NHC-CDI Ligands Boost Multicarbon Production in Electrocatalytic CO2 Reduction by Increasing Accumulated Charged Intermediates and Promoting *CO Dimerization on Cu

Kirstine Nygaard Kolding; Matias Bretlau; Siqi Zhao; Marcel Ceccato; Kristian Torbensen; Kim Daasbjerg; Alonso Rosas-Hernández

doi:10.1021/jacs.3c14306

NHC-CDI Ligands Boost Multicarbon Production in Electrocatalytic CO₂ Reduction by Increasing Accumulated Charged Intermediates and Promoting *CO Dimerization on Cu

Kirstine Nygaard Kolding, Matias Bretlau, Siqi Zhao, Marcel Ceccato, Kristian Torbensen, Kim Daasbjerg, Alonso Rosas-Hernández^*

^*Corresponding author for this work

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

7 Citations (Scopus)

Abstract

Copper-based materials exhibit significant potential as catalysts for electrochemical CO2 reduction, owing to their capacity to generate multicarbon hydrocarbons. The molecular functionalization of Cu electrodes represents a simple yet powerful strategy for improving the intrinsic activity of these materials by favoring specific reaction pathways through the creation of tailored microenvironments around the surface active sites. However, despite its success, comprehensive mechanistic insights derived from experimental techniques are often limited, leaving the active role of surface modifiers inconclusive. In this work, we show that N-heterocyclic carbene-carbodiimide-functionalized Cu catalysts display a remarkable activity for multicarbon product formation, surpassing bare Cu electrodes by more than an order of magnitude. These hybrid catalysts operate efficiently using an electrolyzer equipped with a gas diffusion electrode, achieving a multicarbon product selectivity of 58% with a partial current density of ca. -80 mA cm-2. We found that the activity for multicarbon product formation is closely linked to the surface charge that accumulates during electrocatalysis, stemming from surface intermediate buildup. Through X-ray photoelectron spectroscopy, we elucidated the role of the molecular additives in altering the electronic structure of the Cu electrodes, promoting the stabilization of surface CO. Additionally, in situ Raman measurements established the identity of the reaction intermediates that accumulate during electrocatalysis, indicating preferential CO binding on Cu step sites, known for facilitating C-C coupling. This study underscores the significant potential of molecular surface modifications in developing efficient electrocatalysts for CO2 reduction, highlighting surface charge as a pivotal descriptor of multicarbon product activity.

Original language	English
Journal	Journal of the American Chemical Society
Volume	146
Issue	19
Pages (from-to)	13034-13045
Number of pages	12
ISSN	0002-7863
DOIs	https://doi.org/10.1021/jacs.3c14306
Publication status	Published - May 2024

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Kolding, K. N., Bretlau, M., Zhao, S., Ceccato, M., Torbensen, K., Daasbjerg, K., & Rosas-Hernández, A. (2024). NHC-CDI Ligands Boost Multicarbon Production in Electrocatalytic CO₂ Reduction by Increasing Accumulated Charged Intermediates and Promoting *CO Dimerization on Cu. Journal of the American Chemical Society, 146(19), 13034-13045. https://doi.org/10.1021/jacs.3c14306

@article{31cc4460ccca455abb57d01877b0b1ca,

title = "NHC-CDI Ligands Boost Multicarbon Production in Electrocatalytic CO2 Reduction by Increasing Accumulated Charged Intermediates and Promoting *CO Dimerization on Cu",

abstract = "Copper-based materials exhibit significant potential as catalysts for electrochemical CO2 reduction, owing to their capacity to generate multicarbon hydrocarbons. The molecular functionalization of Cu electrodes represents a simple yet powerful strategy for improving the intrinsic activity of these materials by favoring specific reaction pathways through the creation of tailored microenvironments around the surface active sites. However, despite its success, comprehensive mechanistic insights derived from experimental techniques are often limited, leaving the active role of surface modifiers inconclusive. In this work, we show that N-heterocyclic carbene-carbodiimide-functionalized Cu catalysts display a remarkable activity for multicarbon product formation, surpassing bare Cu electrodes by more than an order of magnitude. These hybrid catalysts operate efficiently using an electrolyzer equipped with a gas diffusion electrode, achieving a multicarbon product selectivity of 58% with a partial current density of ca. -80 mA cm-2. We found that the activity for multicarbon product formation is closely linked to the surface charge that accumulates during electrocatalysis, stemming from surface intermediate buildup. Through X-ray photoelectron spectroscopy, we elucidated the role of the molecular additives in altering the electronic structure of the Cu electrodes, promoting the stabilization of surface CO. Additionally, in situ Raman measurements established the identity of the reaction intermediates that accumulate during electrocatalysis, indicating preferential CO binding on Cu step sites, known for facilitating C-C coupling. This study underscores the significant potential of molecular surface modifications in developing efficient electrocatalysts for CO2 reduction, highlighting surface charge as a pivotal descriptor of multicarbon product activity.",

author = "Kolding, {Kirstine Nygaard} and Matias Bretlau and Siqi Zhao and Marcel Ceccato and Kristian Torbensen and Kim Daasbjerg and Alonso Rosas-Hern{\'a}ndez",

year = "2024",

month = may,

doi = "10.1021/jacs.3c14306",

language = "English",

volume = "146",

pages = "13034--13045",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

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Kolding, KN , Bretlau, M, Zhao, S, Ceccato, M , Torbensen, K , Daasbjerg, K & Rosas-Hernández, A 2024, 'NHC-CDI Ligands Boost Multicarbon Production in Electrocatalytic CO₂ Reduction by Increasing Accumulated Charged Intermediates and Promoting *CO Dimerization on Cu', Journal of the American Chemical Society, vol. 146, no. 19, pp. 13034-13045. https://doi.org/10.1021/jacs.3c14306

