Journal Home > Volume 16 , Issue 3
Nano Research 2023, 16(3): 3649-3657 https://doi.org/10.1007/s12274-022-4578-x
Research Article | Issue | Published: 18 June 2022

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

Show Author's Information 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
Keywords:
cobalt tetracarboxylphthalocyanine, amino functionalized carbon nanotubes, amidation, electrocatalytic CO2 reduction
Topics:
Electrolytic reduction
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
Download citation
EndNote(RIS)
BibTeX

1064

Views

70

Downloads

Citations

12

Crossref

14

WoS

14

Scopus

0

CSCD

Abstract Full text Electronic supplementary material About this article

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.


menu
Abstract
Full text
Outline
Electronic supplementary material
About this article

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

Show Author's information 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

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: cobalt tetracarboxylphthalocyanine, amino functionalized carbon nanotubes, amidation, electrocatalytic CO2 reduction

References(49)

[1]

Chen, S. H.; Li, W. H.; Jiang, W. J.; Yang, J. R.; Zhu, J. X.; Wang, L. Q.; Ou, H. H.; Zhuang, Z. C.; Chen, M. Z.; Sun, X. H. et al. MOF encapsulating N-heterocyclic carbene-ligated copper single-atom site catalyst towards efficient methane electrosynthesis. Angew. Chem., Int. Ed. 2022, 61, e202114450.
DOI Google Scholar
[2]

Tomboc, G. M.; Choi, S.; Kwon, T.; Hwang, Y. J.; Lee, K. Potential link between Cu surface and selective CO2 electroreduction: Perspective on future electrocatalyst designs. Adv. Mater. 2020, 32, 1908398.
DOI Google Scholar
[3]

Zhu, S. Q.; Delmo, E. P.; Li, T. H.; Qin, X. P.; Tian, J.; Zhang, L. L.; Shao, M. H. Recent advances in catalyst structure and composition engineering strategies for regulating CO2 electrochemical reduction. Adv. Mater. 2021, 33, 2005484.
DOI Google Scholar
[4]

Wagner, A.; Sahm, C. D.; Reisner, E. Towards molecular understanding of local chemical environment effects in electro- and photocatalytic CO2 reduction. Nat. Catal. 2020, 3, 775–786.
DOI Google Scholar
[5]

Jing, H. Y.; Zhu, P.; Zheng, X. B.; Zhang, Z. D.; Wang, D. S.; Li, Y. D. Theory-oriented screening and discovery of advanced energy transformation materials in electrocatalysis. Adv. Powder Mater. 2022, 1, 100013.
DOI Google Scholar
[6]

Wang, Y.; Zheng, X. B.; Wang, D. S. Design concept for electrocatalysts. Nano Res. 2022, 15, 1730–1752.
DOI Google Scholar
[7]

Rosen, J.; Hutchings, G. S.; Lu, Q.; Rivera, S.; Zhou, Y.; Vlachos, D. G.; Jiao, F. Mechanistic insights into the electrochemical reduction of CO2 to CO on nanostructured Ag surfaces. ACS Catal. 2015, 5, 4293–4299.
DOI Google Scholar
[8]

Marshall-Roth, T.; Libretto, N. J.; Wrobel, A. T.; Anderton, K. J.; Pegis, M. L.; Ricke, N. D.; Voorhis, T. V.; Miller, J. T.; Surendranath, Y. A pyridinic Fe-N4 macrocycle models the active sites in Fe/N-doped carbon electrocatalysts. Nat. Commun. 2020, 11, 5283.
DOI Google Scholar
[9]

Chen, C. J.; Sun, X. F.; Yan, X. P.; Wu, Y. H.; Liu, H. Z.; Zhu, Q. G.; Bediako, B. B. A.; Han, B. X. Boosting CO2 electroreduction on N, P-co-doped carbon aerogels. Angew. Chem., Int. Ed. 2020, 59, 11123–11129.
DOI Google Scholar
[10]

Jiang, Z.; Wang, Y.; Zhang, X.; Zheng, H. Z.; Wang, X. J.; Liang, Y. Y. Revealing the hidden performance of metal phthalocyanines for CO2 reduction electrocatalysis by hybridization with carbon nanotubes. Nano Res. 2019, 12, 2330–2334.
DOI Google Scholar
[11]

Zhu, H. L.; Zheng, Y. Q.; Shui, M. Synergistic interaction of nitrogen-doped carbon nanorod array anchored with cobalt phthalocyanine for electrochemical reduction of CO2. ACS Appl. Energy Mater. 2020, 3, 3893–3901.
DOI Google Scholar
[12]

