Atomically Thin, Ionic–Covalent Organic Nanosheets for Stable, High-Performance Carbon Dioxide Electroreduction

Yun Song; Jun-Jie Zhang; Yubing Dou; Zhaohua Zhu; Jianjun Su; Libei Huang; Weihua Guo; Xiaohu Cao; Le Cheng; Zonglong Zhu; Zhenhua Zhang; Xiaoyan Zhong; Dengtao Yang; Zhaoyu Wang; Ben Zhong Tang; Boris I. Yakobson; Ruquan Ye

doi:10.1002/adma.202110496

Atomically Thin, Ionic–Covalent Organic Nanosheets for Stable, High-Performance Carbon Dioxide Electroreduction

Yun Song, Jun-Jie Zhang, Yubing Dou, Zhaohua Zhu, Jianjun Su, Libei Huang, Weihua Guo, Xiaohu Cao, Le Cheng, Zonglong Zhu, Zhenhua Zhang, Xiaoyan Zhong, Dengtao Yang^*, Zhaoyu Wang, Ben Zhong Tang, Boris I. Yakobson^*, Ruquan Ye^*

^*Corresponding author for this work

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

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Abstract

The incorporation of charged functional groups is effective to modulate the activity of molecular complexes for the CO₂ reduction reaction (CO₂RR), yet long-term heterogeneous electrolysis is often hampered by catalyst leaching. Herein, an electrocatalyst of atomically thin, cobalt-porphyrin-based, ionic–covalent organic nanosheets (CoTAP-iCONs) is synthesized via a post-synthetic modification strategy for high-performance CO₂-to-CO conversion. The cationic quaternary ammonium groups not only enable the formation of monolayer nanosheets due to steric hindrance and electrostatic repulsion, but also facilitate the formation of a *COOH intermediate, as suggested by theoretical calculations. Consequently, CoTAP-iCONs exhibit higher CO₂RR activity than other cobalt-porphyrin-based structures: an 870% and 480% improvement of CO current densities compared to the monomer and neutral nanosheets, respectively. Additionally, the iCONs structure can accommodate the cationic moieties. In a flow cell, CoTAP-iCONs attain a very small onset overpotential of 40 mV and a stable total current density of 212 mA cm^–2 with CO Faradaic efficiency of >95% at −0.6 V for 11 h. Further coupling the flow electrolyzer with commercial solar cells yields a solar-to-CO conversion efficiency of 13.89%. This work indicates that atom-thin, ionic nanosheets represent a promising structure for achieving both tailored activity and high stability.

Original language	English
Article number	2110496
Journal	Advanced Materials
Volume	34
Issue number	42
Online published	14 Sept 2022
DOIs	https://doi.org/10.1002/adma.202110496
Publication status	Published - 20 Oct 2022

Funding

R.Y. thanks the support from the Guangdong Basic and Applied Basic Research Fund (No. 2022A1515011333), the Science, Technology and Innovation Commission of Shenzhen under Shenzhen Virtual University Park Special Fund (No. 2021Szvup129), the Hong Kong Research Grant Council under Early Career Scheme (No. 21300620) and General Research Fund (No. 11307120), Shenzhen-Hong Kong-Macau Science and Technology Grant [type C; SGDX2020110309300301] from the Science, Technology and Innovation Commission of Shenzhen Municipality, and State Key Laboratory of Marine Pollution Seed Collaborative Research Fund (SKLMP/IRF/0029).

