Role of Bismuth Promoters in Heterogeneous Pt-Bi and Pd-Bi Catalysts: Computational Insights into Main Group Promotion

在这项由化学系化学催化计划资助的项目中，威斯康星大学麦迪逊分校的J.R.施密特教授正在研究金属表面催化反应中“促进剂”添加剂的作用。促进剂是添加到催化剂中以提高各种化学转化的效率(在能量和材料使用方面)的元素或化合物。虽然这类促进剂在化学工业中被广泛使用，但人们往往对它们的详细作用知之甚少。该项目正在使用基于计算机的建模来确定启动子影响化学反应的分子水平机制，并利用这一见解来推动新的和有效的化学转化的发展。具体地说，本研究重点研究了铋等P-嵌段助剂在铂族金属催化好氧醇氧化反应中的作用。使用密度泛函理论和动力学模型的组合，几个促进的假设正在被批判性地评估。这些结果是统一的，以发展有效的“理论”的P-嵌段促进，以促进发现新的选择性氧化反应和优化现有的催化氧化过程。施密特教授开发了一个推广项目，让本科生接触到使用基于网络的软件包的计算化学方法，重点是催化。因此，这项工作的更广泛影响包括为各种与工业相关的化学转化优化铂族金属催化剂的潜力，以及对威斯康星大学和全国各地的本科生和研究生进行现代计算方法培训。

In this project funded by the Chemical Catalysis program of the Chemistry Division, Professor J. R. Schmidt of the University of Wisconsin-Madison is examining the role of "promoter" additives in metal surface catalytic reactions. Promoters are elements or compounds that are added to catalysts to enhance the efficiency (both in terms of energy and the use of materials) of a wide variety of chemical transformations. Although such promoters are used broadly within the chemical industry, their detailed roles are often poorly understood. This project is using computer-based modeling to identify the molecular level mechanisms by which promoters influence chemical reactions, and to exploit this insight to advance the development of novel and efficient chemical transformations. Such work could lead to new and more energy efficient industrial chemical synthesis processes.Specifically, this study focuses on the role of bismuth and other p-block promoters in platinum-group metal catalyzed aerobic alcohol oxidation. Using a combination of density functional theory and kinetic modeling, several hypotheses of promotion are being critically evaluated. These results are unified to develop validated "theories" for p-block promotion in order to facilitate the discovery of novel selective oxidation reactions and to optimize existing catalytic oxidation processes. An outreach program, developed by Professor Schmidt, is exposing undergraduate students to computational chemistry methods using a web-based software package, with an emphasis on catalysis. The broader impacts of this work thus include both the potential for optimization of platinum-group metal catalysts for a wide variety of industrially-relevant chemical transformations, as well as the training of undergraduate and graduate students, both at University of Wisconsin and around the country, in modern computational methods.