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Progress in Chemistry 2024, Vol. 36 Issue (3): 285-296 DOI: 10.7536/PC231115   Next Articles

• Review •

Conductive Phthalocyanine-Based Metal-Organic Frameworks for Efficient Electrocatalysis

Shun Lu, Yuan Liu, Hong Liu()   

  1. Chongqing Institute of Green and Intelligent Technology, Chinese Academy of Sciences, Chongqing 400715, China
  • Received: Revised: Online: Published:
  • Contact: * email: liuhong@cigit.ac.cn (Liu H)
  • Supported by:
    National Natural Science Foundation of China(52131003); National Natural Science Foundation of China(52122007); National Natural Science Foundation of China(52200076); Specific Research Fellowship of Chinese Academy of Sciences(E329620101); Natural Science Foundation of Chongqing(cstb2022nscq-bhx0035)
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The development of innovative catalysts for various electrochemical scenarios is crucial in satisfying the growing demands for sustainable energy and environmental conservation. Conductive metal-organic frameworks (c-MOFs) based on phthalocyanine complexes known as phthalocyanine-based c-MOFs, have shown promising potential in electrochemical energy conversion and environmental research. These c-MOFs represent a new category of layer-stacked porous MOFs with in-plane extended π-conjugation structure, which can enhance electrocatalytic activity by facilitating the mass diffusion of reactants and electron/charge transfer. The exceptional promising for a variety electrocatalytic reactions, such as water, oxygen, CO2, and nitrogen conversion. In this work, we focus primarily on phthalocyanine-based c-MOFs rather than other types of c-MOFs, providing a comprehensive overview of their conductive mechanisms and main electrocatalytic reactions. We also cover recent progress in the utilization of phthalocyanine-based c-MOFs as heterogeneous catalysts in electrocatalysis. Furthermore, we explore the challenges related to the utilization of phthalocyanine-based c-MOFs in electrocatalysis. The state-of-the-art research and insights into the future perspectives of phthalocyanine-based c-MOFs as electrocatalysts are also presented and discussed. This work aim to guide the development of phthalocyanine-based c-MOF electrocatalysts with enhanced activity.

Contents

1 Introduction

2 Conductive mechanisms

3 Electrocatalysis

3.1 Water electrolysis

3.2 Oxygen reduction reaction

3.3 Carbon dioxide reduction reaction

3.4 Nitrogen reduction reaction

4 Challenges and outlook

4.1 Catalytic activity

4.2 Conductivity

4.3 Selectivity

4.4 Stability

4.5 Other possible reactions

5 Summary

Key words: conductive metal-organic frameworks, phthalocyanine-based MOFs, conjugated structure, electrocatalysis
Fig. 1 (a) Synthetic illustration for phthalocyanine-based c-MOFs; (b) top and side view of a general structural representation of phthalocyanine-based c-MOFs in eclipsed stacking mode. Reproduced with permission from Ref 19. Copyright 2021. American Chemical Society
Fig. 2 (a) The through-bond pathway. (b) The extended conjugation pathway also involves π-d conjugation. (c) The through-space pathway involves π-π stacking of organic moieties. Reproduced with permission from Ref 12. Copyright 2021. American Chemical Society
Fig. 3 Scheme of electron/charge transport via (a) a redox hopping mechanism and (b) a guest-promoted pathway. Reproduced with permission from Ref 12. Copyright 2020. American Chemical Society
Fig. 4 (a) Schematic model structure of MPc-pz. (b) DFT calculation: free energy diagrams of HER on MPc-pz. Reproduced with permission from Ref 34. Copyright 2020. American Chemical Society
Fig. 5 (a) Strategy for constructing MPc-M’-MOF; (b) TEM image of NiPc-Ni c-MOF; (c) linear sweep voltammetry (LSV) curves of MPc-M’ c-MOF; (d) PDOS of different dual-metal c-MOFs; (e) scheme of Ni-O4 and Ni-N4 sites in NiPc-Ni c-MOF. Reproduced with permission from Ref 35. Copyright 2021. Royal Society of Chemistry
Fig. 6 (a) Simulated structure of PcCu-O8-M (red: O, blue: C, white: H, brown: Cu, green: metal atoms, M = Co, Fe, Ni, Cu). (b) ORR polarization curves of PcCu-O8-Co/CNT. (c) In situ Raman analysis during the ORR process. (d) proposed reaction mechanism. Reproduced with permission from Ref 38. Copyright 2021. Wiley-VCH GmbH
Fig. 7 (a) Scheme of NiPc-NiO4 c-MOF nanosheets. Top and side view of their structures with 2 × 2 square grids in AA-stacking mode; (b) LSV curves of NiPc-based c-MOFs in CO2/Ar-saturated 0.5 M KHCO3; (c) Illustration of the CO2RR. Reproduced with permission from Ref 46. Copyright 2021. Wiley-VCH GmbH
Fig. 8 (a) Scheme of MPc-pz; (b) XRD patterns of MPc-pz; (c) charge density differences of N2 adsorbed on FePc-pz; (d) optimized structures of various intermediates for NRR. (e) Free energy profiles of NRR along the alternating pathway on MPc-pz. Reproduced with permission from Ref 34. Copyright 2021. American Chemical Society
Fig. 9 The challenges in phthalocyanine-based c-MOFs
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