Chemical upgrade of carbon monoxide to acetate on an atomically dispersed copper catalyst via CO-insertion

Fu, Xianbiao; Wang, Yuxuan; Shen, Hao; Yu, Yanan; Xu, Fei; Zhou, Guangye; Xie, Wenjun; Qin, Ruixuan; Dun, Chaochao; Pao, C. -W.; Chen, J. -L.; Liu, Yisheng; Guo, Jinghua; Yue, Qin; Urban, Jeffrey J.; Wang, Chao; Kang, Yijin

doi:10.1016/j.mtphys.2021.100418

Title: Chemical upgrade of carbon monoxide to acetate on an atomically dispersed copper catalyst via CO-insertion

Abstract

Electrochemical conversion of small molecules such as carbon dioxide (CO₂) and carbon monoxide (CO) to high-value multi-carbon products (C₂₊) offers a chemical upgrade approach for fuels and chemical feedstock production using renewable energy, in the possible absence of the petrochemical industry under the new energy system such as hydrogen economy. Identifying robust and efficient electrocatalysts to selectively produce C₂₊ products remains a challenge. In this study, we report a synthetic strategy of atomically dispersing copper atoms on nitrogen-rich porous carbon (Cu–N–C) through pyrolysis of a supramolecular assembly. Benefitting from the unsaturated coordination structure, in KOH electrolyte, the Cu–N–C with a Cu content of 6.9 wt% exhibits a maximum acetate Faradaic efficiency (FE) of 30% with an acetate partial current density as high as 48 mA cm^–2 in electrochemical CO reduction. Different from the C–C coupling mechanism on metallic copper, we propose a CO insertion mechanism for the acetate production on the single site copper catalyst.

Authors:

^[1]; Wang, Yuxuan ^[2]; Shen, Hao ^[3]; Yu, Yanan ^[4]; Xu, Fei ^[3]; Zhou, Guangye ^[3];

^[5];

^[6];

^[7]; Pao, C. -W. ^[8];

^[8]; Liu, Yisheng ^[7];

^[7]; Yue, Qin ^[4]; Urban, Jeffrey J. ^[7]; Wang, Chao ^[3];

^[4]

Univ. of Electronic Science and Technology of China, Chengdu (China); Johns Hopkins Univ., Baltimore, MD (United States); Xiamen Univ. (China)
Johns Hopkins Univ., Baltimore, MD (United States); Xiamen Univ. (China)
Johns Hopkins Univ., Baltimore, MD (United States)
Univ. of Electronic Science and Technology of China, Chengdu (China)
Johns Hopkins Univ., Baltimore, MD (United States); Nankai Univ., Tianjin (China)
Xiamen Univ. (China)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
National Synchrotron Radiation Research Center, Hsinchu (Taiwan)

Publication Date:: Fri Apr 30 00:00:00 EDT 2021

Research Org.:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Natural Science Foundation of China (NSFC); Sichuan Science and Technology Program

OSTI Identifier:: 1807525

Alternate Identifier(s):: OSTI ID: 1817253

Grant/Contract Number:: AC02-05CH11231; 21701153; 21773023; 2020YJ0243

Resource Type:: Accepted Manuscript

Journal Name:: Materials Today Physics

Additional Journal Information:: Journal Volume: 19; Journal ID: ISSN 2542-5293

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE; CO/CO2 electroreduction; single-site catalyst; CO insertion; supramolecular assembly; partial pressure

Citation Formats


                    Fu, Xianbiao, Wang, Yuxuan, Shen, Hao, Yu, Yanan, Xu, Fei, Zhou, Guangye, Xie, Wenjun, Qin, Ruixuan, Dun, Chaochao, Pao, C. -W., Chen, J. -L., Liu, Yisheng, Guo, Jinghua, Yue, Qin, Urban, Jeffrey J., Wang, Chao, and Kang, Yijin. Chemical upgrade of carbon monoxide to acetate on an atomically dispersed copper catalyst via CO-insertion.  United States: N. p., 2021. 
Web.  doi:10.1016/j.mtphys.2021.100418.

