Well-defined Metal-Oxide Catalysts to Understand Fundamental Chemical Transformations
EMSL Project ID
47582
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
2012-10-01
End Date
2014-09-30
Status
Closed
Released Data Link
Team
Principal Investigator
Co-Investigator(s)
Team Members
Related Publications
Deshlahra P, and E Iglesia. 2014. "Methanol Oxidative Dehydrogenation on Oxide Catalysts: Molecular and Dissociative Routes and Hydrogen Addition Energies as Descriptors of Reactivity." Journal of Physical Chemistry C 118(45):26115–26129. doi:10.1021/jp507922u
Deshlahra P, RT Carr, and E Iglesia. 2014. "Ionic and Covalent Stabilization of Intermediates and Transition States in Catalysis by Solid Acids." Journal of the American Chemical Society 136(43):15229–15247. doi:10.1021/ja506149c
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
Kovarik L, A Genc, CM Wang, A Qiu, CHF Peden, J Szanyi, and JH Kwak. 2013. "Tomography and High-Resolution Electron Microscopy Study of Surfaces and Porosity in a Plate-Like ?-Al2O3." Journal of Physical Chemistry C 117(1):179?186. doi:10.1021/jp306800h
Li WZ, L Kovarik, D Mei, J Liu, Y Wang, and CHF Peden. 2013. "Stable platinum nanoparticles on specific MgAl2O4 spinel facets at high temperatures in oxidizing atmospheres." Nature Communications 4:Article No. 2481. doi:10.1038/ncomms3481
Li WZ, L Kovarik, D Mei, MH Engelhard, F Gao, J Liu, Y Wang, and CHF Peden. 2014. "A general mechanism for stabilizing the small sizes of precious metal nanoparticles on oxide supports." Chemistry of Materials 26(19):5475-5481. doi:10.1021/cm5013203
Li Y, Z Wei, F Gao, L Kovarik, CHF Peden, and Y Wang. 2014. "Effects of CeO2 Support Facets on VOx/CeO2 Catalysts in Oxidative Dehydrogenation of Methanol." Journal of Catalysis 315(1):15-24. doi:10.1016/j.jcat.2014.04.013
Li Y, Z Wei, J Sun, F Gao, CHF Peden, and Y Wang. 2013. "Effect of Sodium on the Catalytic Properties of VOx/CeO2 Catalysts for Oxidative Dehydrogenation of Methanol." Journal of Physical Chemistry C 117(11):5722-5729. doi:10.1021/jp310512m
Peterson E, A DelaRiva, S Lin, RS Johnson, H Guo, J Miller, JH Kwak, CHF Peden, B Kiefer, LF Allard, F Ribeiro, and AK Datye. 2014. "Low-Temperature Carbon Monoxide Oxidation Catalysed by Regenerable Atomically Dispersed Palladium on Alumina." Nature Communications 5:Article No. 4885. doi:10.1038/ncomms5885
Ramasamy KK, and Y Wang. 2013. "Catalyst Activity Comparison of Alcohols over Zeolites." Journal of Energy Chemistry 22(1):65-71.
Shi H, OY Gutierrez, GL Haller, D Mei, RJ Rousseau, and JA Lercher. 2013. "Structure sensitivity of hydrogenolytic cleavage of endocyclic and exocyclic C-C bonds in methylcyclohexane over supported iridium particles." Journal of Catalysis 297:70-78. doi:10.1016/j.jcat.2012.09.018
Sun J, AM Karim, D Mei, M Engelhard, X Bao, and Y Wang. "New Insight into Reaction Mechanisms of Ethanol Steam Reforming on Co-ZrO2." Applied Catalysis B: Environmental. doi:10.1016/j.apcatb.2014.06.043
Vjunov A, MY Hu, J Feng, DM Camaioni, D Mei, JZ Hu, C Zhao, and JA Lercher. 2014. "Following Solid-Acid-Catalyzed Reactions by MAS NMR Spectroscopy in Liquid Phase -Zeolite-Catalyzed Conversion of Cyclohexanol in Water." Angewandte Chemie International Edition 53(2):479-482. doi:10.1002/anie.201306673
Zhao Z, S Xu, MY Hu, X Bao, CHF Peden, and JZ Hu. 2015. "Investigation of Aluminum Site Changes of Dehydrated Zeolite H-Beta during a Rehydration Process by High Field Solid State NMR." Journal of Physical Chemistry C 119(3):1410?1417. doi:10.1021/jp509982r