介孔材料负载纳米镍基合金催化水合肼分解制氢研究

The present project focuses on catalytic decomposition of hydrous hydrazine, a promising hydrogen generation system for on-board/mobile applications. The three key issues to be addressed are preparation of nanosized Ni-based alloy catalysts supported on mesoporous materials, elucidation of the mechanism of property modification arising upon alloying of the catalyst, and kinetic study of catalytic decomposition of hydrous hydrazine. By using evaporation-induced self-assembly and co-precipitation methods, a series of Ni-based alloy catalysts will be prepared, which are composed of tiny alloy nanoparticles immobilized on mesoporous supports containing strongly basic sites. The effects of preparation conditions on the morphology, microstructure, phase structure and surface electronic structure of the catalysts will be studied systematically. The composition-structure-property correlations of the Ni-based catalysts will be established on the basis of the coupled experimental and theoretical studies. The hydrous hydrazine-based hydrogen generation system will be constructed using Ni-based alloy catalyst with an optimal catalytic performance, and the effects of reaction conditions on reaction rate and hydrogen selectivity will be studied in detail. The reaction kinetics of catalytic decomposition of hydrous hydrazine will be studied by coupling experimental testing and theoretical model analysis. The studies conducted in the present project may lay experimental and theoretical foundations for the development of practical hydrous hydrazine-based hydrogen generation system.

项目选取水合肼这一颇具车载/移动氢源应用潜力的新型化学氢化物为研究对象，拟重点围绕介孔材料负载纳米镍基合金催化剂的制备、催化剂的合金化改性机理以及水合肼催化分解反应动力学开展研究。拟采用蒸发诱导自组装和共沉淀等方法制备具有不同化学组成、介孔结构特征并富含强碱性位的负载型纳米镍基合金催化剂；研究制备工艺对催化剂形貌、微观结构、物相组成及表面电子结构的影响规律；结合实验研究与理论计算，建立催化剂成分-结构-性能的内在关联。优选性能优异的催化剂构建水合肼催化分解制氢体系，系统考察反应条件对体系反应速率和制氢选择性的影响，结合实验测试与理论模型分析揭示水合肼催化分解反应动力学规律。本项目研究将为发展实用型水合肼催化分解制氢技术奠定实验/理论基础。

发展具有车载/移动氢源应用前景的水合肼（N2H4•H2O）制氢体系对于解决能源与环境等问题，实现可持续性发展具有重要意义。水合肼制氢体系的研究关键在于研发兼具高催化活性、高制氢选择性、高耐久性的催化剂。本项目针对此问题，采用不同的化学合成方法制备了一系列镍基合金负载型催化剂，重点围绕催化剂的制备、结构及性能的关联开展研究。项目研究计划要点包括：（1）镍基合金催化剂的制备及其对水合肼分解制氢的影响；（2）揭示水合肼催化分解制氢反应动力学规律；（3）构建高容量水合肼可控制氢体系。本项目在水合肼催化分解制氢高性能催化剂的制备、反应机理的认识等方面取得了创新性研究成果: 基于理论计算和实验解释了镍基合金化对水合肼分解制氢的反应机理，并揭示了水合肼催化分解反应动力学规律，为研制高性能水合肼分解催化剂提供了成分设计指导原则；基于研制的催化剂构建了高储氢容量的水合肼制氢体系，实验证实了该制氢体系的材料基储氢容量可达6.54wt%，该储氢容量为目前报道的最高值。项目的研究提供了高容量可控制氢体系，为研发实用型可控制氢系统提供了实验/理论基础。基于本项目研究结果，已发表SCI 论文12篇，申请专利2件。项目执行期间，培养毕业硕士研究生2名，博士研究生1名。项目研究全面达到了预期研究目标。