Planar defect-driven electrocatalysis of CO2-to-C2H4 conversion

Li, Zhengyuan; Fang, Yanbo; Zhang, Jianfang; Zhang, Tianyu; Jimenez, Juan D.; Senanayake, Sanjaya D.; Shanov, Vesselin; Yang, Shize; Wu, Jingjie

doi:10.1039/d1ta02565a

Title: Planar defect-driven electrocatalysis of CO₂-to-C₂H₄ conversion

Abstract

The selectivity towards a specific C₂₊ product, such as ethylene (C₂H₄), is sensitive to the surface structure of copper (Cu) catalysts in carbon dioxide (CO₂) electro-reduction. The fundamental understanding of such sensitivity can guide the development of advanced electrocatalysts, although it remains challenging at the atomic level. In this work, we demonstrated that planar defects, such as stacking faults, could drive the electrocatalysis of CO₂-to-C₂H₄ conversion with higher selectivity and productivity than Cu(100) facets in the intermediate potential region (–0.50 ~ –0.65 V vs. RHE). The unique right bipyramidal Cu nanocrystals containing a combination of (100) facets and a set of parallel planar defects delivered 67% faradaic efficiency (FE) for C₂H₄ and a partial current density of 217 mA cm^–2 at –0.63 V vs. RHE. In contrast, Cu nanocubes with exclusive (100) facets exhibited only 46% FE for C₂H₄ and a partial current density of 87 mA cm^–2 at an identical potential. Both ex situ CO temperature-programmed desorption and in situ Raman spectroscopy analysis implied that the stronger *CO adsorption on planar defect sites facilitates CO generation kinetics, which contributes to a higher surface coverage of *CO and in turn an enhanced reaction rate of C–C coupling towards C₂₊ products,more » especially C₂H₄.« less

Authors:

Li, Zhengyuan ^[1]; Fang, Yanbo ^[1]; Zhang, Jianfang ^[1]; Zhang, Tianyu ^[1];

^[2];

^[2]; Shanov, Vesselin ^[1]; Yang, Shize ^[3];

^[1]

Univ. of Cincinnati, OH (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)
Arizona State Univ., Tempe, AZ (United States)

Publication Date:: Tue Jun 15 00:00:00 EDT 2021

Research Org.:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

OSTI Identifier:: 1812505

Alternate Identifier(s):: OSTI ID: 1805111

Report Number(s):: BNL-221966-2021-JAAM
Journal ID: ISSN 2050-7488

Grant/Contract Number:: SC0012704; CBET-2033343; NNCI-ECCS-1542160

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Materials Chemistry. A

Additional Journal Information:: Journal Volume: 9; Journal Issue: 35; Journal ID: ISSN 2050-7488

Publisher:: Royal Society of Chemistry

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE; CO2 electro-reduction; ethylene; planar defects; Cu(100) facet; in situ Raman

Citation Formats


                    Li, Zhengyuan, Fang, Yanbo, Zhang, Jianfang, Zhang, Tianyu, Jimenez, Juan D., Senanayake, Sanjaya D., Shanov, Vesselin, Yang, Shize, and Wu, Jingjie. Planar defect-driven electrocatalysis of CO2-to-C2H4 conversion.  United States: N. p., 2021. 
Web.  doi:10.1039/d1ta02565a.

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                    Li, Zhengyuan, Fang, Yanbo, Zhang, Jianfang, Zhang, Tianyu, Jimenez, Juan D., Senanayake, Sanjaya D., Shanov, Vesselin, Yang, Shize, & Wu, Jingjie. Planar defect-driven electrocatalysis of CO2-to-C2H4 conversion.  United States.  https://doi.org/10.1039/d1ta02565a

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                    Li, Zhengyuan, Fang, Yanbo, Zhang, Jianfang, Zhang, Tianyu, Jimenez, Juan D., Senanayake, Sanjaya D., Shanov, Vesselin, Yang, Shize, and Wu, Jingjie. Tue .  
"Planar defect-driven electrocatalysis of CO2-to-C2H4 conversion".  United States.  https://doi.org/10.1039/d1ta02565a.  https://www.osti.gov/servlets/purl/1812505.

