Fundamentals of (Mixed) Transition Metal Oxides for Chemical Transformations
EMSL Project ID
50625
Abstract
The main objective of the proposal is to tackle the fundamental issues associated with moleculartransformations of biomass derived oxygenates (e.g., alcohols, aldehydes, ketones, and carboxylic
acids) to produce platform chemicals (i.e., olefins) using (mixed) transition metal oxide catalysts (e.g.,
ZrO2, CeO2, TiO2, and ZnxZryOz). We aim to develop accurate and unambiguous atomic-scale
structure/function relationships and identify catalytic site requirements for these reactions and catalysts.
Specifically, we will focus on: 1) determining the proximity, strength, and electronic properties of surface
acid-base site pairs; 2) examining the interaction/activation between oxygenates and the surface acidbase
site pairs; 3) understanding the synergy role interplayed by the reactant solvent (i.e., H2O) and
surface acid-base site pairs in controlling the reaction pathway and thus product selectivity. Our working
hypothesis is that the incorporation of a guest metal (M1) in the framework of host metal oxide (MOz)
leads to the polarization of the adjacent M-O bond, thus changing the electron density at both M and the
peripheral O atoms, or vice versa. Consequently, the generated M1-Os-M moieties will create tunable
Lewis acid (Mdelta+ and M1gamma+) and base (Osv-) site pairs, in turn influences the
interaction/activation of reactant, intermediate, and solvent (i.e., H2O). Our approach combines
synthesis of transition metal oxide catalysts with controlled structure, kinetic measurements and
mechanistic studies, extensive characterization, and theoretical investigation. To achieve these goals,
we propose using the critical capabilities available at EMSL (STEM, APT, XPS, NMR, SFG, EPR,
SSITKA, and High Performance Computing) to understand the chemistries occurring at the gas/solid
interfaces that will lead to better design and control of acid-base catalysts for chemical transformations
of biomass derived oxygenates to produce fuels and chemicals.
Project Details
Start Date
2018-11-07
End Date
2019-09-30
Status
Closed
Released Data Link
Team
Principal Investigator
Team Members
Related Publications
Dahal A.P., N.G. Petrik, Y. Wu, G. Kimmel, F. Gao, Y. Wang, and Z. Dohnalek. 2019. "Adsorption and Reaction of Methanol on Anatase TiO2(101) Single Crystals and Faceted Nanoparticles." Journal of Physical Chemistry C 123, no. 39:24133-24145. PNNL-SA-146554. doi:10.1021/acs.jpcc.9b07080
Stewart M.L., C.J. Kamp, F. Gao, Y. Wang, and M.H. Engelhard. 2018. "Coating Distribution in a Commercial SCR-Filter." Emissions Control Science and Technology 4, no. 4:260-270. PNNL-SA-132157. doi:10.1007/s40825-018-0097-3
Zhang J., J. Sun, L. Kovarik, M.H. Engelhard, L. Du, B. Sudduth, and H. Li, et al. 2020. "Surface Engineering of Earth-abundant Fe Catalysts for Selective Hydrodeoxygenation of Phenolics in Liquid Phase." Chemical Science 11, no. 23:5874-5880. PNNL-SA-149539. doi:10.1039/d0sc00983k