Cationic-group-functionalized electrocatalysts enable stable acidic CO2 electrolysis

Mengyang Fan; Jianan Erick Huang; Rui Kai Miao; Yu Mao; Pengfei Ou; Feng Li; Xiao Yan Li; Yufei Cao; Zishuai Zhang; Jinqiang Zhang; Yu Yan; Adnan Ozden; Weiyan Ni; Ying Wang; Yong Zhao; Zhu Chen; Behrooz Khatir; Colin P. O’Brien; Yi Xu; Yurou Celine Xiao; Geoffrey I.N. Waterhouse; Kevin Golovin; Ziyun Wang; Edward H. Sargent; David Sinton

doi:10.1038/s41929-023-01003-5

Cationic-group-functionalized electrocatalysts enable stable acidic CO₂ electrolysis

Mengyang Fan, Jianan Erick Huang, Rui Kai Miao, Yu Mao, Pengfei Ou, Feng Li, Xiao Yan Li, Yufei Cao, Zishuai Zhang, Jinqiang Zhang, Yu Yan, Adnan Ozden, Weiyan Ni, Ying Wang, Yong Zhao, Zhu Chen, Behrooz Khatir, Colin P. O’Brien, Yi Xu, Yurou Celine XiaoGeoffrey I.N. Waterhouse, Kevin Golovin, Ziyun Wang^*, Edward H. Sargent^*, David Sinton^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

135 Scopus citations

Abstract

Acidic electrochemical CO₂ reduction (CO₂R) addresses CO₂ loss and thus mitigates the energy penalties associated with CO₂ recovery; however, acidic CO₂R suffers low selectivity. One promising remedy—using a high concentration of alkali cations—steers CO₂R towards multi-carbon (C₂₊) products, but these same alkali cations result in salt formation, limiting operating stability to <15 h. Here we present a copper catalyst functionalized with cationic groups (CG) that enables efficient CO₂ activation in a stable manner. By replacing alkali cations with immobilized benzimidazolium CG within ionomer coatings, we achieve over 150 h of stable CO₂R in acid. We find the water-management property of CG minimizes proton migration that enables operation at a modest voltage of 3.3 V with mildly alkaline local pH, leading to more energy-efficient CO₂R with a C₂₊ Faradaic efficiency of 80 ± 3%. As a result, we report an energy efficiency of 28% for acidic CO₂R towards C₂₊ products and a single-pass CO₂ conversion efficiency exceeding 70%. [Figure not available: see fulltext.]

Original language	English (US)
Pages (from-to)	763-772
Number of pages	10
Journal	Nature Catalysis
Volume	6
Issue number	9
DOIs	https://doi.org/10.1038/s41929-023-01003-5
State	Published - Sep 2023