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@article{osti_1812505,

  title        = {Planar defect-driven electrocatalysis of CO2-to-C2H4 conversion},

  author       = {Li, Zhengyuan and Fang, Yanbo and Zhang, Jianfang and Zhang, Tianyu and Jimenez, Juan D. and Senanayake, Sanjaya D. and Shanov, Vesselin and Yang, Shize and Wu, Jingjie},

  abstractNote = {The selectivity towards a specific C2+ product, such as ethylene (C2H4), is sensitive to the surface structure of copper (Cu) catalysts in carbon dioxide (CO2) electro-reduction. The fundamental understanding of such sensitivity can guide the development of advanced electrocatalysts, although it remains challenging at the atomic level. In this work, we demonstrated that planar defects, such as stacking faults, could drive the electrocatalysis of CO2-to-C2H4 conversion with higher selectivity and productivity than Cu(100) facets in the intermediate potential region (–0.50 ~ –0.65 V vs. RHE). The unique right bipyramidal Cu nanocrystals containing a combination of (100) facets and a set of parallel planar defects delivered 67% faradaic efficiency (FE) for C2H4 and a partial current density of 217 mA cm–2 at –0.63 V vs. RHE. In contrast, Cu nanocubes with exclusive (100) facets exhibited only 46% FE for C2H4 and a partial current density of 87 mA cm–2 at an identical potential. Both ex situ CO temperature-programmed desorption and in situ Raman spectroscopy analysis implied that the stronger *CO adsorption on planar defect sites facilitates CO generation kinetics, which contributes to a higher surface coverage of *CO and in turn an enhanced reaction rate of C–C coupling towards C2+ products, especially C2H4.},

  doi          = {10.1039/d1ta02565a},

  journal      = {Journal of Materials Chemistry. A},

  number       = 35,

  volume       = 9,

  place        = {United States},

  year         = {Tue Jun 15 00:00:00 EDT 2021},

  month        = {Tue Jun 15 00:00:00 EDT 2021}

}

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Title: Planar defect-driven electrocatalysis of CO2-to-C2H4 conversion

Abstract

Citation Formats

Theoretical Considerations on the Electroreduction of CO to C 2 Species on Cu(100) Electrodes journal, June 2013

Microkinetic Modeling: A Tool for Rational Catalyst Design journal, November 2020

Highly Electrocatalytic Ethylene Production from CO 2 on Nanodefective Cu Nanosheets journal, July 2020

Operando time-resolved X-ray absorption spectroscopy reveals the chemical nature enabling highly selective CO2 reduction journal, July 2020

What would it take for renewably powered electrosynthesis to displace petrochemical processes? journal, April 2019

Electroreduction of carbon monoxide to liquid fuel on oxide-derived nanocrystalline copper journal, April 2014

CO-CO coupling on Cu facets: Coverage, strain and field effects journal, December 2016

The nature of active sites for carbon dioxide electroreduction over oxide-derived copper catalysts journal, January 2021

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Shape-Controlled Synthesis of Copper Nanocrystals in an Aqueous Solution with Glucose as a Reducing Agent and Hexadecylamine as a Capping Agent journal, September 2011

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Suppression of Competing Reaction Channels by Pb Adatom Decoration of Catalytically Active Cu Surfaces During CO 2 Electroreduction journal, December 2018

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Underpotential Deposition at Single Crystal Surfaces of Au, Pt, Ag and Other Materials journal, July 2001

Theoretical Insights into a CO Dimerization Mechanism in CO 2 Electroreduction journal, May 2015

Tuning the Selectivity of Carbon Dioxide Electroreduction toward Ethanol on Oxide-Derived Cu x Zn Catalysts journal, November 2016