Research Keywords

carbon dioxide reduction
covalent organic frameworks
ionic nanosheets
positive charge
ultrathin materials

Publisher's Copyright Statement

COPYRIGHT TERMS OF DEPOSITED POSTPRINT FILE: This is the peer reviewed version of the following article: Song, Y., Zhang, J-J., Dou, Y., Zhu, Z., Su, J., Huang, L., Guo, W., Cao, X., Cheng, L., Zhu, Z., Zhang, Z., Zhong, X., Yang, D., Wang, Z., Tang, B. Z., Yakobson, B. I., & Ye, R. (2022). Atomically Thin, Ionic–Covalent Organic Nanosheets for Stable, High-Performance Carbon Dioxide Electroreduction. Advanced Materials, 34(42), [2110496], which has been published in final form at https://doi.org/10.1002/adma.202110496.
This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. This article may not be enhanced, enriched or otherwise transformed into a derivative work, without express permission from Wiley or by statutory rights under applicable legislation. Copyright notices must not be removed, obscured or modified. The article must be linked to Wiley’s version of record on Wiley Online Library and any embedding, framing or otherwise making available the article or pages thereof by third parties from platforms, services and websites other than Wiley Online Library must be prohibited.

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UN SDGs

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

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Song, Y., Zhang, J.-J., Dou, Y., Zhu, Z., Su, J., Huang, L., Guo, W., Cao, X., Cheng, L., Zhu, Z., Zhang, Z., Zhong, X., Yang, D., Wang, Z., Tang, B. Z., Yakobson, B. I., & Ye, R. (2022). Atomically Thin, Ionic–Covalent Organic Nanosheets for Stable, High-Performance Carbon Dioxide Electroreduction. Advanced Materials, 34(42), Article 2110496. https://doi.org/10.1002/adma.202110496

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abstract = "The incorporation of charged functional groups is effective to modulate the activity of molecular complexes for the CO2 reduction reaction (CO2RR), yet long-term heterogeneous electrolysis is often hampered by catalyst leaching. Herein, an electrocatalyst of atomically thin, cobalt-porphyrin-based, ionic–covalent organic nanosheets (CoTAP-iCONs) is synthesized via a post-synthetic modification strategy for high-performance CO2-to-CO conversion. The cationic quaternary ammonium groups not only enable the formation of monolayer nanosheets due to steric hindrance and electrostatic repulsion, but also facilitate the formation of a *COOH intermediate, as suggested by theoretical calculations. Consequently, CoTAP-iCONs exhibit higher CO2RR activity than other cobalt-porphyrin-based structures: an 870% and 480% improvement of CO current densities compared to the monomer and neutral nanosheets, respectively. Additionally, the iCONs structure can accommodate the cationic moieties. In a flow cell, CoTAP-iCONs attain a very small onset overpotential of 40 mV and a stable total current density of 212 mA cm–2 with CO Faradaic efficiency of >95% at −0.6 V for 11 h. Further coupling the flow electrolyzer with commercial solar cells yields a solar-to-CO conversion efficiency of 13.89%. This work indicates that atom-thin, ionic nanosheets represent a promising structure for achieving both tailored activity and high stability.",

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author = "Yun Song and Jun-Jie Zhang and Yubing Dou and Zhaohua Zhu and Jianjun Su and Libei Huang and Weihua Guo and Xiaohu Cao and Le Cheng and Zonglong Zhu and Zhenhua Zhang and Xiaoyan Zhong and Dengtao Yang and Zhaoyu Wang and Tang, {Ben Zhong} and Yakobson, {Boris I.} and Ruquan Ye",

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AU - Song, Yun

AU - Zhang, Jun-Jie

AU - Dou, Yubing

AU - Zhu, Zhaohua

AU - Su, Jianjun

AU - Huang, Libei

AU - Guo, Weihua

AU - Cao, Xiaohu

AU - Cheng, Le

AU - Zhu, Zonglong

AU - Zhang, Zhenhua

AU - Zhong, Xiaoyan

AU - Yang, Dengtao

AU - Wang, Zhaoyu

AU - Tang, Ben Zhong

AU - Yakobson, Boris I.