Funding

We acknowledge support from the Natural Sciences and Engineering Research Council (NSERC) of Canada and TotalEnergies SE. Support from Canada Research Chairs Program is also gratefully acknowledged. Infrastructure provided through the Canada Foundation for Innovation and the Ontario Research Fund supported the work. R.K.M. thanks NSERC, Hatch and the Government of Ontario for their support through graduate scholarships. P.O. thanks the Climate Positive Energy for its support through Rising Stars in Clean Energy Postdoctoral Fellowship. Density functional theory calculations were performed on the Niagara supercomputer at the SciNet HPC Consortium. SciNet is funded by: the Canada Foundation for Innovation; the Government of Ontario; Ontario Research Fund - Research Excellence; and the University of Toronto. The computational study is supported by the Marsden Fund Council from Government funding (21-UOA-237) and Catalyst: Seeding General Grant (22-UOA-031-CGS), managed by Royal Society Te Apārangi. Z.W. and Y.M. acknowledge the use of New Zealand eScience Infrastructure (NeSI) high-performance computing facilities, consulting support and/or training services as part of this research. G.I.N.W. and Y.M. acknowledge funding support from the MacDiarmid Institute for Advanced Materials and Nanotechnology, the Energy Education Trust of New Zealand and the Royal Society Te Apārangi. Z.W. and Y.M. graciously acknowledge D. J. Searles (University of Queensland) and J. Cheng (Xiamen University) for their support and scientific discussions on the computational work. We acknowledge support from the Natural Sciences and Engineering Research Council (NSERC) of Canada and TotalEnergies SE. Support from Canada Research Chairs Program is also gratefully acknowledged. Infrastructure provided through the Canada Foundation for Innovation and the Ontario Research Fund supported the work. R.K.M. thanks NSERC, Hatch and the Government of Ontario for their support through graduate scholarships. P.O. thanks the Climate Positive Energy for its support through Rising Stars in Clean Energy Postdoctoral Fellowship. Density functional theory calculations were performed on the Niagara supercomputer at the SciNet HPC Consortium. SciNet is funded by: the Canada Foundation for Innovation; the Government of Ontario; Ontario Research Fund - Research Excellence; and the University of Toronto. The computational study is supported by the Marsden Fund Council from Government funding (21-UOA-237) and Catalyst: Seeding General Grant (22-UOA-031-CGS), managed by Royal Society Te Apārangi. Z.W. and Y.M. acknowledge the use of New Zealand eScience Infrastructure (NeSI) high-performance computing facilities, consulting support and/or training services as part of this research. G.I.N.W. and Y.M. acknowledge funding support from the MacDiarmid Institute for Advanced Materials and Nanotechnology, the Energy Education Trust of New Zealand and the Royal Society Te Apārangi. Z.W. and Y.M. graciously acknowledge D. J. Searles (University of Queensland) and J. Cheng (Xiamen University) for their support and scientific discussions on the computational work.

ASJC Scopus subject areas

Catalysis
Bioengineering
Biochemistry
Process Chemistry and Technology

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This output contributes to the following UN Sustainable Development Goals (SDGs)

Access to Document

10.1038/s41929-023-01003-5

Cite this

Fan, M., Huang, J. E., Miao, R. K., Mao, Y., Ou, P., Li, F., Li, X. Y., Cao, Y., Zhang, Z., Zhang, J., Yan, Y., Ozden, A., Ni, W., Wang, Y., Zhao, Y., Chen, Z., Khatir, B., O’Brien, C. P., Xu, Y., ... Sinton, D. (2023). Cationic-group-functionalized electrocatalysts enable stable acidic CO₂ electrolysis. Nature Catalysis, 6(9), 763-772. https://doi.org/10.1038/s41929-023-01003-5

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title = "Cationic-group-functionalized electrocatalysts enable stable acidic CO2 electrolysis",

abstract = "Acidic electrochemical CO2 reduction (CO2R) addresses CO2 loss and thus mitigates the energy penalties associated with CO2 recovery; however, acidic CO2R suffers low selectivity. One promising remedy—using a high concentration of alkali cations—steers CO2R towards multi-carbon (C2+) products, but these same alkali cations result in salt formation, limiting operating stability to <15 h. Here we present a copper catalyst functionalized with cationic groups (CG) that enables efficient CO2 activation in a stable manner. By replacing alkali cations with immobilized benzimidazolium CG within ionomer coatings, we achieve over 150 h of stable CO2R in acid. We find the water-management property of CG minimizes proton migration that enables operation at a modest voltage of 3.3 V with mildly alkaline local pH, leading to more energy-efficient CO2R with a C2+ Faradaic efficiency of 80 ± 3%. As a result, we report an energy efficiency of 28% for acidic CO2R towards C2+ products and a single-pass CO2 conversion efficiency exceeding 70%. [Figure not available: see fulltext.]",

author = "Mengyang Fan and Huang, {Jianan Erick} and Miao, {Rui Kai} and Yu Mao and Pengfei Ou and Feng Li and Li, {Xiao Yan} and Yufei Cao and Zishuai Zhang and Jinqiang Zhang and Yu Yan and Adnan Ozden and Weiyan Ni and Ying Wang and Yong Zhao and Zhu Chen and Behrooz Khatir and O{\textquoteright}Brien, {Colin P.} and Yi Xu and Xiao, {Yurou Celine} and Waterhouse, {Geoffrey I.N.} and Kevin Golovin and Ziyun Wang and Sargent, {Edward H.} and David Sinton",

note = "Publisher Copyright: {\textcopyright} 2023, The Author(s), under exclusive licence to Springer Nature Limited.",