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                    Fu, Xianbiao, Wang, Yuxuan, Shen, Hao, Yu, Yanan, Xu, Fei, Zhou, Guangye, Xie, Wenjun, Qin, Ruixuan, Dun, Chaochao, Pao, C. -W., Chen, J. -L., Liu, Yisheng, Guo, Jinghua, Yue, Qin, Urban, Jeffrey J., Wang, Chao, & Kang, Yijin. Chemical upgrade of carbon monoxide to acetate on an atomically dispersed copper catalyst via CO-insertion.  United States.  https://doi.org/10.1016/j.mtphys.2021.100418

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                    Fu, Xianbiao, Wang, Yuxuan, Shen, Hao, Yu, Yanan, Xu, Fei, Zhou, Guangye, Xie, Wenjun, Qin, Ruixuan, Dun, Chaochao, Pao, C. -W., Chen, J. -L., Liu, Yisheng, Guo, Jinghua, Yue, Qin, Urban, Jeffrey J., Wang, Chao, and Kang, Yijin. Fri .  
"Chemical upgrade of carbon monoxide to acetate on an atomically dispersed copper catalyst via CO-insertion".  United States.  https://doi.org/10.1016/j.mtphys.2021.100418.  https://www.osti.gov/servlets/purl/1807525.

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@article{osti_1807525,

  title        = {Chemical upgrade of carbon monoxide to acetate on an atomically dispersed copper catalyst via CO-insertion},

  author       = {Fu, Xianbiao and Wang, Yuxuan and Shen, Hao and Yu, Yanan and Xu, Fei and Zhou, Guangye and Xie, Wenjun and Qin, Ruixuan and Dun, Chaochao and Pao, C. -W. and Chen, J. -L. and Liu, Yisheng and Guo, Jinghua and Yue, Qin and Urban, Jeffrey J. and Wang, Chao and Kang, Yijin},

  abstractNote = {Electrochemical conversion of small molecules such as carbon dioxide (CO2) and carbon monoxide (CO) to high-value multi-carbon products (C2+) offers a chemical upgrade approach for fuels and chemical feedstock production using renewable energy, in the possible absence of the petrochemical industry under the new energy system such as hydrogen economy. Identifying robust and efficient electrocatalysts to selectively produce C2+ products remains a challenge. In this study, we report a synthetic strategy of atomically dispersing copper atoms on nitrogen-rich porous carbon (Cu–N–C) through pyrolysis of a supramolecular assembly. Benefitting from the unsaturated coordination structure, in KOH electrolyte, the Cu–N–C with a Cu content of 6.9 wt% exhibits a maximum acetate Faradaic efficiency (FE) of 30% with an acetate partial current density as high as 48 mA cm–2 in electrochemical CO reduction. Different from the C–C coupling mechanism on metallic copper, we propose a CO insertion mechanism for the acetate production on the single site copper catalyst.},

  doi          = {10.1016/j.mtphys.2021.100418},

  journal      = {Materials Today Physics},

  number       = ,

  volume       = 19,

  place        = {United States},

  year         = {Fri Apr 30 00:00:00 EDT 2021},

  month        = {Fri Apr 30 00:00:00 EDT 2021}

}

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Title: Chemical upgrade of carbon monoxide to acetate on an atomically dispersed copper catalyst via CO-insertion

Abstract

Citation Formats

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Electrochemical Reduction of Carbon Dioxide to Methanol on Hierarchical Pd/SnO 2 Nanosheets with Abundant Pd-O-Sn Interfaces journal, June 2018

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Constraining CO coverage on copper promotes high-efficiency ethylene electroproduction journal, November 2019

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

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Intermetallic Alloys as CO Electroreduction Catalysts—Role of Isolated Active Sites journal, May 2014

Ensemble Effect in Bimetallic Electrocatalysts for CO 2 Reduction journal, September 2019

–CH 3 Mediated Pathway for the Electroreduction of CO 2 to Ethane and Ethanol on Thick Oxide-Derived Copper Catalysts at Low Overpotentials journal, August 2017

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

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

Atomic site electrocatalysts for water splitting, oxygen reduction and selective oxidation journal, January 2020

Copper Nanocubes for CO 2 Reduction in Gas Diffusion Electrodes journal, October 2019

Molecular Scaffolding Strategy with Synergistic Active Centers To Facilitate Electrocatalytic CO 2 Reduction to Hydrocarbon/Alcohol journal, November 2017

Golden single-atomic-site platinum electrocatalysts journal, September 2018

Designing materials for electrochemical carbon dioxide recycling journal, July 2019

