduction on Copper Electrodes: The Role of the Kinetics of Elementary Steps
journal, January 2013

  • Nie, Xiaowa; Esopi, Monica R.; Janik, Michael J.
  • Angewandte Chemie International Edition, Vol. 52, Issue 9
  • DOI: 10.1002/anie.201208320

Ionic Liquid-Mediated Selective Conversion of CO2 to CO at Low Overpotentials
journal, September 2011

  • Rosen, B. A.; Salehi-Khojin, A.; Thorson, M. R.
  • Science, Vol. 334, Issue 6056, p. 643-644
  • DOI: 10.1126/science.1209786

Mechanisms of carbon monoxide reduction with zirconium hydrides
journal, April 1980

  • Wolczanski, Peter T.; Bercaw, John E.
  • Accounts of Chemical Research, Vol. 13, Issue 4
  • DOI: 10.1021/ar50148a004

Electrocatalytic Conversion of Carbon Dioxide to Methane and Methanol on Transition Metal Surfaces
journal, August 2014

  • Kuhl, Kendra P.; Hatsukade, Toru; Cave, Etosha R.
  • Journal of the American Chemical Society, Vol. 136, Issue 40
  • DOI: 10.1021/ja505791r

Binding and Reduction of Silver Ions in Thin Polymeric Films of poly-[Fe(vbpy)2(CN)2],poly-vbpy
journal, August 1994

  • Bakir, Mohammed; MacKay, Susan G.; Linton, Richard W.
  • Inorganic Chemistry, Vol. 33, Issue 18
  • DOI: 10.1021/ic00096a019

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

Reduction of carbon dioxide to methane and ethene—an on-line MS study with rotating electrodes
journal, April 1990


A selective and efficient electrocatalyst for carbon dioxide reduction
journal, January 2014

  • Lu, Qi; Rosen, Jonathan; Zhou, Yang
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms4242

A Local Proton Source Enhances CO 2 Electroreduction to CO by a Molecular Fe Catalyst
journal, October 2012


Cu(ii)/Cu(0) electrocatalyzed CO2 and H2O splitting
journal, January 2013

  • Chen, Zuofeng; Kang, Peng; Zhang, Ming-Tian
  • Energy & Environmental Science, Vol. 6, Issue 3
  • DOI: 10.1039/c3ee24487c

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

Monodisperse Au Nanoparticles for Selective Electrocatalytic Reduction of CO 2 to CO
journal, October 2013

  • Zhu, Wenlei; Michalsky, Ronald; Metin, Önder
  • Journal of the American Chemical Society, Vol. 135, Issue 45
  • DOI: 10.1021/ja409445p

Enhanced Electrochemical Methanation of Carbon Dioxide with a Dispersible Nanoscale Copper Catalyst
journal, September 2014

  • Manthiram, Karthish; Beberwyck, Brandon J.; Alivisatos, A. Paul
  • Journal of the American Chemical Society, Vol. 136, Issue 38
  • DOI: 10.1021/ja5065284

Stepwise reduction of coordinated carbon monoxide
journal, May 1982

  • Sweet, James R.; Graham, William A. G.
  • Journal of the American Chemical Society, Vol. 104, Issue 10
  • DOI: 10.1021/ja00374a019

Photoelectrochemistry of tris(bipyridyl)ruthenium(II) covalently attached to n-type tin(IV) oxide
journal, August 1980

  • Ghosh, Pushpito; Spiro, Thomas G.
  • Journal of the American Chemical Society, Vol. 102, Issue 17
  • DOI: 10.1021/ja00537a021

Splitting CO2 into CO and O2 by a single catalyst
journal, June 2012

  • Chen, Z.; Concepcion, J. J.; Brennaman, M. K.
  • Proceedings of the National Academy of Sciences, Vol. 109, Issue 39
  • DOI: 10.1073/pnas.1203122109

How copper catalyzes the electroreduction of carbon dioxide into hydrocarbon fuels
journal, January 2010

  • Peterson, Andrew A.; Abild-Pedersen, Frank; Studt, Felix
  • Energy & Environmental Science, Vol. 3, Issue 9
  • DOI: 10.1039/c0ee00071j

Surfactant-free preparation of supported cubic platinum nanoparticles
journal, January 2012

  • Peng, Zhenmeng; Kisielowski, Christian; Bell, Alexis T.
  • Chemical Communications, Vol. 48, Issue 13
  • DOI: 10.1039/c2cc16962b

Sodium borohydride reduction of carbon monoxide in the cationic iron carbonyl complexes [C5Me5Fe(CO)2L]+ PF6- (L = CO or phosphine)
journal, August 1988