NHC-CDI Ligands Boost Multicarbon Production in Electrocatalytic CO₂ Reduction by Increasing Accumulated Charged Intermediates and Promoting *CO Dimerization on Cu. / Kolding, Kirstine Nygaard ; Bretlau, Matias; Zhao, Siqi et al.
In: Journal of the American Chemical Society, Vol. 146, No. 19, 05.2024, p. 13034-13045.

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

TY - JOUR

T1 - NHC-CDI Ligands Boost Multicarbon Production in Electrocatalytic CO2 Reduction by Increasing Accumulated Charged Intermediates and Promoting *CO Dimerization on Cu

AU - Kolding, Kirstine Nygaard

AU - Bretlau, Matias

AU - Zhao, Siqi

AU - Ceccato, Marcel

AU - Torbensen, Kristian

AU - Daasbjerg, Kim

AU - Rosas-Hernández, Alonso

PY - 2024/5

Y1 - 2024/5

N2 - Copper-based materials exhibit significant potential as catalysts for electrochemical CO2 reduction, owing to their capacity to generate multicarbon hydrocarbons. The molecular functionalization of Cu electrodes represents a simple yet powerful strategy for improving the intrinsic activity of these materials by favoring specific reaction pathways through the creation of tailored microenvironments around the surface active sites. However, despite its success, comprehensive mechanistic insights derived from experimental techniques are often limited, leaving the active role of surface modifiers inconclusive. In this work, we show that N-heterocyclic carbene-carbodiimide-functionalized Cu catalysts display a remarkable activity for multicarbon product formation, surpassing bare Cu electrodes by more than an order of magnitude. These hybrid catalysts operate efficiently using an electrolyzer equipped with a gas diffusion electrode, achieving a multicarbon product selectivity of 58% with a partial current density of ca. -80 mA cm-2. We found that the activity for multicarbon product formation is closely linked to the surface charge that accumulates during electrocatalysis, stemming from surface intermediate buildup. Through X-ray photoelectron spectroscopy, we elucidated the role of the molecular additives in altering the electronic structure of the Cu electrodes, promoting the stabilization of surface CO. Additionally, in situ Raman measurements established the identity of the reaction intermediates that accumulate during electrocatalysis, indicating preferential CO binding on Cu step sites, known for facilitating C-C coupling. This study underscores the significant potential of molecular surface modifications in developing efficient electrocatalysts for CO2 reduction, highlighting surface charge as a pivotal descriptor of multicarbon product activity.

AB - Copper-based materials exhibit significant potential as catalysts for electrochemical CO2 reduction, owing to their capacity to generate multicarbon hydrocarbons. The molecular functionalization of Cu electrodes represents a simple yet powerful strategy for improving the intrinsic activity of these materials by favoring specific reaction pathways through the creation of tailored microenvironments around the surface active sites. However, despite its success, comprehensive mechanistic insights derived from experimental techniques are often limited, leaving the active role of surface modifiers inconclusive. In this work, we show that N-heterocyclic carbene-carbodiimide-functionalized Cu catalysts display a remarkable activity for multicarbon product formation, surpassing bare Cu electrodes by more than an order of magnitude. These hybrid catalysts operate efficiently using an electrolyzer equipped with a gas diffusion electrode, achieving a multicarbon product selectivity of 58% with a partial current density of ca. -80 mA cm-2. We found that the activity for multicarbon product formation is closely linked to the surface charge that accumulates during electrocatalysis, stemming from surface intermediate buildup. Through X-ray photoelectron spectroscopy, we elucidated the role of the molecular additives in altering the electronic structure of the Cu electrodes, promoting the stabilization of surface CO. Additionally, in situ Raman measurements established the identity of the reaction intermediates that accumulate during electrocatalysis, indicating preferential CO binding on Cu step sites, known for facilitating C-C coupling. This study underscores the significant potential of molecular surface modifications in developing efficient electrocatalysts for CO2 reduction, highlighting surface charge as a pivotal descriptor of multicarbon product activity.

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U2 - 10.1021/jacs.3c14306

DO - 10.1021/jacs.3c14306

M3 - Journal article

C2 - 38698544

SN - 0002-7863

VL - 146

SP - 13034

EP - 13045

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 19

ER -

NHC-CDI Ligands Boost Multicarbon Production in Electrocatalytic CO₂ Reduction by Increasing Accumulated Charged Intermediates and Promoting *CO Dimerization on Cu

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