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Fan, M, Huang, JE, Miao, RK, Mao, Y, Ou, P, Li, F, Li, XY, Cao, Y, Zhang, Z, Zhang, J, Yan, Y, Ozden, A, Ni, W, Wang, Y, Zhao, Y, Chen, Z, Khatir, B, O’Brien, CP, Xu, Y, Xiao, YC, Waterhouse, GIN, Golovin, K, Wang, Z, Sargent, EH & Sinton, D 2023, 'Cationic-group-functionalized electrocatalysts enable stable acidic CO₂ electrolysis', Nature Catalysis, vol. 6, no. 9, pp. 763-772. https://doi.org/10.1038/s41929-023-01003-5

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T1 - Cationic-group-functionalized electrocatalysts enable stable acidic CO2 electrolysis

AU - Fan, Mengyang

AU - Huang, Jianan Erick

AU - Miao, Rui Kai

AU - Mao, Yu

AU - Ou, Pengfei

AU - Li, Feng

AU - Li, Xiao Yan

AU - Cao, Yufei

AU - Zhang, Zishuai

AU - Zhang, Jinqiang

AU - Yan, Yu

AU - Ozden, Adnan

AU - Ni, Weiyan

AU - Wang, Ying

AU - Zhao, Yong

AU - Chen, Zhu

AU - Khatir, Behrooz

AU - O’Brien, Colin P.

AU - Xu, Yi

AU - Xiao, Yurou Celine

AU - Waterhouse, Geoffrey I.N.

AU - Golovin, Kevin

AU - Wang, Ziyun

AU - Sargent, Edward H.

AU - Sinton, David

PY - 2023/9

Y1 - 2023/9

N2 - Acidic electrochemical CO2 reduction (CO2R) addresses CO2 loss and thus mitigates the energy penalties associated with CO2 recovery; however, acidic CO2R suffers low selectivity. One promising remedy—using a high concentration of alkali cations—steers CO2R towards multi-carbon (C2+) products, but these same alkali cations result in salt formation, limiting operating stability to <15 h. Here we present a copper catalyst functionalized with cationic groups (CG) that enables efficient CO2 activation in a stable manner. By replacing alkali cations with immobilized benzimidazolium CG within ionomer coatings, we achieve over 150 h of stable CO2R in acid. We find the water-management property of CG minimizes proton migration that enables operation at a modest voltage of 3.3 V with mildly alkaline local pH, leading to more energy-efficient CO2R with a C2+ Faradaic efficiency of 80 ± 3%. As a result, we report an energy efficiency of 28% for acidic CO2R towards C2+ products and a single-pass CO2 conversion efficiency exceeding 70%. [Figure not available: see fulltext.]

AB - Acidic electrochemical CO2 reduction (CO2R) addresses CO2 loss and thus mitigates the energy penalties associated with CO2 recovery; however, acidic CO2R suffers low selectivity. One promising remedy—using a high concentration of alkali cations—steers CO2R towards multi-carbon (C2+) products, but these same alkali cations result in salt formation, limiting operating stability to <15 h. Here we present a copper catalyst functionalized with cationic groups (CG) that enables efficient CO2 activation in a stable manner. By replacing alkali cations with immobilized benzimidazolium CG within ionomer coatings, we achieve over 150 h of stable CO2R in acid. We find the water-management property of CG minimizes proton migration that enables operation at a modest voltage of 3.3 V with mildly alkaline local pH, leading to more energy-efficient CO2R with a C2+ Faradaic efficiency of 80 ± 3%. As a result, we report an energy efficiency of 28% for acidic CO2R towards C2+ products and a single-pass CO2 conversion efficiency exceeding 70%. [Figure not available: see fulltext.]

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