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

Carbon monoxide electroreduction as an emerging platform for carbon utilization journal, December 2019

Recent Advances in Atomic‐Level Engineering of Nanostructured Catalysts for Electrochemical CO 2 Reduction journal, March 2020

Covalent Triazine Framework Confined Copper Catalysts for Selective Electrochemical CO 2 Reduction: Operando Diagnosis of Active Sites journal, March 2020

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

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

Molecular tuning of CO2-to-ethylene conversion journal, November 2019

Two-dimensional copper nanosheets for electrochemical reduction of carbon monoxide to acetate journal, April 2019

Building Blocks for High Performance in Electrocatalytic CO 2 Reduction: Materials, Optimization Strategies, and Device Engineering journal, August 2017

Cu-based nanocatalysts for electrochemical reduction of CO2 journal, August 2018

Net reduction of CO2 via its thermocatalytic and electrocatalytic transformation reactions in standard and hybrid processes journal, April 2019

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

CO 2 electrolysis to multicarbon products at activities greater than 1 A cm −2 journal, February 2020

Effectively Increased Efficiency for Electroreduction of Carbon Monoxide Using Supported Polycrystalline Copper Powder Electrocatalysts journal, April 2019

Size‐Dependent Activity and Selectivity of Atomic‐Level Copper Nanoclusters during CO/CO 2 Electroreduction journal, October 2020

Activity Descriptors for CO 2 Electroreduction to Methane on Transition-Metal Catalysts journal, January 2012

Strategies for Stabilizing Atomically Dispersed Metal Catalysts journal, December 2017

Highly dispersed, single-site copper catalysts for the electroreduction of CO2 to methane journal, October 2020

A Graphene‐Supported Single‐Atom FeN 5 Catalytic Site for Efficient Electrochemical CO 2 Reduction journal, October 2019

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

Atomically Defined Undercoordinated Active Sites for Highly Efficient CO 2 Electroreduction journal, November 2019

Atomically dispersed platinum supported on curved carbon supports for efficient electrocatalytic hydrogen evolution journal, June 2019

Preassembly Strategy To Fabricate Porous Hollow Carbonitride Spheres Inlaid with Single Cu–N 3 Sites for Selective Oxidation of Benzene to Phenol journal, November 2018

Shape-Dependent Electrocatalytic Reduction of CO 2 to CO on Triangular Silver Nanoplates journal, February 2017

Single Cobalt Atoms with Precise N-Coordination as Superior Oxygen Reduction Reaction Catalysts journal, August 2016

Mild oxidation of methane to methanol or acetic acid on supported isolated rhodium catalysts journal, November 2017

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

One-step electrosynthesis of ethylene and ethanol from CO2 in an alkaline electrolyzer journal, January 2016

Directly transforming copper (I) oxide bulk into isolated single-atom copper sites catalyst through gas-transport approach
journal, August 2019

Electrocatalysis of Single-Atom Sites: Impacts of Atomic Coordination
journal, June 2020

Electrochemical Reduction of Carbon Dioxide to Methanol on Hierarchical Pd/SnO ₂ Nanosheets with Abundant Pd-O-Sn Interfaces
journal, June 2018

Copper atom-pair catalyst anchored on alloy nanowires for selective and efficient electrochemical reduction of CO2
journal, January 2019

Understanding the Roadmap for Electrochemical Reduction of CO ₂ to Multi-Carbon Oxygenates and Hydrocarbons on Copper-Based Catalysts
journal, April 2019

Constraining CO coverage on copper promotes high-efficiency ethylene electroproduction
journal, November 2019

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

Electrochemically scrambled nanocrystals are catalytically active for CO ₂ -to-multicarbons
journal, April 2020

Electrochemical reduction of CO ₂ towards multi-carbon products via a two-step process
journal, January 2021

Selective electroreduction of CO2 to acetone by single copper atoms anchored on N-doped porous carbon
journal, May 2020

Boosting oxygen reduction catalysis with abundant copper single atom active sites
journal, January 2018

Directing the selectivity of CO ₂ electroreduction to target C ₂ products via non-metal doping on Cu surfaces
journal, January 2021

Single-atom Rh/N-doped carbon electrocatalyst for formic acid oxidation
journal, March 2020