Xia, Y. J.; Kashtanov, S.; Yu, P. F.; Chang, L. Y.; Feng, K.; Zhong, J.; Guo, J. H.; Sun, X. H. Identification of dual-active sites in cobalt phthalocyanine for electrochemical carbon dioxide reduction. Nano Energy 2020, 67, 104163.
DOI Google Scholar
[13]

Göttle, A. J.; Koper, M. T. M. Determinant role of electrogenerated reactive nucleophilic species on selectivity during reduction of CO2 catalyzed by metalloporphyrins. J. Am. Chem. Soc. 2018, 140, 4826–4834.
DOI Google Scholar
[14]

Liu, J. H.; Yang, L. M.; Ganz, E. Efficient and selective electroreduction of CO2 by single-atom catalyst two-dimensional TM-Pc monolayers. ACS Sustainable Chem. Eng. 2018, 6, 15494–15502.
DOI Google Scholar
[15]

Ma, J. J.; Zhu, H. L.; Zheng, Y. Q.; Shui, M. An insight into anchoring of cobalt phthalocyanines onto carbon: Efficiency of the CO2 reduction reaction. ACS Appl. Energy Mater. 2021, 4, 1442–1448.
DOI Google Scholar
[16]

Zhao, C. X.; Liu, J. N.; Wang, J.; Wang, C. D.; Guo, X.; Li, X. Y.; Chen, X.; Song, L.; Li, B. Q.; Zhang, Q. A clicking confinement strategy to fabricate transition metal single-atom sites for bifunctional oxygen electrocatalysis. Sci. Adv. 2022, 8, eabn5091.
DOI Google Scholar
[17]

Choi, J.; Kim, J.; Wagner, P.; Gambhir, S.; Jalili, R.; Byun, S.; Sayyar, S.; Lee, Y. M.; MacFarlane, D. R.; Wallace, G. G. et al. Energy efficient electrochemical reduction of CO2 to CO using a three-dimensional porphyrin/graphene hydrogel. Energy Environ. Sci. 2019, 12, 747–755.
DOI Google Scholar
[18]

Yang, Z. J.; Zhang, X. F.; Long, C.; Yan, S. H.; Shi, Y. N.; Han, J. Y.; Zhang, J.; An, P. F.; Chang, L.; Tang, Z. Y. Covalently anchoring cobalt phthalocyanine on zeolitic imidazolate frameworks for efficient carbon dioxide electroreduction. CrystEngComm 2020, 22, 1619–1624.
DOI Google Scholar
[19]

Choi, J.; Wagner, P.; Gambhir, S.; Jalili, R.; MacFarlane, D. R.; Wallace, G. G.; Officer, D. L. Steric modification of a cobalt phthalocyanine/graphene catalyst to give enhanced and stable electrochemical CO2 reduction to CO. ACS Energy Lett. 2019, 4, 666–672.
DOI Google Scholar
[20]

Abe, T.; Imaya, H.; Yoshida, T.; Tokita, S.; Schlettwein, D.; Wöhrle, D.; Kaneko, M. Electrochemical CO2 reduction catalysed by cobalt octacyanophthalocyanine and its mechanism. J. Porphyrins Phthalocyanines 1997, 1, 315–321.
DOI Google Scholar
[21]

Chen, K. J.; Cao, M. Q.; Lin, Y. Y.; Fu, J. W.; Liao, H. X.; Zhou, Y. J.; Li, H. M.; Qiu, X. Q.; Hu, J. H.; Zheng, X. S. et al. Ligand engineering in nickel phthalocyanine to boost the electrocatalytic reduction of CO2. Adv. Funct. Mater. 2022, 32, 2111322.
DOI Google Scholar
[22]

Zhang, X.; Wang, Y.; Gu, M.; Wang, M. Y.; Zhang, Z. S.; Pan, W. Y.; Jiang, Z.; Zheng, H. Z.; Lucero, M.; Wang, H. L. et al. Molecular engineering of dispersed nickel phthalocyanines on carbon nanotubes for selective CO2 reduction. Nat. Energy 2020, 5, 684–692.
DOI Google Scholar
[23]

Wu, Y. S.; Liang, Y. Y.; Wang, H. L. Heterogeneous molecular catalysts of metal phthalocyanines for electrochemical CO2 reduction reactions. Acc. Chem. Res. 2021, 54, 3149–3159.
DOI Google Scholar
[24]

