Electron delocalization engineering via hierarchical modulation in single-atom catalysts for highly efficient electrochemical CO2 reduction

Xu Han; Hong Liu; Pengfei Cao; Weiqiang Tang; Chao Yue Zhang; Martí Biset-Peiró; Ke Xiao; Pengyi Tang; Marc Heggen; Miquel Vega-Paredes; Alba Garzón Manjón; Lirong Zheng; Rafal E. Dunin-Borkowski; Andreu Cabot; Kim Daasbjerg; Joan Ramon Morante; Ting Zhang; Jordi Arbiol

doi:10.1016/j.cej.2025.160634

Electron delocalization engineering via hierarchical modulation in single-atom catalysts for highly efficient electrochemical CO₂ reduction

Xu Han, Hong Liu^*, Pengfei Cao, Weiqiang Tang, Chao Yue Zhang, Martí Biset-Peiró, Ke Xiao, Pengyi Tang, Marc Heggen, Miquel Vega-Paredes, Alba Garzón Manjón, Lirong Zheng^*, Rafal E. Dunin-Borkowski, Andreu Cabot, Kim Daasbjerg, Joan Ramon Morante, Ting Zhang^*, Jordi Arbiol^*

^*Corresponding author for this work

Research output: Contribution to journal/Conference contribution in journal/Contribution to newspaper › Journal article › Research › peer-review

Abstract

Modulating the coordination of atomically dispersed MN₄ moieties to enhance electron asymmetry presents a promising strategy for improving catalytic performance in the electrochemical reduction of carbon dioxide (eCO₂RR). By combining small amounts of Au nanoclusters with lateral oxygen coordination in the first coordination shell, the enhanced electron delocalization on Ni centers improves both activity and selectivity. Experimentally, the optimized catalyst demonstrates exceptional catalytic performance, achieving over 95% Faradaic efficiency (FE) for CO across a broad potential range from − 0.50 to − 0.85 V vs. RHE. It also achieves over 90% FE for CO at an overpotential of 340 mV, outperforming state-of-the-art Ni-based single-atom catalysts (SACs). Moreover, the catalyst shows promising potential at a higher current density (∼150 mA cm⁻²) in a flow cell, maintaining high CO selectivity (over 90%). Structural characterizations and theoretical calculations indicate that this structure enhances electron redistribution around Ni sites through a unique electron tug effect. This effectively stabilizes *COOH intermediates, favoring CO production during eCO₂RR at low applied potentials. This work offers a valuable method that extends beyond the first coordination shell, augmenting the complexity of electronic distribution on metal centers, which could be adapted for further fine-tuning the catalytic behavior of SACs in various reactions.

Original language	English
Article number	160634
Journal	Chemical Engineering Journal
Volume	507
Number of pages	10
ISSN	1385-8947
DOIs	https://doi.org/10.1016/j.cej.2025.160634
Publication status	Published - Mar 2025

Keywords

Au nanoclusters
CO electroreduction
Electron tug effect
High CO selectivity
Single atom catalysts
Wide potential range

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10.1016/j.cej.2025.160634

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Han, X., Liu, H., Cao, P., Tang, W., Zhang, C. Y., Biset-Peiró, M., Xiao, K., Tang, P., Heggen, M., Vega-Paredes, M., Garzón Manjón, A., Zheng, L., Dunin-Borkowski, R. E., Cabot, A., Daasbjerg, K., Morante, J. R., Zhang, T., & Arbiol, J. (2025). Electron delocalization engineering via hierarchical modulation in single-atom catalysts for highly efficient electrochemical CO₂ reduction. Chemical Engineering Journal, 507, Article 160634. https://doi.org/10.1016/j.cej.2025.160634

@article{5cf3bca68cb3456bbdcc1121262312be,

title = "Electron delocalization engineering via hierarchical modulation in single-atom catalysts for highly efficient electrochemical CO2 reduction",

abstract = "Modulating the coordination of atomically dispersed MN4 moieties to enhance electron asymmetry presents a promising strategy for improving catalytic performance in the electrochemical reduction of carbon dioxide (eCO2RR). By combining small amounts of Au nanoclusters with lateral oxygen coordination in the first coordination shell, the enhanced electron delocalization on Ni centers improves both activity and selectivity. Experimentally, the optimized catalyst demonstrates exceptional catalytic performance, achieving over 95% Faradaic efficiency (FE) for CO across a broad potential range from − 0.50 to − 0.85 V vs. RHE. It also achieves over 90% FE for CO at an overpotential of 340 mV, outperforming state-of-the-art Ni-based single-atom catalysts (SACs). Moreover, the catalyst shows promising potential at a higher current density (∼150 mA cm−2) in a flow cell, maintaining high CO selectivity (over 90%). Structural characterizations and theoretical calculations indicate that this structure enhances electron redistribution around Ni sites through a unique electron tug effect. This effectively stabilizes *COOH intermediates, favoring CO production during eCO2RR at low applied potentials. This work offers a valuable method that extends beyond the first coordination shell, augmenting the complexity of electronic distribution on metal centers, which could be adapted for further fine-tuning the catalytic behavior of SACs in various reactions.",

keywords = "Au nanoclusters, CO electroreduction, Electron tug effect, High CO selectivity, Single atom catalysts, Wide potential range",

author = "Xu Han and Hong Liu and Pengfei Cao and Weiqiang Tang and Zhang, {Chao Yue} and Mart{\'i} Biset-Peir{\'o} and Ke Xiao and Pengyi Tang and Marc Heggen and Miquel Vega-Paredes and {Garz{\'o}n Manj{\'o}n}, Alba and Lirong Zheng and Dunin-Borkowski, {Rafal E.} and Andreu Cabot and Kim Daasbjerg and Morante, {Joan Ramon} and Ting Zhang and Jordi Arbiol",

