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  • Exfoliation of amorphous phthalocyanine conjugated polymers into ultrathin nanosheets for highly efficient oxygen reduction

    Author(s)
    Liu, Wenping
    Wang, Chiming
    Zhang, Lijie
    Pan, Houhe
    Liu, Wenbo
    Chen, Jun
    Yang, Dongjiang
    Xiang, Yanjuan
    Wang, Kang
    Jiang, Jianzhuang
    Yao, Xiangdong
    Griffith University Author(s)
    Yao, Xiangdong
    Yang, Dongjiang
    Year published
    2019
    Metadata
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    Abstract
    It is a significant challenge to develop a high-efficiency synthetic methodology to access fully conjugated 2D conjugated polymer (CP)/covalent organic framework (COF) nanosheets (NSs) that have great application potential for electronics and energy. Herein, we report the exfoliation of a series of amorphous ethynyl-linked phthalocyanine (Pc) CPs (MPc-CPs, M = Fe, Co, Fe0.5Co0.5) into ultrathin MPc-CP NSs. Random coupling between the four regioisomers (with D4h, D2h, C2v and Cs symmetry) of the two tetra-β-substituted phthalocyanine precursors endows the resulting phthalocyanine conjugated polymers MPc-CPs with intrinsic ...
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    It is a significant challenge to develop a high-efficiency synthetic methodology to access fully conjugated 2D conjugated polymer (CP)/covalent organic framework (COF) nanosheets (NSs) that have great application potential for electronics and energy. Herein, we report the exfoliation of a series of amorphous ethynyl-linked phthalocyanine (Pc) CPs (MPc-CPs, M = Fe, Co, Fe0.5Co0.5) into ultrathin MPc-CP NSs. Random coupling between the four regioisomers (with D4h, D2h, C2v and Cs symmetry) of the two tetra-β-substituted phthalocyanine precursors endows the resulting phthalocyanine conjugated polymers MPc-CPs with intrinsic structural defects and a disordered framework on individual layers. This in turn induces a diminished interlayer overlapping and a weakened interlayer π–π stacking interaction, facilitating the possible exfoliation of MPc-CPs into ultrathin 2D NSs with a yield of over 50%. The direction observation by transmission electron microscopy (TEM) and atomic force microscopy (AFM) demonstrates that the ultrathin MPc-CP NSs possess a smooth surface with a uniform thickness of 1–3 nm and a lateral size of hundreds of nanometers. The as-prepared bimetallic Fe0.5Co0.5Pc-CP NSs were further used to fabricate a heterostructure Fe0.5Co0.5Pc-CP NS@G with graphene NSs as an oxygen reduction reaction (ORR) catalyst, which exhibits an onset potential of 1006 mV and a half-wave potential of 927 mV in 0.1 M KOH, representing one of the best values in an alkaline medium. Moreover, the excellent ORR activity of the exfoliated tetrapyrrole-based conjugated NSs hybridized with graphene has also been demonstrated by a Zn–air battery device, showing an open circuit voltage of 1.34 V and a peak power density of ca. 180 mW cm−2.
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    Journal Title
    Journal of Materials Chemistry A
    Volume
    7
    Issue
    7
    DOI
    https://doi.org/10.1039/c8ta11044a
    Subject
    Macromolecular and materials chemistry
    Materials engineering
    Science & Technology
    Physical Sciences
    Technology
    Chemistry, Physical
    Energy & Fuels
    Publication URI
    http://hdl.handle.net/10072/388365
    Collection
    • Journal articles

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