二元Ni基非贵金属纳米材料催化氨硼烷制氢性能研究

Ammonia borane has been considered as a promising candidate material for hydrogen storage due to its very large hydrogen content. The temperature of pyrolysis from ammonia broane will be lower and the rate of hydrolysis will be faster with proper catalysts. However, the proper catalysts are almost based on noble metal. The binary non-noble metal catalysts are low cost, more stable, and needed to be more systematically and deeply studied. We will use miroemulsions method、solution thermal method、electroless deposition method to synthsize the binary catalysts which are formed by the non-noble metal Ni and Co or Cu. The composition, the crystal form, the combination pattern, and the crystallinity of the catalysts will be studied. We will do research on how the factors influence the catalysis, and get the best Ni-based catalysts. It will point out that the structure characteristic of the high efficiency catalyst, and establish the relationship of the catalysis and the physical properties of the materials. On the basis of the dectection of the intermediate and the simulation of the reaction, it will infer the mechanism of the hydrogen evolution reaction, including pyrolysis and hydrolysis. This subject aims to reveal the key effect of the catalytic performance. It is significant to the study for the hydrogen generation of ammonia borane.

氨硼烷储氢量大，成为储氢材料研究热点。催化剂可以显著降低氨硼烷热解温度，提高水解放氢速度，是影响氨硼烷放氢的关键因素。然而，性能较好的催化剂主要为贵金属或贵金属复合催化剂。二元非贵金属催化剂具有成本低，稳定性好等特点，这方面的研究还有待开展。本项目以此为切入点，采用微乳法、溶剂热法、化学镀法等可控合成Ni与非贵金属（Co、Cu）形成的纳米材料；研究催化材料的组成、晶型、组合方式、结晶度等因素对催化氨硼烷制氢性能的影响，优化得到最佳二元Ni基催化材料，建立材料的微观表面性质与催化性能之间的关联；并且通过催化反应中间产物检测和理论计算相结合，推断氨硼烷热解、水解制氢反应的机理，进而从根本上提出高效催化剂应具备的结构特征。本项目旨在揭示影响催化剂催化性能的关键因素，对氨硼烷制氢研究有重要意义。

氨硼烷储氢量大，成为储氢材料研究热点。催化剂可以显著降低氨硼烷热解温度，提高水解放氢速度，是影响氨硼烷放氢的关键因素。因此，性能较好、成本低的催化剂成为催化剂研究的关键。二元非贵金属催化剂具有成本低、稳定性好等特点。本项目以揭示氨硼烷放氢机理及其影响因素为目标，通过实验和理论计算相结合的方法，对氨硼烷在催化剂作用下放氢的性质，特别是不同催化剂催化的性能进行了一系列研究。.经过两年半的研究，课题组顺利完成了研究内容，达到了预期研究目标，并且研究领域还得到了进一步的扩展。目前，课题组取得的学术成果如下：采用溶剂热法、浸渍法等可控合成Ni与非贵金属（Co、Cu）形成的小颗粒状纳米材料；研究催化材料中各元素组成比例不同、通过煅烧前后制备结晶性不同、等催化剂材料，考察以上因素对催化氨硼烷制氢性能的影响，结果表明催化剂中元素比例是影响催化剂性能的重要因素，最佳的配比根据元素的不同而不尽相同；通过催化反应中间产物检测和理论计算相结合，推断氨硼烷热解、水解制氢反应的机理。具体工作为：（1）完成NiM(M=Co, Cu)及CoCu二元催化剂的制备及催化性能研究；（2）研究了NixCuy/TiO2@PS复合材料制备及催化氨硼烷水解制氢性能；（3）三元催化剂NixCoyCuz催化剂的制备及催化性能研究；（4）研究了催化剂催化氨硼烷水解放氢反应的机理；（5）以氨硼烷作为前驱体制备BN纳米材料。