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Conductive phthalocyanine-based metal-organic framework as a highly efficient electrocatalyst for carbon dioxide reduction reaction

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Abstract

Porous crystalline metal-organic frameworks (MOFs) are one class of promising electrode materials for CO2 electroreduction reaction (CO2RR) by virtue of their large CO2 adsorption capacities and abundant tunable active sites, but their insulating nature usually leads to low current density. Herein, a two-dimensional (2D) Ni-phthalocyanine-based MOF (NiPc-Ni(NH)4) constructed by 2,3,9,10,16,17,23,24-octaaminophthalocyaninato nickel(II) (NiPc-(NH2)8) and nickel(II) ions attained high electrical conductivity due to the high overlap of d-π conjugation orbitals between the nickel node and the Ni-phthalocyanine-substituted o-phenylenediamine. During CO2RR, the NiPc-Ni(NH)4 nanosheets achieved a high CO Faradaic efficiency of 96.4% at −0.7 V and a large CO partial current density of 24.8 mA cm−2 at −1.1 V, which surpassed all the reported two-dimensional MOF electrocatalysts evaluated in an H-cell. The control experiments and density functional theory (DFT) calculations suggested that the Ni-N4 units of the phthalocyanine ring are the catalytic active sites. This work provides a new route to the design of highly efficient porous framework materials for the enhanced electrocatalysis via improving electrical conductivity.

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Acknowledgements

The work was supported by the National Key Research and Development Program of China (2018YFA0208600, 2018YFA0704502), the National Natural Science Foundation of China (21871263, 22071245, 21671188, 22033008), Strategic Priority Research Program of the Chinese Academy of Sciences (XDB20000000) and the Youth Innovation Promotion Association, CAS (Y201850). The authors thank the beamline BL14W1 station for XAS measurements at the Shanghai Synchrotron Radiation Facility, China. The authors thank Associate Prof. Mei-Rong Ke in Fuzhou University and Prof. Vefa Ahsen in Gebze Institute of Technology for guiding the synthesis of NiPc-(NHTs)8.

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, China

    Meng-Di Zhang, Duan-Hui Si, Jun-Dong Yi, Qi Yin, Yuan-Biao Huang & Rong Cao

  2. University of Chinese Academy of Sciences, Beijing, 100049, China

    Jun-Dong Yi, Yuan-Biao Huang & Rong Cao

  3. College of Chemistry and Materials Science, Fujian Normal University, Fuzhou, 350007, China

    Meng-Di Zhang

  4. Fujian College, University of Chinese Academy of Sciences, Fuzhou, 350002, China

    Meng-Di Zhang, Duan-Hui Si, Yuan-Biao Huang & Rong Cao

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  1. Meng-Di Zhang
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  2. Duan-Hui Si
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Correspondence to Yuan-Biao Huang or Rong Cao.

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Conductive phthalocyanine-based metal-organic framework as a highly efficient electrocatalyst for carbon dioxide reduction reaction

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Zhang, MD., Si, DH., Yi, JD. et al. Conductive phthalocyanine-based metal-organic framework as a highly efficient electrocatalyst for carbon dioxide reduction reaction. Sci. China Chem. 64, 1332–1339 (2021). https://doi.org/10.1007/s11426-021-1022-3

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  • DOI: https://doi.org/10.1007/s11426-021-1022-3

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