金属有机骨架/羧基化石墨烯复合物担载Ni基非晶纳米颗粒体系的构建及其水合肼制氢催化特性

Hydrous hydrazine has been considered a promising candidate among hydrogen storage materials towards hydrogen society because of its high H2 content and easy recharging as a liquid. Searching appropriate nanocatalysts with excellent catalytic activity, 100% selectivity for H2 generation from hydrous hydrazine at mild temperature is a key point and difficulty to further promote the application process of hydrous hydrazine. The project employed metal organic frameworks and carboxyl graphene composites with high porosity, well stability, multi dimension as support, meanwhile employed Ni-based amorphous nanoparticles with low-cost and high concentration active sites as active subjects, take advantage of their strong interaction with each other, designed metal organic frameworks/carboxyl graphene composites supported Ni-based amorphous nanoparticles by solution infiltration method and one-step co-reduction method. Through investigating synergistic effect and electron transfer between supports and active subjects, access to obtain efficient catalyst system towards hydrogen generation from hydrous hydrazine, thus will provide the theoretical basis and experimental evidence for rational design of high performance and low cost hydrogen generation catalysts.

水合肼因具有高的含氢量和液体燃料的易填装特性而被认为是实现氢能社会所需的极具潜力的储氢材料候选者。寻求适当的催化剂以保障水合肼在温和条件下高效率、高选择性的释放氢气是进一步推动水合肼实用化进程的关键和难点。本项目以具有强稳定性、高孔隙率、多维度的金属有机骨架与羧基化石墨烯复合物作为催化剂载体材料，以具有低成本、高浓度活性位的Ni基非晶纳米颗粒作为催化剂活性主体，利用二者之间的强相互作用，采用溶液浸渍法及一步共还原法，设计出金属有机骨架/羧基化石墨烯复合物担载的Ni基非晶纳米颗粒。通过研究载体与活性主体之间的协同效应和电子转移，获取高效率的水合肼制氢用催化剂体系，从而将为理性设计高性能、低成本制氢用催化剂提供可靠的理论基础和实验依据。

以氢为燃料的氢燃料电池车被认为是解决能源危机和环境污染的重要选择。以甲酸、水合肼、氨硼烷为代表的化学储氢材料因其具有适宜的体积及质量储氢密度，不易燃，运输储存方便等优点，被认为是一类非常有前途的新型储氢材料。设计与构筑高性能催化剂以实现储氢材料的高活性与高转化率制氢具有重要的科学研究和应用价值。本项目通过对金属有机骨架等多孔材料进行功能化修饰，并将其作为催化剂载体，然后以颗粒尺寸介于1.5-11 nm之间且弥散分布的金属纳米颗粒作为催化剂活性主体，采用溶液浸渍法及一步共还原法制备得到一系列担载型纳米催化材料。利用载体与金属纳米颗粒之间的强相互作用，实现纳米颗粒的分散性、尺寸及电子态密度的调节。此外，通过掺杂、原位还原等方法对纳米颗粒活性主体的成分、结构及结晶度进行了可控调节。将担载型纳米催化材料应用于催化甲酸、水合肼、氨硼烷等储氢材料制氢反应中。通过表征及分析金属催化剂组元间的协同效应与催化性能的构效关系，获取高效率、低成本的储氢材料制氢用催化剂体系。所制备的各催化剂在催化储氢材料制氢反应中的初始转化频率（TOF）均高于目前报道的大多数相同条件下的异相催化剂，反应转化率均达到100%。在项目的实施中，发表SCI论文7篇，EI论文2篇，受理发明专利1项。本项目的完成，为促进储氢材料制氢的应用提供科学的实验依据，同时为新型清洁能源的开发研究奠定基础。