  • Lapinte, Claude.; Catheline, Daniel.; Astruc, Didier.
  • Organometallics, Vol. 7, Issue 8
  • DOI: 10.1021/om00098a002

Electrochemical and Surface Studies of Carbon Dioxide Reduction to Methane and Ethylene at Copper Electrodes in Aqueous Solutions
journal, January 1989

  • DeWulf, David W.
  • Journal of The Electrochemical Society, Vol. 136, Issue 6, p. 1686-1691
  • DOI: 10.1149/1.2096993

Graphene–Polypyrrole Nanocomposite as a Highly Efficient and Low Cost Electrically Switched Ion Exchanger for Removing ClO 4 from Wastewater
journal, August 2011

  • Zhang, Sheng; Shao, Yuyan; Liu, Jun
  • ACS Applied Materials & Interfaces, Vol. 3, Issue 9
  • DOI: 10.1021/am200839m

Synergistic geometric and electronic effects for electrochemical reduction of carbon dioxide using gold–copper bimetallic nanoparticles
journal, September 2014

  • Kim, Dohyung; Resasco, Joaquin; Yu, Yi
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms5948

“Deactivation of copper electrode” in electrochemical reduction of CO2
journal, September 2005


Strategies for Stabilization of Electrodeposited Metal Particles in Electropolymerized Films for H 2 O Oxidation and H + Reduction
journal, July 2013

  • Torelli, Daniel A.; Harrison, Daniel P.; Lapides, Alexander M.
  • ACS Applied Materials & Interfaces, Vol. 5, Issue 15
  • DOI: 10.1021/am401331k

Electrogenerated polypyridyl ruthenium hydride and ligand activation for water reduction to hydrogen and acetone to iso-propanol
journal, January 2013

  • Chen, Zuofeng; Glasson, Christopher R. K.; Holland, Patrick L.
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 24
  • DOI: 10.1039/c3cp51946e

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

Mechanistic features of catalytic carbon monoxide hydrogenation reactions
journal, December 1979

  • Muetterties, E. L.; Stein, Judith.
  • Chemical Reviews, Vol. 79, Issue 6
  • DOI: 10.1021/cr60322a001

Synthetic and mechanistic investigations of the reductive electrochemical polymerization of vinyl-containing complexes of iron(II), ruthenium(II), and osmium(II)
journal, July 1983

  • Calvert, Jeffrey M.; Schmehl, Russell H.; Sullivan, B. Patrick
  • Inorganic Chemistry, Vol. 22, Issue 15
  • DOI: 10.1021/ic00157a013

    Works referencing / citing this record:

    Copper and Copper-Based Bimetallic Catalysts for Carbon Dioxide Electroreduction
    journal, October 2018

    • Birhanu, Mulatu Kassie; Tsai, Meng-Che; Kahsay, Amaha Woldu
    • Advanced Materials Interfaces, Vol. 5, Issue 24
    • DOI: 10.1002/admi.201800919

    Recent Advances in Breaking Scaling Relations for Effective Electrochemical Conversion of CO 2
    journal, April 2016


    Anchoring PdCu Amorphous Nanocluster on Graphene for Electrochemical Reduction of N 2 to NH 3 under Ambient Conditions in Aqueous Solution
    journal, April 2018


    MoP Nanoparticles Supported on Indium-Doped Porous Carbon: Outstanding Catalysts for Highly Efficient CO 2 Electroreduction
    journal, February 2018


    Tuning Gold Nanoparticles with Chelating Ligands for Highly Efficient Electrocatalytic CO 2 Reduction
    journal, August 2018

    • Cao, Zhi; Zacate, Samson B.; Sun, Xiaodong
    • Angewandte Chemie, Vol. 130, Issue 39
    • DOI: 10.1002/ange.201805696

    Highly Efficient Electroreduction of CO 2 to Methanol on Palladium-Copper Bimetallic Aerogels
    journal, October 2018


    Selective Electrochemical Reduction of Carbon Dioxide to Ethanol on a Boron- and Nitrogen-Co-doped Nanodiamond
    journal, October 2017

    • Liu, Yanming; Zhang, Yujing; Cheng, Kai
    • Angewandte Chemie International Edition, Vol. 56, Issue 49
    • DOI: 10.1002/anie.201706311

    MoP Nanoparticles Supported on Indium-Doped Porous Carbon: Outstanding Catalysts for Highly Efficient CO 2 Electroreduction
    journal, February 2018

    • Sun, Xiaofu; Lu, Lu; Zhu, Qinggong
    • Angewandte Chemie International Edition, Vol. 57, Issue 9
    • DOI: 10.1002/anie.201712221

