Design and synthesis of hydrogenation nanocatalyst with synergetic multiple catalytic sites

基于催化剂多活性中心分工协同作用可活化两种或多种反应物,本研究工作以一种新的制备策略对贵金属-过渡金属-过渡金属氧化物催化剂进行合理设计,构筑金属与金属氧化物双活性中心。结果发现,贵金属负载于过渡金属/过渡金属氧化物(nM-TM/TMO)结构的催化剂在加氢反应中具有优异的催化活性。同时,热处理方法可有效调控催化剂微观结构,并对此构效关系进行了较为深入的研究。As synergic multiple active sites catalysts can theoretically activate two or more reactant or substrates simultaneously resulting in significantly increase of activity and stability of catalysts, we herein develop a novel catalysts preparation strategy to design and construct noble metal-transition metal-transition metal oxide(NM-TM/TMO) to form bi-active catalytic sites.The experimental results show that such a catalyst has excellent performance in catalytic hydrogenation, e.g.aromatic compounds hydrogenation as the case studies.It was also found that the nanostructure of catalyst can be tuned via thermal treatments, which are investigated and the relationship between structure and activity is explored to some extent.国家自然科学基金项目(20973140;201106118;21303140)~

In situ dynamic tracking of heterogeneous nanocatalytic processes by shell-isolated nanoparticle-enhanced Raman spectroscopy

原位监测纳米催化反应过程对深入认识反应机理、设计高效催化剂具有重要意义。作为一种具有超高灵敏度的表面分析技术，表面增强拉曼光谱（SERS）是可提供反应过程中催化剂表面吸附物种的丰富信息。然而，仅有Au、Ag、Cu等少数金属在形成特定纳米结构时才能提供较强的拉曼增强，且它们会对催化剂的性质及反应过程产生严重干扰。这就极大地限制了SERS在实际多相催化体系中的应用。鉴于此，该论文发展了一种利用壳层隔绝纳米粒子增强拉曼光谱原位监测纳米催化过程的方法。通过将纳米催化剂组装于壳层隔绝纳米粒子表面，形成SHIENRS卫星结构，利用内核Au纳米粒子增强催化剂表面的拉曼信号，SiO2壳层隔绝Au对催化剂及反应的影响，从而直接获得了纳米催化剂表面物种的真实信息。利用这种SHINERS卫星策略，他们实现了CO氧化反应的原位监测，直接观测到了反应条件下催化剂表面吸附物种。并结合DFT计算，对反应机理进行了阐述。该研究表明SHINERS卫星策略可作为原位跟踪催化反应过程的有效方法，为纳米催化的原位研究提供了一种新的思路。 同时，我校也将在今年12月5-9日举办表面增强拉曼光谱国际会议(International Conference on SERS)，讨论SERS领域的最新进展。会议期间，SERS领域的先驱与权威Richard P. Van Duyne、Martin Moskovits、Andreas Otto以及相关学科的顶级学者Peter G. Bruce、Stefan A. Maier等将作大会报告（会议官方网站http://sers2017.xmu.edu.cn/）。【Abstract】Surface molecular information acquired in situ from a catalytic process can greatly promote the rational design of highly efficient catalysts by revealing structure-activity relationships and reaction mechanisms. Raman spectroscopy can provide this rich structural information, but normal Raman is not sensitive enough to detect trace active species adsorbed on the surface of catalysts. Here we develop a general method for in situ monitoring of heterogeneous catalytic processes through shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) satellite nanocomposites (Au-core silica-shell nanocatalyst-satellite structures), which are stable and have extremely high surface Raman sensitivity. By combining operando SHINERS with density functional theory calculations, we identify the working mechanisms for CO oxidation over PtFe and Pd nanocatalysts, which are typical low- and high-temperature catalysts, respectively. Active species, such as surface oxides, superoxide/peroxide species and Pd–C/Pt–C bonds are directly observed during the reactions. We demonstrate that in situ SHINERS can provide a deep understanding of the fundamental concepts of catalysis.This work was supported by the NSFC (21522508, 21427813, 21373167, 21521004, 21573178 and 21673187), Natural Science Foundation of Guangdong Province (2016A030308012), the Fundamental Research Funds for the Central Universities (20720150039 and 20720160046), ‘111’Project (B16029), and the Thousand Youth Talents Plan of China。 研究工作得到国家自然科学基金优秀青年基金、谱学分析创新研究群体和青年千人计划等资助