Calixarene-functionalized MoS2 nanoparticles as catalysts for HDS reactions

法律法规和全球石油原料质量的下降要求对石油产品的脱硫使用更有效的催化剂。基于二硫化钼（MoS2）的加氢脱硫材料是催化加氢脱硫的一个快速发展的工业应用和学术研究领域。一个关键的方面是获得高表面积以促进催化活性，并在高温还原条件下稳定小颗粒尺寸。基于我在博士论文中合成的小而高质量的二硫化钼纳米颗粒，我的目标是将这些构建块整合到合成具有催化活性和坚固性的结构中，这些结构在工作催化条件下保持其高活性和选择性。我的目标是建立催化结构-功能的理解，这将作为发展我的学术生涯的基础。我想在加州大学伯克利分校Katz教授的研究小组进行博士后研究，因为这个小组在杯芳烃配体的团簇和纳米颗粒的表面功能化方面处于世界领先地位，杯芳烃配体作为立体大体积配体，可以防止团聚，同时在表面产生自由配位。亚历山大·卡茨（Alexander Katz）的研究小组已经证明，非常大的配体和非常小的纳米颗粒的结合会导致配体不能完全覆盖颗粒的表面。协同不饱和位点是稳定高活性和有兴趣的加氢脱硫催化位点的关键。此外，杯芳烃配体上的官能团（给电子或取电子）可以影响纳米粒子的电子结构，从而影响它们的催化性能，以及将关键的镍成分结合到mos2纳米粒子中。

Legislative regulations and decreasing quality of global oil feedstocks require all the more active catalysts for the desulfurization of petroleum products. Materials for hydrodesulfurization (HDS) based on molybdenum disulfide (MoS2) represent a rapidly growing area of industrial application and academic research for HDS catalysis. A crucial aspect is to obtain a high surface area to facilitate catalytic activity, and to stabilize small particle sizes during catalysis under high temperature reducing conditions. Based on the synthesis of small, high quality MoS2 nanoparticles that I have synthesized during my PhD thesis, I aim to incorporate these building blocks to synthesize catalytically active and robust structures that retain their high activity and selectivity under working catalysis conditions. My goal is to create catalytic structure-function understanding that will serve as a foundation for developing my academic career. I seek to perform postdoctoral studies in the research group of Professor Katz at University of California, Berkeley because this group is a world leader in the surface functionalization of clusters and nanoparticles with calixarene ligands, which act as sterically bulky ligands that prevent agglomeration and create free coordination sites at the surface simultaneously. The group of Alexander Katz has demonstrated that the combination of very bulky ligands and very small nanoparticles lead to a situation that the ligands cannot cover the particle's surface completely. Coordinatively unsaturated sites are the result, which are predicted to be crucial for stabilizing highly active and interesting sites for hydrodesulfurization catalysis. Furthermore, functional groups (electron donating or withdrawing) at the calixarene ligand can influence the electronic structure of the nanoparticle and therefore also their catalytic properties, as well as incorporation of crucial nickel components to the MoS2-based nanoparticles.