载体调控Pd结构用于室温高效催化甲酸盐析氢反应

Catalytic high-pure hydrogen evolution from formate at room temperature become one of most important research in hydrogen energy fields. Tremendous efforts have been devoted to solving these issues, however, the catalytic activities still need to further improve. Recently, immobilizing nanoparticle to kinds of supports, the catalytic activity showed significant variations. More importantly, studies on support effects in the single metal system will provide more significant information about H2 evolution. In this project, based on the significant structure parameters of the three vital processes, via controlling the kinds, well-defined facets of the support and the nitrogen-doped of carbon material to tune the surficial and electronic structure, then the H2 evolution from catalytic foramte hydrolysis will be investigated systematically. Combined DFT calculation and in situ characterizations, furthermore, the contributions of lattice strain and electronic structure as well as the active sites of catalytic formate hydrolysis will be investigated. Based on above, the relationships between structure and performance could be constructed, and these results are important to guide the synthesis of high-performance hydrogen evolution catalysts and to achieve high-pure hydrogen storage and evolution from formate at room temperature.

目前，实现室温条件下高纯氢气的释放是氢能源存储领域亟待解决的问题之一。最近报道的不同载体负载金属催化剂，用于催化甲酸/甲酸盐析氢反应已展现出显著的活性差异；而相对于多金属体系，载体调控单一金属催化剂有望为析氢反应的研究提供更多重要信息。本项目基于甲酸盐催化析氢的三个重要催化过程中的关键结构因素，拟在控制金属Pd小尺寸的基础上，通过载体种类和暴露规整晶面以及N掺杂的C载体，来调控金属Pd的晶格应力、表面结构和电子结构；在此基础上评价室温催化甲酸盐析氢活性，然后结合DFT理论计算和原位表征手段，探究催化反应的活性位点以及晶格应力和电子结构对催化过程的贡献，建立Pd催化甲酸盐析氢中的构效关系。实现室温高效催化甲酸盐析氢催化材料的控制合成，并为后续新型储氢材料的设计合成提供理论依据。

实现室温高纯氢气的可控释放是目前氢气存储领域亟待解决的问题。本项目以负载型金属催化剂为研究对象，探索金属和载体之间的相互作用并建立催化剂电子结构与其性能之间的构效关系。首先研究了四种氧化物载体调控Pd纳米颗粒的电子结构，提出了极化电子金属-载体相互作用的概念。实验与理论计算均发现了这种独特电子效应，然后详细分析了电子效应产生的原因。而进一步的析氢性能测试指出表面富电子的Pd原子是催化析氢的活性位点，由此建立了电子结构与析氢反应性能的线性关系。随后，针对能源中的新型载体材料MoCx，其晶相和表面结构是影响与金属相互作用和活性的关键因素，所以我们进行了详细的晶相控制合成，发现β相是最易出现的晶相，而我们通过前驱体的形貌控制成功制备了ɑ相和η相的碳化钼。初步活性探究也证明了相互作用对催化性能的影响。