Well-defined metal-oxide catalysts to understand fundamental chemical transformations
EMSL Project ID
48332
Abstract
Catalytic materials for the full and complex range of chemical transformations being considered for upgrading biomass-derived molecules to fuels and chemicals include metals dispersed on oxide- and carbon-support materials, and oxide materials themselves (including zeolites) that are essential as catalysts for acid/base and redox reactions. Among these materials, oxides have been the subject of far fewer fundamental studies aimed at developing structure/function relationships. Our current DOE/Office of Science/Basic Energy Sciences-funded program focuses on oxide-based acid/base or redox catalysts that are active for a broad range of important chemical transformations in the conversion of biomass-derived molecules to liquid fuels. As one example, acid-catalyzed dehydration of alcohols over oxide supported transition-metal oxide catalysts (e.g., tungsten oxide cluster and oligomeric structures) represent one potentially useful route for deoxygenating fuel precursors formed by deconstruction of cellulosic materials. Current oxide-based heterogeneous catalysts are structurally and chemically complex and their experimental assessment can seldom be interpreted with atomic-level precision. We seek to reduce the complexity of this class of catalyst materials to levels addressable and controllable at the atomic level structurally and mechanistically while maintaining rigorous connections with the conditions and materials relevant to catalysis. We do this via the synthesis of dispersed transition metal oxides with controlled domain size and atomic connectivity supported on high surface area scaffolds with nominally inert and homogeneous surfaces. With such materials, we are able to more precisely probe structure-function relations for supported oxide catalysts. The broad disciplines and expertise within this group allows us to exploit an integrated experimental/theoretical approach, with an overall objective to advance significantly our ability to understand, design, and control chemical transformations of biogenic molecules on oxide catalysts, specifically for redox and acid-base chemistries. For studies of both catalyst structure as well as catalytic reaction mechanisms, we require a wide-variety of state-of-the-art instrumentation that EMSL uniquely provides, including high field NMR and high resolution XPS spectroscopies, as well as state-of-the-art atomic resolution electron and He ion microscopies.
Project Details
Project type
Large-Scale EMSL Research
Start Date
2014-10-01
End Date
2016-09-30
Status
Closed
Released Data Link
Team
Principal Investigator
Co-Investigator(s)
Team Members
Related Publications
Deshlahra P, RT Carr, SH Chai, and E Iglesia. 2014. "Mechanistic Details and Reactivity Descriptors in Oxidation and Acid Catalysis of Methanol." ACS Catalysis 5:Acid and redox reaction rates of CH. doi:10.1021/cs501599y
Fang Z, JH Both, S Li, S Yue, E Apra, M Keceli, AF Wagner, and DA Dixon. 2016. "Benchmark Calculations of Energetic Properties of Groups 4 and 6 Transition Metal Oxide Nanoclusters Including Comparison to Density Functional Theory." Journal of Chemical Theory and Computation 12(8):3689–3710. doi:10.1021/acs.jctc.6b00464
Kwak JH, J Lee, J Szanyi, and CHF Peden. "Modification of the acid/base properties of ?-Al2O3 by oxide additives: An ethanol TPD investigation." Catalysis Today. doi:10.1016/j.cattod.2015.07.042
Li WZ, F Gao, Y Li, ED Walter, J Liu, CHF Peden, and Y Wang. 2015. "Nanocrystalline Anatase Titania Supported Vanadia Catalysts: Facet-dependent Structure of Vanadia." Journal of Physical Chemistry C 119(27):15094?15102. doi:10.1021/acs.jpcc.5b01486
Li Y, Z Wei, F Gao, L Kovarik, RA Baylon, CHF Peden, and Y Wang. 2015. "Effect of Oxygen Defects on the Catalytic Performance of VOx/CeO2 Catalysts for Oxidative Dehydrogenation of Methanol." ACS Catalysis 5(5):3006-3012. doi:10.1021/cs502084g
Sun J, RA Baylon, C Liu, D Mei, KJ Martin, P Venkitasubramanian, and Y Wang. 2016. "Key Roles of Lewis Acid-base Pairs on ZnxZryOz in Direct Ethanol/Acetone to Isobutene Conversion." Journal of the American Chemical Society 138(2):507-517. doi:10. 1021/jacs. 5b07401
Wan C, MY Hu, NR Jaegers, D Shi, H Wang, F Gao, Z Qin, Y Wang, and JZ Hu. 2016. "Investigating the Surface Structure of ?-Al2O3 Supported WOx Catalysts by High-Field 27Al MAS NMR and Electronic Structure Calculations." Journal of Physical Chemistry C 120(40):23093-23103. doi:10.1021/acs.jpcc.6b09060