note = "Publisher Copyright: {\textcopyright} 2025 Elsevier B.V.",

year = "2025",

month = mar,

doi = "10.1016/j.cej.2025.160634",

language = "English",

volume = "507",

journal = "Chemical Engineering Journal",

issn = "1385-8947",

publisher = "Elsevier B.V.",

}

Han, X, Liu, H, Cao, P, Tang, W, Zhang, CY, Biset-Peiró, M, Xiao, K, Tang, P, Heggen, M, Vega-Paredes, M, Garzón Manjón, A, Zheng, L, Dunin-Borkowski, RE, Cabot, A, Daasbjerg, K, Morante, JR, Zhang, T & Arbiol, J 2025, 'Electron delocalization engineering via hierarchical modulation in single-atom catalysts for highly efficient electrochemical CO₂ reduction', Chemical Engineering Journal, vol. 507, 160634. https://doi.org/10.1016/j.cej.2025.160634

Electron delocalization engineering via hierarchical modulation in single-atom catalysts for highly efficient electrochemical CO₂ reduction. / Han, Xu; Liu, Hong; Cao, Pengfei et al.
In: Chemical Engineering Journal, Vol. 507, 160634, 03.2025.

Research output: Contribution to journal/Conference contribution in journal/Contribution to newspaper › Journal article › Research › peer-review

TY - JOUR

T1 - Electron delocalization engineering via hierarchical modulation in single-atom catalysts for highly efficient electrochemical CO2 reduction

AU - Han, Xu

AU - Liu, Hong

AU - Cao, Pengfei

AU - Tang, Weiqiang

AU - Zhang, Chao Yue

AU - Biset-Peiró, Martí

AU - Xiao, Ke

AU - Tang, Pengyi

AU - Heggen, Marc

AU - Vega-Paredes, Miquel

AU - Garzón Manjón, Alba

AU - Zheng, Lirong

AU - Dunin-Borkowski, Rafal E.

AU - Cabot, Andreu

AU - Daasbjerg, Kim

AU - Morante, Joan Ramon

AU - Zhang, Ting

AU - Arbiol, Jordi

PY - 2025/3

Y1 - 2025/3

N2 - Modulating the coordination of atomically dispersed MN4 moieties to enhance electron asymmetry presents a promising strategy for improving catalytic performance in the electrochemical reduction of carbon dioxide (eCO2RR). By combining small amounts of Au nanoclusters with lateral oxygen coordination in the first coordination shell, the enhanced electron delocalization on Ni centers improves both activity and selectivity. Experimentally, the optimized catalyst demonstrates exceptional catalytic performance, achieving over 95% Faradaic efficiency (FE) for CO across a broad potential range from − 0.50 to − 0.85 V vs. RHE. It also achieves over 90% FE for CO at an overpotential of 340 mV, outperforming state-of-the-art Ni-based single-atom catalysts (SACs). Moreover, the catalyst shows promising potential at a higher current density (∼150 mA cm−2) in a flow cell, maintaining high CO selectivity (over 90%). Structural characterizations and theoretical calculations indicate that this structure enhances electron redistribution around Ni sites through a unique electron tug effect. This effectively stabilizes *COOH intermediates, favoring CO production during eCO2RR at low applied potentials. This work offers a valuable method that extends beyond the first coordination shell, augmenting the complexity of electronic distribution on metal centers, which could be adapted for further fine-tuning the catalytic behavior of SACs in various reactions.

AB - Modulating the coordination of atomically dispersed MN4 moieties to enhance electron asymmetry presents a promising strategy for improving catalytic performance in the electrochemical reduction of carbon dioxide (eCO2RR). By combining small amounts of Au nanoclusters with lateral oxygen coordination in the first coordination shell, the enhanced electron delocalization on Ni centers improves both activity and selectivity. Experimentally, the optimized catalyst demonstrates exceptional catalytic performance, achieving over 95% Faradaic efficiency (FE) for CO across a broad potential range from − 0.50 to − 0.85 V vs. RHE. It also achieves over 90% FE for CO at an overpotential of 340 mV, outperforming state-of-the-art Ni-based single-atom catalysts (SACs). Moreover, the catalyst shows promising potential at a higher current density (∼150 mA cm−2) in a flow cell, maintaining high CO selectivity (over 90%). Structural characterizations and theoretical calculations indicate that this structure enhances electron redistribution around Ni sites through a unique electron tug effect. This effectively stabilizes *COOH intermediates, favoring CO production during eCO2RR at low applied potentials. This work offers a valuable method that extends beyond the first coordination shell, augmenting the complexity of electronic distribution on metal centers, which could be adapted for further fine-tuning the catalytic behavior of SACs in various reactions.

KW - Au nanoclusters

KW - CO electroreduction

KW - Electron tug effect

KW - High CO selectivity

KW - Single atom catalysts

KW - Wide potential range

UR - http://www.scopus.com/inward/record.url?scp=85217891095&partnerID=8YFLogxK

U2 - 10.1016/j.cej.2025.160634

DO - 10.1016/j.cej.2025.160634

M3 - Journal article

AN - SCOPUS:85217891095

SN - 1385-8947

VL - 507

JO - Chemical Engineering Journal

JF - Chemical Engineering Journal

M1 - 160634

ER -

Electron delocalization engineering via hierarchical modulation in single-atom catalysts for highly efficient electrochemical CO₂ reduction

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