Determination of Site Specific Adsorption Energies of CO on Copper journal, January 2001

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Efficient Electrocatalytic CO2 Reduction to C2+ Alcohols at Defect-Site-Rich Cu Surface journal, February 2021

Existence of an Electrochemically Inert CO Population on Cu Electrodes in Alkaline pH journal, July 2018

Facet-Dependent Selectivity of Cu Catalysts in Electrochemical CO 2 Reduction at Commercially Viable Current Densities journal, March 2020

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

Low-Overpotential Electroreduction of Carbon Monoxide Using Copper Nanowires journal, June 2017

Grain-Boundary-Rich Copper for Efficient Solar-Driven Electrochemical CO 2 Reduction to Ethylene and Ethanol journal, March 2020

Highly active and stable stepped Cu surface for enhanced electrochemical CO2 reduction to C2H4 journal, September 2020

Enhance CO2-to-C2+ products yield through spatial management of CO transport in Cu/ZnO tandem electrodes journal, July 2020

A Highly Active Star Decahedron Cu Nanocatalyst for Hydrocarbon Production at Low Overpotentials journal, December 2018

Potential-induced nanoclustering of metallic catalysts during electrochemical CO2 reduction journal, August 2018

Catalyst synthesis under CO2 electroreduction favours faceting and promotes renewable fuels electrosynthesis journal, December 2019

Electrochemical Fragmentation of Cu 2 O Nanoparticles Enhancing Selective C–C Coupling from CO 2 Reduction Reaction journal, January 2019

Accelerated discovery of CO2 electrocatalysts using active machine learning journal, May 2020

pH effects on the electrochemical reduction of CO(2) towards C2 products on stepped copper journal, January 2019

Title: Planar defect-driven electrocatalysis of CO₂-to-C₂H₄ conversion

Theoretical Considerations on the Electroreduction of CO to C ₂ Species on Cu(100) Electrodes
journal, June 2013

Microkinetic Modeling: A Tool for Rational Catalyst Design
journal, November 2020

Highly Electrocatalytic Ethylene Production from CO ₂ on Nanodefective Cu Nanosheets
journal, July 2020

Operando time-resolved X-ray absorption spectroscopy reveals the chemical nature enabling highly selective CO2 reduction
journal, July 2020

What would it take for renewably powered electrosynthesis to displace petrochemical processes?
journal, April 2019

Electroreduction of carbon monoxide to liquid fuel on oxide-derived nanocrystalline copper
journal, April 2014

CO-CO coupling on Cu facets: Coverage, strain and field effects
journal, December 2016

The nature of active sites for carbon dioxide electroreduction over oxide-derived copper catalysts
journal, January 2021

Efficient electrically powered CO2-to-ethanol via suppression of deoxygenation
journal, May 2020

Shape-Controlled Synthesis of Copper Nanocrystals in an Aqueous Solution with Glucose as a Reducing Agent and Hexadecylamine as a Capping Agent
journal, September 2011

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

Environment Matters: CO ₂ RR Electrocatalyst Performance Testing in a Gas-Fed Zero-Gap Electrolyzer
journal, October 2020

Suppression of Competing Reaction Channels by Pb Adatom Decoration of Catalytically Active Cu Surfaces During CO ₂ Electroreduction
journal, December 2018

pH Dependence of Cu Surface Speciation in the Electrochemical CO Reduction Reaction
journal, November 2020

Cascade CO2 electroreduction enables efficient carbonate-free production of ethylene
journal, March 2021

Electrocatalytic reduction of CO2 to ethylene and ethanol through hydrogen-assisted C–C coupling over fluorine-modified copper
journal, April 2020

CuO/ZnO/C electrocatalysts for CO2-to-C2+ products conversion with high yield: On the effect of geometric structure and composition
journal, September 2020

Tandem Electrodes for Carbon Dioxide Reduction into C2+ Products at Simultaneously High Production Efficiency and Rate
journal, April 2020

