Black Phosphorus Supported Single Site Catalysts for Hydrocarbon Functionalization

University Of Washington, Seattle WA

Investigators

Abstract

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.