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Nano Research 2022, 15(4): 3056-3064 https://doi.org/10.1007/s12274-021-3962-2
Research Article | Issue | Published: 18 November 2021

Coordination engineering of cobalt phthalocyanine by functionalized carbon nanotube for efficient and highly stable carbon dioxide reduction at high current density

Show Author's Information Hongdong Li1,  Yue Pan1,  Zuochao Wang1,  Yaodong Yu1,  Juan Xiong1,  Haoyang Du1,  Jianping Lai1( ),  Lei Wang1,2( ),  Shouhua Feng1
Key Laboratory of Eco-chemical Engineering, Taishan scholar advantage and characteristic discipline team of Eco-chemical process and technology, College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042, China
Shandong Engineering Research Center for Marine Environment Corrosion and Safety Protection, College of Environment and Safety Engineering, Qingdao University of Science and Technology, Qingdao 266042, China
Keywords:
highly stable, cobalt phthalocyanine (CoPc), functionalized carbon nanotubes (CNT), coordination engineering, carbon dioxide electroreduction
Topics:
Electrocatalysis
Cite this article:
Li H, Pan Y, Wang Z, et al. Coordination engineering of cobalt phthalocyanine by functionalized carbon nanotube for efficient and highly stable carbon dioxide reduction at high current density. Nano Research, 2022, 15(4): 3056-3064. https://doi.org/10.1007/s12274-021-3962-2
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Abstract Full text Electronic supplementary material About this article

Coordination engineering can enhance the activity and stability of the catalyst in heterogeneous catalysis. However, the axial coordination engineering between different groups on the carbon carrier and molecular catalysts in the electrocatalytic carbon dioxide reduction reaction (CO2RR) has been studied rarely. Through coordination engineering strategy, a series of amino (NH2), hydroxyl (OH), and carboxyl (COOH) groups functionalized carbon nanotubes (CNT) immobilized cobalt phthalocyanine (CoPc) catalysts are designed. Compared with no groups, OH groups and COOH groups, NH2 groups can effectively change the coordination environment of the central metal Co, thereby significantly increasing the turnover frequency (TOF) (31.4 s−1 at −0.6 V vs. RHE, CoPc/NH2-CNT > CoPc/OH-CNT > CoPc/COOH-CN > CoPc/CNT). In the flow cell, the CoPc/NH 2-CNT catalyst has high carbon monoxide (CO) selectivity at high current density (~ 100% at −225 mA·cm−2, ~ 96% at −351 mA·cm−2). Importantly, the CoPc/NH2-CNT catalyst can operate stably for 100 h at 225 mA·cm−2. Theoretical calculations reveal that CoPc/NH2-CNT catalyst is beneficial to the formation of *COOH and desorption of *CO, thus promoting CO2RR. This work provides an excellent platform for understanding the effect of coordination engineering on electrocatalytic performance and promotes a way to explore efficient and stable catalysts in other applications.


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Electronic supplementary material
About this article

Coordination engineering of cobalt phthalocyanine by functionalized carbon nanotube for efficient and highly stable carbon dioxide reduction at high current density

Show Author's information Hongdong Li1, Yue Pan1, Zuochao Wang1, Yaodong Yu1, Juan Xiong1, Haoyang Du1, Jianping Lai1( ), Lei Wang1,2( ), Shouhua Feng1
Key Laboratory of Eco-chemical Engineering, Taishan scholar advantage and characteristic discipline team of Eco-chemical process and technology, College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042, China
Shandong Engineering Research Center for Marine Environment Corrosion and Safety Protection, College of Environment and Safety Engineering, Qingdao University of Science and Technology, Qingdao 266042, China

Abstract

Coordination engineering can enhance the activity and stability of the catalyst in heterogeneous catalysis. However, the axial coordination engineering between different groups on the carbon carrier and molecular catalysts in the electrocatalytic carbon dioxide reduction reaction (CO2RR) has been studied rarely. Through coordination engineering strategy, a series of amino (NH2), hydroxyl (OH), and carboxyl (COOH) groups functionalized carbon nanotubes (CNT) immobilized cobalt phthalocyanine (CoPc) catalysts are designed. Compared with no groups, OH groups and COOH groups, NH2 groups can effectively change the coordination environment of the central metal Co, thereby significantly increasing the turnover frequency (TOF) (31.4 s−1 at −0.6 V vs. RHE, CoPc/NH2-CNT > CoPc/OH-CNT > CoPc/COOH-CN > CoPc/CNT). In the flow cell, the CoPc/NH 2-CNT catalyst has high carbon monoxide (CO) selectivity at high current density (~ 100% at −225 mA·cm−2, ~ 96% at −351 mA·cm−2). Importantly, the CoPc/NH2-CNT catalyst can operate stably for 100 h at 225 mA·cm−2. Theoretical calculations reveal that CoPc/NH2-CNT catalyst is beneficial to the formation of *COOH and desorption of *CO, thus promoting CO2RR. This work provides an excellent platform for understanding the effect of coordination engineering on electrocatalytic performance and promotes a way to explore efficient and stable catalysts in other applications.

Keywords: highly stable, cobalt phthalocyanine (CoPc), functionalized carbon nanotubes (CNT), coordination engineering, carbon dioxide electroreduction

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Publication history
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Acknowledgements

Publication history

Received: 02 August 2021
Revised: 21 September 2021
Accepted: 27 October 2021
Published: 18 November 2021
Issue date: April 2022

Copyright

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2021

Acknowledgements

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Nos. 51772162, 22001143, and 52072197), Youth Innovation and Technology Foundation of Shandong Higher Education Institutions, China (No. 2019KJC004), Outstanding Youth Foundation of Shandong Province, China (No. ZR2019JQ14), Taishan Scholar Young Talent Program, China (Nos. tsqn201909114 and tsqn201909123), Natural Science Foundation of Shandong Province, China (No. ZR2020YQ34), Major Scientific and Technological Innovation Project, China (No. 2019JZZY020405), and Major Basic Research Program of Natural Science Foundation of Shandong Province, China (No. ZR2020ZD09).

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