Black Phosphorus Supported Single Site Catalysts for Hydrocarbon Functionalization

在化学系化学催化项目的支持下，华盛顿大学的Alexandra Velian正在研究新一代氢甲酰化催化剂的开发，氢甲酰化是一种与工业相关的过程，负责合成各种制造过程中使用的含氧化合物。由一种叫做黑磷的材料支持的过渡金属氢甲酰化催化剂的形成、结构和有效性正在被评估，以确定它们是否可以被调整成比现有系统更节能、更有选择性。此外，这项工作还揭示了设计由磷元素最稳定形式的磷原子扩展网络支持的多相催化剂的基本科学知识。这项工作是作为一个平台，培养不同群体的研究生和本科生在无机化学和催化。Velian博士和她的团队正在为初高中学生创建“在家”的科学实验，重点关注与无机材料和催化有关的主题。Velian博士还通过“化学前沿”课程积极促进和让学生接触到本科研究。在工业规模上使用的最成功的氢甲酰化催化剂是均相铑催化剂，在较小程度上是钴催化剂，具有氢化物、羰基和膦配体。铑的高价格和回收均相催化剂的挑战使得通过使用单原子催化混合均相催化和多相催化的优点的想法成为开发新的氢甲酰化体系的一个有吸引力的选择。Velian博士和她的研究小组正在开发由黑磷支持的氢甲酰化单原子催化剂。支持这一总体目标的活动包括：1)探索黑磷作为氢甲酰化催化剂的支持物的特性，并确定催化活性与同质类似物的区别；2)评估黑磷不同寻常的立体电子性质如何影响烯烃氢甲酰化的区域选择性和立体选择性；3)确定黑磷是否可以为多组分单原子催化剂（即烯烃异构化和氢甲酰化）提供一个协同工作的平台。进一步的基础研究集中在阐明黑磷作为配体的性质，以及如何利用其独特的物理化学性质来开发下一代单原子催化剂。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

With the support of the Chemical Catalysis Program in the Division of Chemistry, Alexandra Velian of the University of Washington is studying the development of a new generation of catalysts for hydroformylation, a process of industrial relevance that is responsible for the synthesis of oxo compounds used in a variety of manufacturing processes. The formation, structure, and effectiveness of transition metal hydroformylation catalysts supported by a material called black phosphorus are being evaluated to determine if they can be tuned to be more energy efficient and selective than established systems. Additionally, this work is uncovering basic scientific knowledge regarding the design of heterogeneous catalysts supported by the extended network of phosphorus atoms in the most stable form of the element phosphorus. This work is serving as a platform to train a diverse group of graduate and undergraduate students in inorganic chemistry and catalysis. Dr. Velian and her team are creating “at home” science experiments for middle school and high school students that focus on topics related to inorganic materials and catalysis. Dr. Velian is also actively promoting and exposing students to undergraduate research through a “Chemistry Frontiers” course. The most successful hydroformylation catalysts used at industrial scales are homogeneous rhodium catalysts and, to a lesser extent, cobalt catalysts, with hydride, carbonyl, and phosphine ligands. The high price of rhodium and the challenges in recycling homogeneous catalysts make the idea of blending the advantages of homogeneous catalysis and heterogeneous catalysis through the use of single-atom catalysis to be an appealing option for the development of new hydroformylation systems. Dr. Velian and her research group are developing single-atom catalysts for hydroformylation supported by black phosphorus. Activities supporting this over-arching goal include: 1) probing the characteristics of black phosphorous as a support for hydroformylation catalysts and determining how catalytic activity differs from homogenous analogues; 2) evaluating how the unusual stereoelectronic properties of black phosphorus influence the regioselectivity and stereoselectivity of olefin hydroformylation, and 3) determining if black phosphorus can provide a canvas for multi-component single atom catalysts that can work synergistically (i.e. for olefin isomerization and hydroformylation). Further foundational studies are focused on elucidating the nature of black phosphorus as a ligand, and how its unique physicochemical properties can be leveraged in developing next-generation single atom catalysts.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.