碳载金属单原子催化剂的构筑 及其清洁能源器件应用

时代发展对清洁能源的需求推动人们研发下一代电化学储能器件。锂硫电池、锌-空气电池等新型储能器件由于具有理论容量高、成本低廉、环境友好和高安全性等优势，而备受瞩目。然而硫/氧物种可逆转换过程中的缓慢动力学和反应过电势，制约了锂硫电池和锌-空气电池的输出功率、能量密度和可逆性能等关键电池指标。研究发现电催化作用能显著提高硫/氧物种电化学可逆转化能力，提升锂硫和锌-空气电池性能。因此，设计高性价比、高活性的硫/氧物种氧化还原反应多功能催化剂是发展新型电化学储能器件的关键。

常用贵金属催化剂（如Pt、Ir、Ru等）因为成本高，储量少，耐久性差等缺点，限制了其可持续性发展与商业化应用。基于碳基过渡金属（如Fe、Co、Ni、V等）单原子催化剂被认为是贵金属催化剂最有前途的替代品之一。本课题从活性位点设计和催化剂结构调控两个方面开展研究。首先，设计合成了纳米碳纤维负载的Co纳米颗粒修饰的V单原子材料，CoNP-VSA@CF，其在锂硫电池领域表现出优异的催化性能，表明异核金属掺杂的金属单原子催化剂在锂硫电池催化领域具有广阔的应用前景。然后制备了多孔碳负载FeCo基双单原子催化剂，FeCo-NCD。研究发现FeCo-NCD具备高度碳缺陷和高金属负载量的特点，在电催化领域中表现出卓越的多功能催化性能。由于孔隙结构尺寸较大，FeCo-NCD在锂硫电池中表现不突出。而该催化剂表现出优异氧还原和氧析出性能，在锌-空气电池中表现出高功率密度和长循环稳定性等特点。利用密度泛函理论计算，深入研究了FeCo基双单原子催化剂的反应机理，解析了氧还原反应和氧析出反应的活性位点，在理论角度证明了高度碳缺陷对于催化反应的优化作用。

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