Improvement of Heterogeneous Catalyst Using Continuous Plug Flow Reactors and High-Resolution Magic Angle Spinning Solid State NMR

The proposed project is seeking funding to support the new faculties efforts to equip and supply a laboratory space to carry out heterogeneous catalyst research. The pIs long-term vision is use flow reactors, along with solid- state NMR to develop a high-level generalized methodology to study complex phenomena including catalyst support interactions, solvent effects, and operando surface reactions. Several specific catalyst systems have been identified which can be investigated once the proper laboratory infrastructure has been established with minimal additional required equipment including CH-activation, CO2 utilization, supercritical fluid extraction, and hydrodesulphurization. In the short term, the pI has identified hydrodesulfurization as the highest priority and is currently working in collaboration with fellow faculty in the chemistry department to move this project forward with support from Aramco. The research effort will build off the pIs background in physical chemistry and chemical engineering to first synthesize and screen a suite of catalyst materials using a laboratory scale flow reactor to determine kinetic parameters, and test stability for novel catalyst systems produced at KFUPM. Flow reactor experiments will determine activation energy, turnover frequency, and selectivity and deactivation rates. During the NMR phase of the research, the pI will build off his extensive solid state NMR experience to probe molecular interactions occurring at the catalyst surface-liquid interface. HR-MAS NMR will be the principle approach utilized, although quantitative 13C NMR, and homonuclear and heteronuclear 2D experiments will also be utilized. Intellectual Merit of the project: This project will improve the current understand of heterogeneous catalyst in the condensed phase, and lay the foundation to engineer more effective catalyst materials. HR-MAS MAS in compliment to flow reactor experiments will provide a detailed picture of the molecular scale interactions occurring at catalyst surface, important for activity, selectivity and stability. HR-MAS NMR of solid liquid interfaces is a new area of research which the PI has been on the forefront of, and has the capability to measure critical phenomena Including determination of deactivation mechanisms, (molecular mobility with CP filters) quantitation of binding strength, (metal support interactions) comparison of the influence of the solvent, (solvent effects/micro-kinetic modeling). When using these advanced characterization techniques in parallel flow reactor experiments the project has the potential to create some seminal work in understanding critical factors that affect key properties, and aid in improvement of catalyst for specific applications. Broader Impacts: This research will aid in the continued development of a tier I catalyst research program at KFUPM in the department of chemistry. With the resources currently available in the department of chemistry, and the unique research background of the PI, this proposal will set the groundwork to developing unique capabilities to connect solid state NMR to heterogeneous catalyst is a novel manner. These experimental data will also serve as a footing to foster collaborations within the department with computation chemists to further probe these complex phenomena. Lastly, the project will include undergraduate students in research activities and provide opportunities to participate research at the interface between chemical engineering and physical chemistry.