Copper nanocavities confine intermediates for efficient electrosynthesis of C3 alcohol fuels from carbon monoxide
journal, October 2018

Structure Sensitivity in the Electrocatalytic Reduction of CO ₂ with Gold Catalysts
journal, February 2019

A Rationally Designed Route to the One-Pot Synthesis of Right Bipyramidal Nanocrystals of Copper
journal, September 2018

Underpotential Deposition at Single Crystal Surfaces of Au, Pt, Ag and Other Materials
journal, July 2001

Theoretical Insights into a CO Dimerization Mechanism in CO ₂ Electroreduction
journal, May 2015

Tuning the Selectivity of Carbon Dioxide Electroreduction toward Ethanol on Oxide-Derived Cu _x Zn Catalysts
journal, November 2016

Determination of Site Specific Adsorption Energies of CO on Copper
journal, January 2001

Progress and Perspectives of Electrochemical CO ₂ Reduction on Copper in Aqueous Electrolyte
journal, April 2019

A Direct Grain-Boundary-Activity Correlation for CO Electroreduction on Cu Nanoparticles
journal, March 2016

Spectroscopic Observation of Reversible Surface Reconstruction of Copper Electrodes under CO ₂ Reduction
journal, May 2017

A silver catalyst activated by stacking faults for the hydrogen evolution reaction
journal, October 2019

Identification of Possible Pathways for C–C Bond Formation during Electrochemical Reduction of CO ₂ : New Theoretical Insights from an Improved Electrochemical Model
journal, April 2016

An industrial perspective on catalysts for low-temperature CO2 electrolysis
journal, January 2021

Facile Synthesis of Palladium Right Bipyramids and Their Use as Seeds for Overgrowth and as Catalysts for Formic Acid Oxidation
journal, October 2013

Electrochemical Reduction of CO ₂ Using Copper Single-Crystal Surfaces: Effects of CO* Coverage on the Selective Formation of Ethylene
journal, February 2017

The reactivity of copper clusters supported on carbon studied by XPS
journal, January 1999

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

Efficient electrocatalytic conversion of carbon monoxide to propanol using fragmented copper
journal, February 2019

Plasmon-Mediated Synthesis of Silver Triangular Bipyramids
journal, October 2009

Efficient Electrocatalytic CO2 Reduction to C2+ Alcohols at Defect-Site-Rich Cu Surface
journal, February 2021

Existence of an Electrochemically Inert CO Population on Cu Electrodes in Alkaline pH
journal, July 2018

Facet-Dependent Selectivity of Cu Catalysts in Electrochemical CO ₂ Reduction at Commercially Viable Current Densities
journal, March 2020

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

Low-Overpotential Electroreduction of Carbon Monoxide Using Copper Nanowires
journal, June 2017

Grain-Boundary-Rich Copper for Efficient Solar-Driven Electrochemical CO ₂ Reduction to Ethylene and Ethanol
journal, March 2020

Highly active and stable stepped Cu surface for enhanced electrochemical CO2 reduction to C2H4
journal, September 2020

Enhance CO2-to-C2+ products yield through spatial management of CO transport in Cu/ZnO tandem electrodes
journal, July 2020

A Highly Active Star Decahedron Cu Nanocatalyst for Hydrocarbon Production at Low Overpotentials
journal, December 2018

Potential-induced nanoclustering of metallic catalysts during electrochemical CO2 reduction
journal, August 2018

Catalyst synthesis under CO2 electroreduction favours faceting and promotes renewable fuels electrosynthesis
journal, December 2019

Electrochemical Fragmentation of Cu ₂ O Nanoparticles Enhancing Selective C–C Coupling from CO ₂ Reduction Reaction
journal, January 2019

Accelerated discovery of CO2 electrocatalysts using active machine learning
journal, May 2020

pH effects on the electrochemical reduction of CO(2) towards C2 products on stepped copper
journal, January 2019