Single-Atomic Cu with Multiple Oxygen Vacancies on Ceria for Electrocatalytic CO ₂ Reduction to CH ₄
journal, June 2018

Domino electroreduction of CO2 to methanol on a molecular catalyst
journal, November 2019

Advantages of CO over CO2 as reactant for electrochemical reduction to ethylene, ethanol and n-propanol on gas diffusion electrodes at high current densities
journal, June 2019

Atomically dispersed manganese catalysts for oxygen reduction in proton-exchange membrane fuel cells
journal, October 2018

Intermetallic Alloys as CO Electroreduction Catalysts—Role of Isolated Active Sites
journal, May 2014

Ensemble Effect in Bimetallic Electrocatalysts for CO ₂ Reduction
journal, September 2019

–CH ₃ Mediated Pathway for the Electroreduction of CO ₂ to Ethane and Ethanol on Thick Oxide-Derived Copper Catalysts at Low Overpotentials
journal, August 2017

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

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

Atomic site electrocatalysts for water splitting, oxygen reduction and selective oxidation
journal, January 2020

Copper Nanocubes for CO ₂ Reduction in Gas Diffusion Electrodes
journal, October 2019

Molecular Scaffolding Strategy with Synergistic Active Centers To Facilitate Electrocatalytic CO ₂ Reduction to Hydrocarbon/Alcohol
journal, November 2017

Golden single-atomic-site platinum electrocatalysts
journal, September 2018

Designing materials for electrochemical carbon dioxide recycling
journal, July 2019

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

Carbon monoxide electroreduction as an emerging platform for carbon utilization
journal, December 2019

Recent Advances in Atomic‐Level Engineering of Nanostructured Catalysts for Electrochemical CO ₂ Reduction
journal, March 2020

Covalent Triazine Framework Confined Copper Catalysts for Selective Electrochemical CO ₂ Reduction: Operando Diagnosis of Active Sites
journal, March 2020

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

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

Molecular tuning of CO2-to-ethylene conversion
journal, November 2019

Two-dimensional copper nanosheets for electrochemical reduction of carbon monoxide to acetate
journal, April 2019

Building Blocks for High Performance in Electrocatalytic CO ₂ Reduction: Materials, Optimization Strategies, and Device Engineering
journal, August 2017

Cu-based nanocatalysts for electrochemical reduction of CO2
journal, August 2018

Net reduction of CO2 via its thermocatalytic and electrocatalytic transformation reactions in standard and hybrid processes
journal, April 2019

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

CO ₂ electrolysis to multicarbon products at activities greater than 1 A cm ⁻²
journal, February 2020

Effectively Increased Efficiency for Electroreduction of Carbon Monoxide Using Supported Polycrystalline Copper Powder Electrocatalysts
journal, April 2019

Size‐Dependent Activity and Selectivity of Atomic‐Level Copper Nanoclusters during CO/CO ₂ Electroreduction
journal, October 2020

Activity Descriptors for CO ₂ Electroreduction to Methane on Transition-Metal Catalysts
journal, January 2012

Strategies for Stabilizing Atomically Dispersed Metal Catalysts
journal, December 2017

Highly dispersed, single-site copper catalysts for the electroreduction of CO2 to methane
journal, October 2020

A Graphene‐Supported Single‐Atom FeN ₅ Catalytic Site for Efficient Electrochemical CO ₂ Reduction
journal, October 2019

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

Atomically Defined Undercoordinated Active Sites for Highly Efficient CO ₂ Electroreduction
journal, November 2019

Atomically dispersed platinum supported on curved carbon supports for efficient electrocatalytic hydrogen evolution
journal, June 2019

Preassembly Strategy To Fabricate Porous Hollow Carbonitride Spheres Inlaid with Single Cu–N ₃ Sites for Selective Oxidation of Benzene to Phenol
journal, November 2018

Shape-Dependent Electrocatalytic Reduction of CO ₂ to CO on Triangular Silver Nanoplates
journal, February 2017

Single Cobalt Atoms with Precise N-Coordination as Superior Oxygen Reduction Reaction Catalysts
journal, August 2016

Mild oxidation of methane to methanol or acetic acid on supported isolated rhodium catalysts
journal, November 2017

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

One-step electrosynthesis of ethylene and ethanol from CO2 in an alkaline electrolyzer
journal, January 2016