直接醇燃料电池阳极非贵金属杂原子共掺杂碳化物量子点/三维石墨烯催化剂的性能与机理研究

Development of novel non-precious metal electrocatalysts for fuel cells replacing precious metal electrocatalysts is considered as the key issue of this filed. However, there are few reports on non-precious metal electrocatalysts with reasonable activity for direct alcohol fuel cells (DAFCs) in acidic medium. Metal carbides have been reported as non-precious metal electrocatalysts for methanol oxidation reaction (MOR) with slight catalytic activies based on its Pt-like electronic structure and catalytic behavior. For designing and developing novel non-precious anodic electrocatalysts for DAFCs with potential applications, metal carbides (TaC and WC) are intended to be modified according to electronic structure tuned by muti-heteroatoms doping and nano-structures designing. Thus, an ion exchange and activation methodology are proposed using for preparing multi-heteroatoms doped TaC or WC quantum dots supported on three dimentional graphene. Doping structure and particle size of metal carbides and pores structure will be controllable by optimization of the methodology. Furthermore, relationships between electrochemical pewrformance including activities, durabilities and CO tolerance for alcohol oxidation reaction (AOR) in acidic medium and the content and structure of non-precious metal electrocatalysts will be studyed. Meanwhile, density functional theory (DFT) will be used for explaining the electrocatalytic active sites and mechanism. The successful implementation of this project will provide important basics on developments of overall noble metal free fuel cells.

用非贵金属代替贵金属一直是燃料电池催化剂研究中的一个重要努力方向。然而，具有应用潜力的直接醇类燃料电池阳极非贵金属催化剂一直鲜有报道。基于类Pt电子结构和催化行为，碳化物具有微弱的醇氧化反应催化活性。本项目拟通过对碳化物（TaC和WC）微观结构的设计和电子结构的掺杂调控，提高其催化活性，实现醇燃料电池阳极非贵金属催化剂的开发。为此，本项目拟利用离子交换-交联活化法合成三维石墨烯负载的杂原子共掺杂碳化物量子点催化剂，并对其结构进行详细表征。通过对合成条件的优化，实现对碳化物掺杂结构、粒径大小及载体结构的调控。同时，对所制备的复合催化剂在酸性介质中不同醇类氧化反应的催化活性、稳定性与抗CO毒化能力等，以及催化剂的组成、结构与催化性能的关系进行研究。在此基础上，利用密度泛函理论计算，阐明其催化活性中心及催化机理。本项目的实施将对拓展醇类燃料电池阳极非贵金属催化剂具有重要的科学和实际意义。

本项目研究了多种杂原子掺杂过渡金属碳化物的合成，并制备了掺杂过渡金属碳化物量子点。在此基础上，对研究体系进行拓展，制备了若干高性能燃料电池和电化学水分解池非贵金属催化剂。主要成果包括：杂原子掺杂过渡金属碳化物的可控合成；掺杂过渡金属碳化物颗粒的纳米化制备；电子调谐构筑燃料电池高性能阳极催化剂及酸性水分解阳极催化剂的机理研究；缺陷，包括掺杂、空位等对非贵金属催化剂结构设计和性能促进作用的设计和研究等。

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