Sun, L. B.; Reddu, V.; Fisher, A. C.; Wang, X. Electrocatalytic reduction of carbon dioxide: Opportunities with heterogeneous molecular catalysts. Energy Environ. Sci. 2020, 13, 374–403.
DOI Google Scholar
[25]

Zhang, X.; Wu, Z. S.; Zhang, X.; Li, L. W.; Li, Y. Y.; Xu, H. M.; Li, X. X.; Yu, X. L.; Zhang, Z. S.; Liang, Y. Y. et al. Highly selective and active CO2 reduction electrocatalysts based on cobalt phthalocyanine/carbon nanotube hybrid structures. Nat. Commun. 2017, 8, 14675.
DOI Google Scholar
[26]

Morlanés, N.; Takanabe, K.; Rodionov, V. Simultaneous reduction of CO2 and splitting of H2O by a single immobilized cobalt phthalocyanine electrocatalyst. ACS Catal. 2016, 6, 3092–3095.
DOI Google Scholar
[27]

Gong, S. H.; Wang, W. B.; Xiao, X. X.; Liu, J.; Wu, C. D.; Lv, X. M. Elucidating influence of the existence formation of anchored cobalt phthalocyanine on electrocatalytic CO2-to-CO conversion. Nano Energy 2021, 84, 105904.
DOI Google Scholar
[28]

Han, N.; Wang, Y.; Ma, L.; Wen, J. G.; Li, J.; Zheng, H. C.; Nie, K. Q.; Wang, X. X.; Zhao, F. P.; Li, Y. F. et al. Supported cobalt polyphthalocyanine for high-performance electrocatalytic CO2 reduction. Chem 2017, 3, 652–664.
DOI Google Scholar
[29]

Zhu, M. H.; Chen, J. C.; Guo, R.; Xu, J.; Fang, X. C.; Han, Y. F. Cobalt phthalocyanine coordinated to pyridine-functionalized carbon nanotubes with enhanced CO2 electroreduction. Appl. Catal. B:Environ. 2019, 251, 112–118.
DOI Google Scholar
[30]

Liu, Y. S.; McCrory, C. C. L. Modulating the mechanism of electrocatalytic CO2 reduction by cobalt phthalocyanine through polymer coordination and encapsulation. Nat. Commun. 2019, 10, 1683.
DOI Google Scholar
[31]

Ma, D. D.; Han, S. G.; Cao, C. S.; Wei, W. B.; Li, X. F.; Chen, B.; Wu, X. T.; Zhu, Q. L. Bifunctional single-molecular heterojunction enables completely selective CO2-to-CO conversion integrated with oxidative 3D nano-polymerization. Energy Environ. Sci. 2021, 14, 1544–1552.
DOI Google Scholar
[32]

Zhu, M. H.; Chen, J. C.; Huang, L. B.; Ye, R. Q.; Xu, J.; Han, Y. F. Covalently grafting cobalt porphyrin onto carbon nanotubes for efficient CO2 electroreduction. Angew. Chem., Int. Ed. 2019, 58, 6595–6599.
DOI Google Scholar
[33]

Wang, M.; Torbensen, K.; Salvatore, D.; Ren, S. X.; Joulié, D.; Dumoulin, F.; Mendoza, D.; Lassalle-Kaiser, B.; Işci, U.; Berlinguette, C. P. et al. CO2 electrochemical catalytic reduction with a highly active cobalt phthalocyanine. Nat. Commun. 2019, 10, 3602.
DOI Google Scholar
[34]

Pan, Y.; Lin, R.; Chen, Y. J.; Liu, S. J.; Zhu, W.; Cao, X.; Chen, W. X.; Wu, K. L.; Cheong, W. C.; Wang, Y. et al. Design of single-atom Co-N5 catalytic site: A robust electrocatalyst for CO2 reduction with nearly 100% CO selectivity and remarkable stability. J. Am. Chem. Soc. 2018, 140, 4218–4221.
DOI Google Scholar
[35]

Ma, D. D.; Han, S. G.; Cao, C. S.; Li, X. F.; Wu, X. T.; Zhu, Q. L. Remarkable electrocatalytic CO2 reduction with ultrahigh CO/H2 ratio over single-molecularly immobilized pyrrolidinonyl nickel phthalocyanine. Appl. Catal. B: Environ. 2020, 264, 118530.
DOI Google Scholar
[36]