AU - Ye, Ruquan

PY - 2022/10/20

Y1 - 2022/10/20

N2 - The incorporation of charged functional groups is effective to modulate the activity of molecular complexes for the CO2 reduction reaction (CO2RR), yet long-term heterogeneous electrolysis is often hampered by catalyst leaching. Herein, an electrocatalyst of atomically thin, cobalt-porphyrin-based, ionic–covalent organic nanosheets (CoTAP-iCONs) is synthesized via a post-synthetic modification strategy for high-performance CO2-to-CO conversion. The cationic quaternary ammonium groups not only enable the formation of monolayer nanosheets due to steric hindrance and electrostatic repulsion, but also facilitate the formation of a *COOH intermediate, as suggested by theoretical calculations. Consequently, CoTAP-iCONs exhibit higher CO2RR activity than other cobalt-porphyrin-based structures: an 870% and 480% improvement of CO current densities compared to the monomer and neutral nanosheets, respectively. Additionally, the iCONs structure can accommodate the cationic moieties. In a flow cell, CoTAP-iCONs attain a very small onset overpotential of 40 mV and a stable total current density of 212 mA cm–2 with CO Faradaic efficiency of >95% at −0.6 V for 11 h. Further coupling the flow electrolyzer with commercial solar cells yields a solar-to-CO conversion efficiency of 13.89%. This work indicates that atom-thin, ionic nanosheets represent a promising structure for achieving both tailored activity and high stability.

AB - The incorporation of charged functional groups is effective to modulate the activity of molecular complexes for the CO2 reduction reaction (CO2RR), yet long-term heterogeneous electrolysis is often hampered by catalyst leaching. Herein, an electrocatalyst of atomically thin, cobalt-porphyrin-based, ionic–covalent organic nanosheets (CoTAP-iCONs) is synthesized via a post-synthetic modification strategy for high-performance CO2-to-CO conversion. The cationic quaternary ammonium groups not only enable the formation of monolayer nanosheets due to steric hindrance and electrostatic repulsion, but also facilitate the formation of a *COOH intermediate, as suggested by theoretical calculations. Consequently, CoTAP-iCONs exhibit higher CO2RR activity than other cobalt-porphyrin-based structures: an 870% and 480% improvement of CO current densities compared to the monomer and neutral nanosheets, respectively. Additionally, the iCONs structure can accommodate the cationic moieties. In a flow cell, CoTAP-iCONs attain a very small onset overpotential of 40 mV and a stable total current density of 212 mA cm–2 with CO Faradaic efficiency of >95% at −0.6 V for 11 h. Further coupling the flow electrolyzer with commercial solar cells yields a solar-to-CO conversion efficiency of 13.89%. This work indicates that atom-thin, ionic nanosheets represent a promising structure for achieving both tailored activity and high stability.

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KW - covalent organic frameworks

KW - ionic nanosheets

KW - positive charge

KW - ultrathin materials

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DO - 10.1002/adma.202110496

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SN - 0935-9648

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JO - Advanced Materials

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ER -

Atomically Thin, Ionic–Covalent Organic Nanosheets for Stable, High-Performance Carbon Dioxide Electroreduction

Abstract

Funding

Research Keywords

Publisher's Copyright Statement

RGC Funding Information

UN SDGs

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Permanent Link

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ECS: Investigating the Inductive Effect and Kinetics of Covalently Immobilized Molecular Catalysts for High-performance Electrochemical CO2 Reduction

GRF: Pre-Concentrating and Detecting Natural-Water Heavy Metals by Sulfur-Equipped Porous Crystals

Cite this

Atomically Thin, Ionic–Covalent Organic Nanosheets for Stable, High-Performance Carbon Dioxide Electroreduction

Abstract

Funding

Research Keywords

Publisher's Copyright Statement

RGC Funding Information

UN SDGs

Access Output

Other Access Options

Permanent Link

Other Files and Links

Fingerprint

Projects

ECS: Investigating the Inductive Effect and Kinetics of Covalently Immobilized Molecular Catalysts for High-performance Electrochemical CO2 Reduction

GRF: Pre-Concentrating and Detecting Natural-Water Heavy Metals by Sulfur-Equipped Porous Crystals

Cite this