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Research Article

Molecular modulating of cobalt phthalocyanines on amino-functionalized carbon nanotubes for enhanced electrocatalytic CO2 conversion

Huajian Xu1, Huizhu Cai1, Linxia Cui2, Limei Yu1( ), Rui Gao2( ), Chuan Shi1( )
State Key Laboratory of Fine Chemicals, College of Chemical Engineering, Dalian University of Technology, Dalian 116024, China
College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021, China
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Graphical Abstract

Cobalt(II) phthalocyanine (CoPc)-COOH/carbon nanotube (CNT)-NH2 catalyst was obtained by amidation reaction. The presence of amide bonds not only increased the active site concentration, but also modulated the electron density of the active site. Density functional theory (DFT) calculations proved the formation of *COOH intermediate was the rate-determining step for CO2 reduction reaction (CO2RR).

Abstract

Metal porphyrins and metal phthalocyanines (Pc) constitute a promising class of metal molecular catalysts (MMCs) for efficient CO2-to-CO electrocatalytic conversion due to their well-defined molecular structures. How to adjust the local coordination and electronic environment of the metal center and enhance the molecular-level dispersion of the active components remains as great challenges for further improving the performance. Herein, a cobalt(II) Pc (CoPc)-COOH/carbon nanotube (CNT)-NH2 hybrid catalyst was rationally designed by clicking the CoPc-COOH molecules onto the surface of CNT-NH2 through amidation reaction. This novel hybrid catalyst exhibited the enhanced current density of 22.4 mA/cm2 and CO selectivity of 91% at −0.88 V vs. reversible hydrogen electrode (RHE) in the CO2 electroreduction, as compared with CoPc-COOH/CNT and CoPc/CNT samples. The superior activity was ascribed to the charge transfer induced by introduction of –COOH and –NH2 functional groups to CoPc and CNT, respectively, facilitating the active centers of CoI being generated at lower potentials, and leading to the highest turnover frequency (TOF) being obtained over the CoPc-COOH/CNT-NH2 hybrid catalyst. The inherent directivity and saturability of covalent bonds formed via the amidation reaction ensure not only a higher density of Co active centers, but also an improved stability for CO2 reduction reaction (CO2RR). The present study represents an effective strategy for improving MMCs performance by molecular modulating of metal phthalocyanines on functionalized carbon substrates directed by click confinement chemistry.

Keywords

electrocatalytic CO2 reductioncobalt tetracarboxylphthalocyanineamino functionalized carbon nanotubesamidation

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Nano Research
Volume 16 Issue 3,
March 2023
Pages 3649-3657
DOI: 10.1007/s12274-022-4578-x
Cite this article:
Xu H, Cai H, Cui L, et al. Molecular modulating of cobalt phthalocyanines on amino-functionalized carbon nanotubes for enhanced electrocatalytic CO2 conversion. Nano Research, 2023, 16(3): 3649-3657. https://doi.org/10.1007/s12274-022-4578-x
Topics:
Electrolytic reduction
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Women’s Special Issue: Nanomaterials: Preparation, Applications, and ChallengesWomen’s special issuse in nanomaterials

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Received: 26 April 2022
Revised: 22 May 2022
Accepted: 24 May 2022
Published: 18 June 2022
© Tsinghua University Press 2022
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