Cai, H. Z.; Chen, B. B.; Zhang, X.; Deng, Y. C.; Xiao, D. Q.; Ma, D.; Shi, C. Highly active sites of low spin FeIIN4 species: The identification and the ORR performance. Nano Res. 2021, 14, 122–130.
DOI Google Scholar
[37]

Kresse, G.; Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 1996, 54, 11169–11186.
DOI Google Scholar
[38]

Kresse, G.; Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 1996, 6, 15–50.
DOI Google Scholar
[39]

Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 1996, 77, 3865–3868.
DOI Google Scholar
[40]

Monkhorst, H. J.; Pack, J. D. Special points for Brillouin-zone integrations. Phys. Rev. B 1976, 13, 5188–5192.
DOI Google Scholar
[41]

Grimme, S.; Antony, J.; Ehrlich, S.; Krieg, H. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J. Chem. Phys. 2010, 132, 154104.
DOI Google Scholar
[42]

Grimme, S.; Ehrlich, S.; Goerigk, L. Effect of the damping function in dispersion corrected density functional theory. J. Comput. Chem. 2011, 32, 1456–1465.
DOI Google Scholar
[43]

Li, H. D.; Pan, Y.; Wang, Z. C.; Yu, Y. D.; Xiong, J.; Du, H. Y.; Lai, J. P.; Wang, L.; Feng, S. H. Coordination engineering of cobalt phthalocyanine by functionalized carbon nanotube for efficient and highly stable carbon dioxide reduction at high current density. Nano Res. 2022, 15, 3056–3064.
DOI Google Scholar
[44]

Nørskov, J. K.; Rossmeisl, J.; Logadottir, A.; Lindqvist, L.; Kitchin, J. R.; Bligaard, T.; Jónsson, H. Origin of the overpotential for oxygen reduction at a fuel-cell cathode. J. Phys. Chem. B 2004, 108, 17886–17892.
DOI Google Scholar
[45]

Ni, W. P.; Liu, Z. X.; Guo, X. G.; Zhang, Y.; Ma, C.; Deng, Y. J.; Zhang, S. G. Dual single-cobalt atom-based carbon electrocatalysts for efficient CO2-to-syngas conversion with industrial current densities. Appl. Catal. B: Environ. 2021, 291, 120092.
DOI Google Scholar
[46]

Ma, Z. J.; Zhang, X. L.; Han, X. Y.; Wu, D. P.; Wang, H. J.; Gao, Z. Y.; Xu, F.; Jiang, K. Synergistic adsorption and activation of nickel phthalocyanine anchored onto ketjenblack for CO2 electrochemical reduction. Appl. Surf. Sci. 2021, 538, 148134.
DOI Google Scholar
[47]

Wu, H. H.; Zeng, M.; Zhu, X.; Tian, C. C.; Mei, B. B.; Song, Y.; Du, X. L.; Jiang, Z.; He, L.; Xia, C. G. et al. Defect engineering in polymeric cobalt phthalocyanine networks for enhanced electrochemical CO2 reduction. ChemElectroChem 2018, 5, 2717–2721.
DOI Google Scholar
[48]

Zhang, M. D.; Si, D. H.; Yi, J. D.; Zhao, S. S.; Huang, Y. B.; Cao, R. Conductive phthalocyanine-based covalent organic framework for highly efficient electroreduction of carbon dioxide. Small 2020, 16, 2005254.
DOI Google Scholar
[49]

Zhu, M. H.; Ye, R. Q.; Jin, K.; Lazouski, N.; Manthiram, K. Elucidating the reactivity and mechanism of CO2 electroreduction at highly dispersed cobalt phthalocyanine. ACS Energy Lett. 2018, 3, 1381–1386.
DOI Google Scholar
File
12274_2022_4578_MOESM1_ESM.pdf (578.9 KB)
Publication history
Copyright
Acknowledgements

Publication history

Received: 26 April 2022
Revised: 22 May 2022
Accepted: 24 May 2022
Published: 18 June 2022
Issue date: March 2023

Copyright

© Tsinghua University Press 2022

Acknowledgements

Acknowledgements

The work was supported by the National Natural Science Foundation of China (Nos. 21872014, 21932002, 21902018, 21962013, and 22172083), the National Key Research and Development (R&D) Program of China (No. 2017YFA0700103), the Fundamental Research Funds for the Central Universities (No. DUT20ZD205), the Natural Science Foundation of Liaoning Province (No. 2019-MS-053), and the Liaoning Revitalization Talent Program (No. XLYC2008032). The authors thank Zirui Gao from Peking university for providing the AC-HAADF-STEM measurement.

Return