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化学进展 2024, Vol. 36 Issue (3): 285-296 DOI: 10.7536/PC231115   后一篇

• 综述 •

导电酞菁基金属有机框架的高效电催化研究

陆顺, 刘元, 刘鸿*()   

  1. 中国科学院重庆绿色智能技术研究院 重庆 400715
  • 收稿日期:2023-11-21 修回日期:2024-01-15 出版日期:2024-03-24 发布日期:2024-01-26
  • 作者简介:

    刘鸿 研究员，博士生导师，中国科学院重庆绿色智能技术研究院院长。研究方向为环境电化学及污水处理技术。主持国家杰出青年科学基金、国家重大科研仪器研制项目和国家自然科学基金重点项目11项，发表SCI论文100余篇，参编中英文专著5部（章），获授权中国发明专利17件，软件著作权6件。获广东省自然科学一等奖、重庆市自然科学奖励二等奖。

  • 基金资助:
    国家自然科学基金项目(52131003); 国家自然科学基金项目(52122007); 国家自然科学基金项目(52200076); 中国科学院特别研究助理资助项目(E329620101); 重庆市自然科学基金(cstb2022nscq-bhx0035)
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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:2023-11-21 Revised:2024-01-15 Online:2024-03-24 Published:2024-01-26
  • 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)

在满足日益增长的可持续能源和环境保护需求下，开发用于多种电化学场景的新型催化剂发挥着重要作用。导电酞菁基金属有机框架（MOFs）是一类新型的层叠多孔MOFs，具有面内扩展π共轭结构，可以通过促进传质和电子/电荷转移来增强电催化活性。导电酞菁基MOFs具有优异的导电性，使其在如水、氧、二氧化碳和氮还原等各种电催化反应中非常有前景。导电酞菁基MOFs在电化学能量转换和环境研究中表现出良好的活性。本文主要关注导电酞菁基MOFs，而非其他类型的导电MOFs，并全面概述其导电机理和主要的电催化反应，还将讨论在电催化中使用导电酞菁基MOFs作为非均相催化剂的最新进展。此外，本文将探讨与导电酞菁基MOFs在电催化中的应用的挑战和展望。

关键词： 导电金属有机框架, 酞菁基金属有机骨架, 共轭结构, 电催化

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
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图1 （a）酞菁基MOFs的合成图；（b）酞菁基MOFs在堆叠模式下的一般结构反应的俯视图和侧视图[19]
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
图2 导电机理：（a）贯穿键；（b）扩展偶联及π-d偶联；（c）通过空间及有机部分的π-π堆积[12]
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
图3 （a）氧化还原跳跃机制；（b）客体促进途径的电子/电荷传输机制[12]
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
图4 （a）MPc-pz的模型结构；（b）DFT计算：HER在MPc-pz上的自由能图[34]
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
图5 （a）构建MPc-M'-MOF的示意图；（b）NiPc-Ni-MOF的TEM图；（c）MPc-M'-c-MOF的LSV曲线；（d）不同双金属c-MOFs的PDOS谱图；（e）NiPc-Ni c-MOF中Ni-O4和Ni-N4位点的示意图[35]
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
图6 （a）PcCu-O8-M的模拟结构；（b） PcCu-O8-Co/CNT的极化曲线；（c） ORR过程中的原位拉曼分析；（d）ORR反应机理[38]
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
图7 （a）NiPc-NiO4 c-MOF的合成示意图;（b）NiPc基c-MOFs在CO2/Ar饱和0.5 M KHCO3中的LSV曲线;（c）CO2RR示意图[46]
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
图8 （a）MPc-pz的合成示意图；（b） MPc-pz的XRD图谱；（c）FePc-pz上吸附的N2电荷密度差异图；（d）NRR各种中间体的优化结构；（e）NRR在MPc-pz上沿交替路径的自由能分布[34]
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
图9 酞菁基MOFs面临的挑战
Fig. 9 The challenges in phthalocyanine-based c-MOFs
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