高效多元过渡金属氧化物催化剂的设计、制备及其在液态有机储氢材料催化加/脱氢中的应用

With the development of polyheterocyclic liquid organic hydrogen storage technology, the storage and transport of hydrogen under ambient temperature and atmospheric pressure has been realized, and become one of the most potential hydrogen storage technology in application. However, one of the key issue in hydrogen storage technology is catalyst, which are normally used to be precious metals, such as Pt, Pd, Ru and so on. As the most effective catalysts, there are still essentially defects in the material, such as limited resources, high cost, easy to poisoning and disproportionation, etc., which makes the exploitation of cheap and highly efficient catalyst become necessary. This project is intend to work around the design and synthesis of highly efficient MxOy-type polynary transition metal oxide catalyst (M= the binary or ternary combination of Mo, W and V) and its application in catalytic hydrogenation/dehydrogenation. The proposed research will employ the state-of-the-art first principles based methods to calculate the thermochemical, kinetic and dynamic properties of various hydrogenation process and to guide our experimental work to design and discover new catalysts. By the binary or ternary combination of Mo, W and V, we could obtain the rearrangement of the electrons in the catalyst, particular research emphasis will be placed on the fundamental understanding of the relationship between the catalyst composition, microstructure and the catalytic performance. From deeply understanding the catalytic mechanisms to the control of the catalytic performance, we will finally establish a therotial method in the design of highly efficient polynary transition metal oxide catalyst that makes the calculation data match with the experiment results.

稠杂环液态有机储氢材料的出现使得氢能在常温常压下的存储和输运成为现实，是最具应用前景的储氢技术之一。然而，储氢技术中的关键环节之一催化剂大多使用贵金属催化剂，如Pt、Pd、Ru等。作为当前最有效的催化剂，它们还存在本质上的缺陷，比如资源有限、价格昂贵、易中毒和发生歧化反应等，这使得开发高效、廉价新型催化剂的工作极其重要。本项目围绕MxOy型（M = Mo、W、V中的两元或三元组合）过渡金属氧化物催化剂的设计、制备及其加氢/脱氢性能调控开展研究。拟采用理论计算与实验相结合的技术路线，通过对Mo、W、V等过渡金属间的组合设计出多元过渡金属氧化物，使得催化剂中的电荷重新排布，重点研究催化剂组成—微观结构—催化性能之间的关系，从深入认识反应机理到实现催化剂性能可控，最终实现建立一套精确的理论计算与实验结果相匹配的高效多元过渡金属氧化物催化剂材料理论设计方法和催化性能调控体系这一目标。

稠杂环液态有机储氢技术使得氢能在常温常压下的存储和输运成为现实，是最具应用前景的储氢技术之一。然而，储氢技术中的关键环节之一催化剂大多使用贵金属催化剂，如Pt、Pd、Ru等。作为当前最有效的催化剂，它们还存在本质上的缺陷，比如资源有限、价格昂贵、易中毒和发生歧化反应等，这使得开发高效、廉价新型催化剂的工作极其重要。本项目围绕MxOy型（M是过渡金属中的二元或三元组合）过渡金属氧化物催化剂的设计、制备及其加氢/脱氢性能调控开展研究。采用理论计算与实验相结合的技术路线，通过对MxOy型多元过渡金属氧化物催化剂的组成、微观结构对其催化性能的影响规律的研究，结果发现，MxOy型多元过渡金属氧化物可以通过增加缺陷浓度来获得更多的L酸性位点从而提升其本征活性。获得了对其催化作用机理及其与贵金属催化剂在催化加氢/脱氢反应机理上的本质区别的认知。结果发现，基于MxOy型多元过渡金属氧化物的催化剂能极大地降低催化脱氢反应的活化能，从而使得LOHC中所储存的氢气能快速释放，180度下5分钟可释放2.48wt%的氢气，比传统贵金属效率高出3倍以上。本项目研究实现了对催化剂性能进行调控，为开发出更为高效廉价的非贵金属催化剂，实现在针对特定基团或分子的催化上替代贵金属催化剂打下了坚实基础。此外，本项目研究出的多元过渡金属氧化物催化剂，在改善加氢/脱氢过程中出现的问题，如避免歧化反应、催化剂中毒等方面具有明显的优势，为解决液态有机储氢技术在氢能规模化推广应用提供了新的思路，且具有应用于国防军工领域的巨大潜力，应用前景广泛。