Computational Studies of Catalyzed Chemical Transformations of Biomass
EMSL Project ID
47800
Abstract
There is a critical need to develop new, renewable sources of energy as well as feedstocks for the chemical industry. Biomass is a carbon neutral source of energy and can also address issues related to the sustainability of petroleum-based resources. An issue with biomass is that it is heavily oxygenated (glucose = (C(H2O))6) and catalytic processes are needed to convert the oxygenated biomass into deoxygenated fuels and intermediates. We propose electronic structure theoretical studies of a variety of catalytic processes for the conversion of biomass intermediates to useful fuels and feedstocks. These processes are explicitly controlled by the intrinsic bonds that form between the reactants or intermediates and the active catalytic site as well as by the local nanoscale environment/interface about the site. Catalytic behavior is governed by the size and shape, interaction with the support, composition and atomic configuration for metal alloys and mixed metal oxides, and the influence of solvent. The potential role of an aqueous solvent is important for biomass conversions because of the source of the raw material. We propose to use advanced computational chemistry approaches implemented on EMSL's massively parallel computers to develop a quantitative description of catalytic processes for biomass conversion to develop new design criteria and new understanding of the physical phenomena that occur at different spatial and temporal scales that underlie the catalytic behavior. We will apply computational chemistry at the density functional theory (molecular and plane-wave) and correlated molecular orbital theory levels to study a range of catalytic processes including: acid-base (Bronsted and Lewis) and redox reactions representative of relevant biomass transformations (e.g. deoxygenation, hydrogenolysis, dehydration, and hydroalkylation) on polyoxometalates and (MO3)n (M= Group VIB) clusters of glycerol, levulinic acid, and gamma-valerolactone; polyol and ring-opening hydrogenolysis over bifunctional metal catalysts; formic acid decomposition on Au nanoparticles and bimetallic alloys; selective hydrogenation of lactic acid on Cu-based and Pt-based bimetallic alloys; aldol condensation over metal and metal oxide particles; and hydroalkylation of cyclohexanol in mesoporous zeolites for lignin conversion. A team of researchers from four universities and PNNL with direct ties to experimental efforts will address these problems using appropriate computational methods with the goal of understanding interfacial processes and advancing our ability to understand catalytic processes leading to the design of new catalysts. The proposed computational work is being done in close collaboration with experimental teams, a number of which use EMSL resources or are located in the EMSL.
Project Details
Project type
Large-Scale EMSL Research
Start Date
2013-10-01
End Date
2015-09-30
Status
Closed
Released Data Link
Team
Principal Investigator
Co-Investigator(s)
Team Members
Related Publications
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