    Highly Efficient Electroreduction of CO 2 to Methanol on Palladium-Copper Bimetallic Aerogels
    journal, October 2018

    • Lu, Lu; Sun, Xiaofu; Ma, Jun
    • Angewandte Chemie International Edition, Vol. 57, Issue 43
    • DOI: 10.1002/anie.201808964

    Aqueous CO 2 Reduction with High Efficiency Using α‐Co(OH) 2 ‐Supported Atomic Ir Electrocatalysts
    journal, February 2019

    • Sun, Xiaofu; Chen, Chunjun; Liu, Shoujie
    • Angewandte Chemie International Edition, Vol. 58, Issue 14
    • DOI: 10.1002/anie.201900981

    A Rational Design of Cu 2 O−SnO 2 Core‐Shell Catalyst for Highly Selective CO 2 ‐to‐CO Conversion
    journal, May 2019


    CuSn Alloy Nanoparticles on Nitrogen‐Doped Graphene for Electrocatalytic CO 2 Reduction
    journal, October 2019


    Supported Porous Nanomaterials as Efficient Heterogeneous Catalysts for CO 2 Fixation Reactions
    journal, April 2018

    • Bhanja, Piyali; Modak, Arindam; Bhaumik, Asim
    • Chemistry – A European Journal, Vol. 24, Issue 29
    • DOI: 10.1002/chem.201800075

    Steric Hindrance in Sulfur Vacancy of Monolayer MoS 2 Boosts Electrochemical Reduction of Carbon Monoxide to Methane
    journal, April 2018


    Cobalt Complex with Redox-Active Imino Bipyridyl Ligand for Electrocatalytic Reduction of Carbon Dioxide to Formate
    journal, May 2018


    Lattice Engineering on Metal Cocatalysts for Enhanced Photocatalytic Reduction of CO 2 into CH 4
    journal, August 2018


    Electrocatalytic Reduction of CO 2 to Methanol by Iron Tetradentate Phosphine Complex Through Amidation Strategy
    journal, April 2019


    Switchable CO2 electroreduction via engineering active phases of Pd nanoparticles
    journal, April 2017


    Bimetallic Electrocatalysts for CO2 Reduction
    journal, October 2018

    • Zhu, Wenlei; Tackett, Brian M.; Chen, Jingguang G.
    • Topics in Current Chemistry, Vol. 376, Issue 6
    • DOI: 10.1007/s41061-018-0220-5

    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

    Understanding activity and selectivity of metal-nitrogen-doped carbon catalysts for electrochemical reduction of CO2
    journal, October 2017


    High-rate electroreduction of carbon monoxide to multi-carbon products
    journal, August 2018


    Recent advances in the nanoengineering of electrocatalysts for CO 2 reduction
    journal, January 2018

    • Li, Fengwang; MacFarlane, Douglas R.; Zhang, Jie
    • Nanoscale, Vol. 10, Issue 14
    • DOI: 10.1039/c7nr09620h

    Cathodized copper porphyrin metal–organic framework nanosheets for selective formate and acetate production from CO 2 electroreduction
    journal, January 2019

    • Wu, Jian-Xiang; Hou, Shu-Zhen; Zhang, Xiang-Da
    • Chemical Science, Vol. 10, Issue 7
    • DOI: 10.1039/c8sc04344b

    Shaping well-defined noble-metal-based nanostructures for fabricating high-performance electrocatalysts: advances and perspectives
    journal, January 2019

    • Yin, Hai-Jing; Zhou, Jun-Hao; Zhang, Ya-Wen
    • Inorganic Chemistry Frontiers, Vol. 6, Issue 10
    • DOI: 10.1039/c9qi00689c

    Interface engineering on Janus Pd–Au heterojunction co-catalysts for selective photocatalytic reduction of CO 2 to CH 4
    journal, January 2019

    • Cai, Xiaotong; Wang, Jiawei; Wang, Ruoxin
    • Journal of Materials Chemistry A, Vol. 7, Issue 10
    • DOI: 10.1039/c9ta00172g

    CO 2 reduction to acetate in mixtures of ultrasmall (Cu) n ,(Ag) m bimetallic nanoparticles
    journal, December 2017

    • Wang, Ying; Wang, Degao; Dares, Christopher J.
    • Proceedings of the National Academy of Sciences, Vol. 115, Issue 2
    • DOI: 10.1073/pnas.1713962115

    Controlled Substrate Transport to Electrocatalyst Active Sites for Enhanced Selectivity in the Carbon Dioxide Reduction Reaction
    journal, June 2019