金属酞菁基电催化剂的分子工程及应用研究

新能源时代背景下，电化学能源转化技术以其清洁、高效特点，在可持续能源的生产、存储与利用中扮演着关键角色。电化学能源转化过程一般需要电催化剂来促进化学反应的进行，而电催化剂性能的优劣制约着电化学转化效率。金属酞菁（MPc）基电催化剂因其结构明确和性能良好等特点而受到关注。但在面向工业级条件的实际应用方面，MPc基电催化剂还存在着明显不足。为了拓展MPc基电催化剂的应用潜力，本论文选择了催化性能较好、易于制备的三种非贵金属MPc（CoPc、NiPc、FePc），并构建了MPc分子锚定于多壁碳纳米管（CNTs）的单分子分散电催化剂（MPc MDEs）体系。通过分子结构与基底等分子工程调控，优化电催化性能，并研究了它们在相应电化能源转化系统中的应用。

在电解水析氢反应（HER）中，发展了多尺度工程调控策略，实现了CoPc MDEs在工业级电流密度下的稳定运行。通过理论计算和实验测试，发现MDE的构建能有效保障分子与碳基底的强相互作用，揭示了电荷传输是影响分子电催化剂表观性能的关键；通过氰基（CN）引入的结构调控，优化了电催化剂本征活性，有效降低了CoPc MDE催化剂在-10 mA cm-2电流密度下的过电位；基于三维自支撑电极的构筑和亲水基团（DEG）的引入，提升了电催化剂整体传质能力。优化后的CoPc-DEG MDE@CC可在-1000 mA cm-2的电流密度下稳定工作25小时。

在水相二氧化碳还原反应（CO2RR）中，发展了氟（F）修饰调控策略，构筑的NiPc-F MDEs在工业级电流密度下能够快速、稳定、高选择性地实现CO2电还原至CO。在NiPc MDE电极的构筑中，发现疏水组分PTFE的引入可以有效提高电极材料的选择性和稳定性，但会损失部分催化活性。通过在NiPc配体中引入8个F原子，可以增强分子在催化反应中的结构稳定性以及与碳基底的相互作用强度，提高NiPc-F MDE的催化选择性和活性。进一步通过多尺度工程调控策略，在气体扩散层中引入强疏水性分子（C8SiF13Cl3H4）以及催化层碳基底结构的调控，增强了电极的传质能力和三相界面稳定性。将优化后的催化剂电极NiPc-F MDE-GDE-A组装于流动型电解池中，可在-300 mA cm-2工业级电流密度下稳定运行45小时，产CO法拉第效率≥98%。

在基于有机电解质的锂-二氧化碳（Li-CO2）电池应用中，开发了放电电压为2.67 V，电容量达10800 mAh g-1的NiPc MDE阴极电催化剂。NiPc MDE的构建可以实现NiPc分子催化性能优势和CNTs结构优势互补，能有效地电催化CO2还原，并促进Li2CO3的可逆转化。将CN引入NiPc配体中，显著增强了NiPc分子与CNTs之间的相互作用。将优化后的NiPc-CN MDE应用在Li-CO2电池阴极中，展现出2.72 V的高放电电压和1.4 V的充放电位差，并能够稳定运行120次循环以上，展现出良好的充放电可逆性。

在氧气还原反应（ORR）中，发展了双重分子结构调控方法，构筑的FePc MDEs实现了高效四电子转移的ORR催化。通过取代基修饰，发展的十六氟基（16F）取代的FePc-16F MDEs，有效避免了CN调控引入的副活性中心问题，综合提升了FePc MDEs电催化活性和选择性。进一步地，利用碘离子（I-）对酞菁金属中心Fe进行轴向配位，所制备的FePc-16F-I MDE表现出更高的ORR催化活性，在碱性环境中半波电位达0.951 V。在锌-空气气电池中，FePc-16F-I MDE最大功率密度和比容量分别可达203 mW cm-2和821 mAh g-1Zn，高于商业Pt/C催化剂126 mW cm-2的最大功率密度和755 mAh g-1Zn的比容量。

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