金属碳化物和碳氮化物的合成和碱性溶液中氧还原电化学催化性能研究

发布时间：2021-07-31 08:44

　　氧还原反应（Oxygen reduction reaction,ORR）催化剂,作为燃料电池的阴极材料,在其电化学能量转换中起着重要的作用。催化材料决定了氧气还原反应的速率,目前商业化的催化剂是负载在碳上的高度分散的铂（Pt）纳米粒子材料。然而,Pt价格昂贵,且在碱性/酸性溶液中易被腐蚀。过渡金属碳化物和碳氮化物具有导电性高(104Ω^-1m^-1)、结构容易调控、化学稳定性好等优点。它们的合成方法简单且环境友好;同时,用于制备相关材料的前驱体在地球上储量丰富。为了降低成本,实现可持续电化学能量转换,该材料被广泛地用于取代贵金属基催化剂。近年来金属碳化物在燃料电池应用方面取得了很大的进展,已有报道相关材料的功率密度在（14.5-120 mW/cm²）范围内。在此基础上,本文研究了利用新的合成方法来调控金属碳化物和碳氮化物的结构性能,以提高在碱性溶液中的ORR活性。研究内容具体如下:第一,研究了碳氮化钛在氧还原反应（ORR）中的催化性能。碳氮化物的合成通常需要在高温（1200-1800 ^oC）下进行,从而... 

【文章来源】：中国科学院大学(中国科学院宁波材料技术与工程研究所)浙江省

【文章页数】：152 页

【学位级别】：博士

【文章目录】：
摘要
Abstract
Chapter 1:Introduction
    1.1 The early proposed catalysts for oxygen reduction reaction
    1.2 Physicochemical properties of carbides relevant for ORR activity
    1.3 Carbides as supports for ORR activity
    1.4 Carbides and non-metal support as ORR electrocatalysts
    1.5 Carbonitride support
    1.6 Methods relevant for tuning physicochemical properties of carbon and carbonitrides support
    1.7 Reference
Chapter 2:Experimental Preparation
    2.1 Main reagent adopted in experiments
    2.2 Instruments
    2.3 Synthetic methods for metal carbides
        2.3.1 Direct element combination
        2.3.2 Carbothermal Synthesis
        2.3.3 Sol-gel synthesis
        2.3.4 Gas phase reaction synthesis
        2.3.5 Solvothermal Synthesis
        2.3.6 Sonochemical synthesis
        2.3.7 Electrochemical synthesis
        2.3.8 Solid State Metal Oxide-Organic Reaction
    2.4 Post-synthesis heat treatment of carbides
    2.5 Reference
Chapter 3:Catalytic Effect of Co@TiC_(0.25)N_(0.75):the Electrocatalyst for Oxygen Reduction Reaction Activity in Alkaline Water
    3.1 Introduction
    3.2 Experimental section
        3.2.1 Electrocatalysts preparation
        3.2.2 Electrocatalysts synthetic mechanism
        3.2.3 Oxygen Reduction Reaction in Alkaline water
    3.3 Result and discussion
        3.3.1 The structural property of the electrocatalyst
        3.3.2 Co distribution on TiC_(0.25)N_(0.75) support
        3.3.3 Discussion of Oxygen Reduction Reaction Performance
        3.3.4 Kinetic modeling
    3.4 Conclusions
    3.5 Reference
Chapter 4:Solid-Solid Separation derived C@CoC_x for High Current Density and Efficient Oxygen Reduction Activity in Alkaline Water
    4.1 Introduction
    4.2 Experimental section
        4.2.1 Catalyst preparation
        4.2.2 Oxygen reduction of alkaline water
    4.3 Result and discussion
        4.3.1 Effect of synthesis design on structural properties of catalyst
        4.3.2 Structural property of the catalysts,surface area and pore distributions
        4.3.3 Oxygen reduction reaction activity and Kinetics modeling
    4.4 Conclusion
    4.5 References
Chapter 5:Single Phase Anti-perovskite Ternary Metal carbides for Oxygen Reduction Reaction on the Surface of Alkaline Water
    5.1 Introduction
    5.2 Experiment
        5.2.1 Anti-perovskite ternary metal carbides preparation
        5.2.2 Characterization
    5.3 Results and discussion
        5.3.1 Physicochemical property of anti-perovskite metal carbides
        5.3.2 Electrochemical performance of anti-perovskite metal carbides
    5.4 Conclusion
    5.5 References
Chapter 6:Summary and Outlook
    6.1 Summary
        6.1.1 Titanium carbonitride as a support for nanoparticles for ORR activity
        6.1.2 Hollow carbon supported CoC_x catalyst for alkaline water oxygen reduction activity
        6.1.3 Modified catalytic property of anti-perovskite metal carbides
    6.2 Outlook
Appendix
Acknowledgement
Author's resume and academic papers and research results published during the course of this degree


【参考文献】：
期刊论文
[1]氮、硫共掺杂的碳负载的钴@碳化钴:一种高效的非贵金属氧还原电催化剂（英文）[J]. 申海波,江浩,刘易斯,郝佳瑜,李文章,李洁.  物理化学学报. 2017(09)



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