金属有机框架（MOF）衍生的非贵金属氧还原催化剂的研究

发布时间：2024-05-19 02:40

　　燃料电池和金属-空气电池作为能源转换装置具有较高的能量转换率、高能量密度以及低环境影响等优点。氧还原反应是这些能源转换装置中非常关键的一个反应。开发高性能的氧还原电催化剂对于实现这些装置得规模化应用非常重要。氧还原催化剂的电催化活性常常与其比表面积、晶面结构、导电性等因素有关。因此通过优化这些因素实现氧还原催化剂的活性提升是非常可行的。近年来,金属有机框架(MOFs)由于其具有高比表面积、均匀的孔隙分布和可调控的机能等优势,已广泛应用作为前驱体制备杂原子修饰的多孔碳材料。不仅如此,应用该类材料所制备的催化剂相比于其他前驱体制备得到的催化剂具有更高的催化活性。因此,本文中,我们应用MOFs制备了多种杂原子(N,Fe,Mn,和Co)掺杂的具有高比表面积的多孔碳材料,并研究了这些催化剂在碱性溶液和酸性溶液中的电催化氧还原性能。由于MOFs独特的结构,所制备的碳基催化剂不仅具有大量的活性位点,而且其良好的介孔结构为物质的传输提供大量的通道。此外,本文重点探讨了不同的掺杂金属原子对MOFs衍生的过渡金属掺杂碳催化剂活性的影响,并且总结了不同金属影响催化活性的规律。进一步地,我们合成了二元金属/三...

【文章页数】：115 页

【学位级别】：博士

【文章目录】：
中文摘要
ABSTRACT
1 INTRODUCTION
    1.1 FOSSIL FUELS AND THE NEED FOR RESEARCH INTO ALTERNATIVES
    1.2 THE CURRENT ELECTROCHEMICAL DEVICES
    1.3 OXYGEN REDUCTION ELECTROCATALYSIS – A CHALLENGE
    1.4 NON-Pt CATALYSTS
        1.4.1 Metal Free Carbon Catalysts
        1.4.2 Transition Metal–Nitrogen–Carbon Catalysts
        1.4.3 The Mechanisms for ORR
    1.5 NANO-STRUCTURES DERIVED FROM MOFS
    1.6 SCOPE AND OBJECTIVE
2 EXPERIMENTAL METHODS AND CHARACTERIZATION TECHNIQUES
    2.1 EXPERIMENTAL METHODS
        2.1.1 General considerations about MOF mediated synthesis
        2.1.2 Cobalt (Co)-MOFMS
        2.1.3 Zinc (Zn)-MOFMS
    2.2 CHARACTERIZATION TECHNIQUES
        2.2.1 Scanning Electron Microscopy (SEM)
        2.2.2 Transmission Electron Microscopy (TEM)
        2.2.3 Brunauer, Emmet, Teller Adsorption Isotherm (BET)
        2.2.4 X-Ray Photoelectron Spectroscopy (XPS)
        2.2.5 X-Ray Diffraction (XRD)
    2.3 ELECTROCATALYSIS FOR ORR
        2.3.1 Rotating Ring Disk Electrode (RRDE) and Potentiostat
        2.3.2 Half-cell
        2.3.3 Linear Sweep Voltammetry (LSV)
        2.3.4 Cyclic Voltammetry (CV)
        2.3.5 Ring current analysis
3 REPERCUSSION AND DATA ANALYSIS
    3.1 SYNTHESIS OF ORR ELECTROCATALYST FROM ZIF-8 AND ZIF-67 AND BIMETALIC
        3.1.1 Introduction
        3.1.2 Experimental Section
        3.1.3 Results and Discussions
        3.1.4 Electrocatalytic Activity
        3.1.5 Conclusion
    3.2 DESIGN AND SYNTHESIS OF Mn/ZIF-8 DERIVED POLYHEDRONS ENRICHED WITH Mn-OXIDE ACTIVE-CENTRES
        3.2.1 Introduction
        3.2.2 Experimental
        3.2.3 Structural Characterization and Catalytic Activity
        3.2.4 ORR Electrocatalytic Acitvity
        3.2.5 Conclusion
    3.3 Fe/Zn-DICYANOIMIDAZOLATE FRAMEWORK DERIVED CARBON MICROSTRUCTURES FOR ORR
        3.3.1 Introduction
        3.3.2 Experimental
        3.3.3 Detailed Results and Discussion
    3.4 Fe-DOPED ZIF-67/8 MOFS DERIVED ORR CATALYSTS
        3.4.1 Experimental
        3.4.2 Structure Analysis and Electrocatalytic Activity
    3.5 INFLUENCE OF Mn DOPING ON MESOPOROUS CO-N/C DERIVED FROM ZIF
        3.5.1 Introduction
        3.5.2 Experimental
        3.5.3 Characterizations and Electrocatalytic Activity
4 CONCLUSION AND OUTLOOK
ACKNOWLEDGEMENTS
REFERENCES AND NOTES
PUBLICATIONS



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