电沉积法制备氮硫双掺杂三维石墨烯担载纳米Co1-xSe催化剂及其氧还原机理研究

Proton exchange membrane fuel cell (PEMFC) is an environmentally friendly power generation technology with high energy density. The commercial applications of PEMFC are mainly limited by the ORR catalyst due to its high cost and short life. In order to solve those problems, a low cost, highly active, and high stability ORR catalyst is proposed in this project. . Co1-xSe nano-particles will be prepared by electrodeposition from the ionic liquids. The deposition conditions of Co1-xSe nano-particles with suitable composition and appropriate structure will be investigated in order to maximize the characteristic and the co-deposition mechanism will be explored. Nitrogen and sulfur dual-doped three-dimensional graphene (3D N,S-RGO), which is suitable for supporting Co1-xSe nanoparticles, will be prepared by hydrothermal method. Then Co1-xSe/N,S-RGO catalyst will be obtained via electrodeposition. The structure-activity relationship between the composition and structure of Co1-xSe/N,S-RGO catalyst and the oxygen reduction performance is also investigated. At the same time, the synergistic mechanism between Co1-xSe, NS and RGO and the mechanism of ORR are further elucidated, then single cell will be assembled and the performance will be tested.. This project is of great significance for the preparation of non-precious metal catalysts, the development of oxygen reduction catalyst theory and the commercialization of PEMFC.

质子交换膜燃料电池(PEMFC)是一种能量密度高、环境友好的发电技术，其商业化应用主要受氧还原催化剂成本高、寿命短的制约。针对上述问题，本项目研究一种制备低成本、高活性和高稳定性氧还原催化剂的新方法。. 在离子液体中电沉积Co1-xSe纳米颗粒，确定组成和结构可调控的电沉积参数，提出离子液体中Co1-xSe的共沉积机理；采用水热法制备适合于担载Co1-xSe纳米颗粒的氮硫双掺杂三维石墨烯（3D N,S-RGO）；采用电沉积法制备Co1-xSe/N,S-RGO催化剂，探讨Co1-xSe/N,S-RGO催化剂组成及结构与氧还原性能之间的构效关系，弄清Co1-xSe、NS、RGO三者之间的协同作用机制及其氧还原机理。组装单体电池，进行电池性能测试。. 本项目的研究对制备非贵金属催化剂、发展氧还原电催化理论、推动PEMFC的商业化进程具有重要意义。

开发适用于氧反应的新型非贵金属电催化剂是推动质子交换膜燃料电池(PEMFC)和锌-空气电池（ZAB）技术发展的关键。在众多候选中，钴-硒类化合物因具备利于催化吸脱附行为的电子结构，被认为是具有前途的催化剂材料。而采取可靠的改性策略，使钴-硒催化剂能够在不同溶液体系中兼顾高效且持久的催化氧析出(OER)和氧还原（ORR）进行具有很大的研究意义。. 项目提出采用电沉积法制备出具有OER/ORR双功能催化活性的纳米 Co-Se 催化剂，同时将高活性催化剂负载于氮硫双掺杂三维石墨烯载体表面，进一步改善催化剂的活性及稳定性。首先，系统揭示了Co-Se的电化学共沉积机理，并探究在不同溶液体系中电沉积制备Co-Se纳米颗粒的机制与工艺优化条件，实现高活性Co-Se镀层的可控合成。随后，采用水热和高温固相策略制备出适用于担载高活性催化剂的多种非金属掺杂型石墨烯材料（GNHCNs和NS-C），明确掺杂改性方法对载体结构、组成及其催化性能的影响；以高活性Fe-N-C结构为研究对象，探讨其在石墨烯和不同碳基载体上催化剂组成及结构与氧还原性能之间的构效关系，揭示载体与催化剂层之间的协同作用及其氧还原促进机制。基于高活性的负载型碳基催化剂，组装单体电池进行性能测试，综合评估实用价值。本研究对发展氧析出与氧还原电催化理论，开发新型高效氧反应催化剂，推进ZAB和PEMFC产业化进程具有重要意义。