Volume 64, Issue 24 e202505399

Communication

Dimensionality Reduction of Metal–Organic Frameworks to Monolayers for Enhanced Electrocatalysis

Zi Yang

Beijing National Laboratory for Molecular Science, State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871 China

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An Li,

An Li

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Hao Li,

Hao Li

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Guotao Lai,

Guotao Lai

Department of Chemistry, Southern University of Science and Technology, Shenzhen, Guangdong, 518055 China

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Yifan Fu,

Yifan Fu

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Yufeng Zhang,

Yufeng Zhang

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Kun Wang,

Kun Wang

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Senhai Zeng,

Senhai Zeng

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Lin Xie,

Lin Xie

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Mufan Li,

Mufan Li

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Jun Gu,

Corresponding Author

Jun Gu

[email protected]

Department of Chemistry, Southern University of Science and Technology, Shenzhen, Guangdong, 518055 China

Email: [email protected]; [email protected]

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Guangxu Lan,

Corresponding Author

Guangxu Lan

[email protected]

Email: [email protected]; [email protected]

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Zi Yang,

Zi Yang

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An Li,

An Li

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Hao Li,

Hao Li

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Guotao Lai,

Guotao Lai

Department of Chemistry, Southern University of Science and Technology, Shenzhen, Guangdong, 518055 China

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Yifan Fu,

Yifan Fu

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Yufeng Zhang,

Yufeng Zhang

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Kun Wang,

Kun Wang

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Senhai Zeng,

Senhai Zeng

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Lin Xie,

Lin Xie

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Mufan Li,

Mufan Li

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Jun Gu,

Corresponding Author

Jun Gu

[email protected]

Department of Chemistry, Southern University of Science and Technology, Shenzhen, Guangdong, 518055 China

Email: [email protected]; [email protected]

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Guangxu Lan,

Corresponding Author

Guangxu Lan

[email protected]

Email: [email protected]; [email protected]

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First published: 07 April 2025

https://doi.org/10.1002/anie.202505399

Citations: 1

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Graphical Abstract

Dimensionality reduction of 3D MOFs into 1.8-nm-thick monoMOF maximizes catalytic site exposure and enhances CO₂ electroreduction. The cobalt(II)–porphyrin-embedded monoMOF-Co achieves 93% CO Faradaic efficiency (versus 51% for 3D_MOF-Co) at −0.8 V versus RHE, with a 10,600 h⁻¹ turnover frequency and 47-hour stability in near-neutral electrolyte, demonstrating superior electron/mass transfer through dimensional engineering.

Abstract

Metal–organic frameworks (MOFs) are potential candidates for electrocatalysis due to their well-defined, tunable structures, and ability to incorporate diverse active sites. However, their inherent insulating nature restricts electron transfer from electrode to remote active sites, leading to diminished catalytic performance. In this work, we present a novel strategy to overcome this limitation by reducing 3D MOFs (3D_MOFs) into monolayered MOFs (monoMOFs) with a thickness of ∼1.8 nm, maximizing the exposure of catalytic sites to the electrode and enhancing electrocatalytic performance. We designed and synthesized a monoMOF incorporating cobalt(II)–porphyrin sites in the linker (monoMOF-Co) for CO₂ electroreduction. After being grafted onto graphene oxide, the monoMOF-Co exhibited a peak faradaic efficiency for CO production (FE_CO = 93%), surpassing the performance of a 3D_MOF incorporating the same porphyrin–Co-based linker (3D_MOF-Co, FE_CO = 51%). Additionally, monoMOF-Co achieved a turnover frequency of 10 600 h⁻¹ at −0.8 V versus the reversible hydrogen electrode (RHE) and maintained stability over 47 h in a near-neutral aqueous solution. In situ spectroscopic studies further confirmed the distinct electric field environment in the Stern layer between monoMOF-Co and 3D_MOF-Co. Furthermore, similar enhancement effects of monoMOFs over 3D_MOFs were observed in the nitrate and oxygen electroreduction reactions, highlighting the broader applicability of monoMOFs in electrocatalysis.

Conflict of Interests

The authors declare no conflict of interest.

Open Research

Data Availability Statement

The data that support the findings of this study are available from the corresponding author upon reasonable request.

Supporting Information

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Volume64, Issue24

June 10, 2025

e202505399

Dimensionality Reduction of Metal–Organic Frameworks to Monolayers for Enhanced Electrocatalysis

Graphical Abstract

Abstract

Conflict of Interests

Open Research

Data Availability Statement

Supporting Information

References

Citing Literature

References

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Dimensionality Reduction of Metal–Organic Frameworks to Monolayers for Enhanced Electrocatalysis

Graphical Abstract

Abstract

Conflict of Interests

Open Research

Data Availability Statement

Supporting Information

References

Citing Literature

References

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