Hello, A change in allocation has been requested: Requester: coliu (Cong Liu) Project: Bio_catalysis Title: Biomass Catalysis for Energy Description: Quantum mechanical calculations will be carried out as follows: a. Identifying suitable computational methods The overall reactions involved in the investigations will be identified and the thermodynamic data for these reactions will be analyzed with a series of candidate computational methods, including both DFT and higher level ab initio methods. Based on our experience, B3LYP (DFT) will be utilized to carry out geometry optimizations and frequency calculations. The energy calculations will be performed with also G4MP2, CCSD(T) and MP2 methods. The highly accurate G4MP2 method that was developed by our group will be used as the bench mark method. The reaction energy and barrier will be calculated for these overall reactions. The most suitable method will be chosen based on efficient computational time and acceptable accuracy. b. Reaction pathways The themochemistry of individual reactions with detailed reaction pathways including important intermediates and transition states is the essential first step towards the understanding of the chemical transformations. This will be investigated using the suitable computational method from step a. Since the chemical transformations such as C-C coupling reactions are rather complicated and will generate many possible intermediate and product species, detailed reaction pathways and all the possible species will be calculated. In addition to gas phase calculations, non-aqueous solvent effect will be considered for reaction energies and barriers. c. The catalysis of C-C coupling reactions The C-C coupling reaction is the key step to convert C5-C6 compounds from the biomass pyrolysis to C8-C21 diesel fuel compounds. Diels-Alder (DA) reactions and aldol condensation are available reactions to achieve this type of transformations. Both homogeneous and heterogeneous catalysts will be studied, in which transition metal complexes (will be used for homogeneous catalysis and metal/metal oxide/alloy nanoparticles will be used for heterogeneous catalysis. For the homogeneous catalysis of the DA reaction, for instance, Lewis acid metal complexes will be considered as potential molecular catalysts. The catalytic properties of Lewis acid metal for DA reaction are due to the coordination of the metal to the functional groups of 1,3-diene, causing the decrease of the LUMO energy of the diene.12 Thus in the studies of the homogeneous catalysts the effect of the metal center will be the focus of interest. Examples of potential catalysts include 3d metal complexes such as titan ium dichloride diisopropoxide (Ti(IV)Cl2(iPrO)2), Cr(III), Ni(II) and Cu(II) pincer complexes, and Pd (II)(acac)2 complex. These fundamental studies of molecular models will provide constructive guidance for choosing heterogeneous catalysts, and a set of nanoparticle catalysts will be selected for further investigations, and examples include BaTiO3, Pd and Cu nanoparticles. The correlations and differences between the homogeneous and heterogeneous catalysis will be analyzed, in terms of the catalytic properties of the metal, the impact of the ligands, and the steric/structural effects. d. Multi-functional catalysts for ring opening and hydrogenation reaction An important step of getting the diesel fuel products is to remove the unsaturated bonds and oxygens in the longer chain carbon compounds. In many cases, this step involves both ring opening (breaking C-O bond in a ring) and hydrogenation (removing oxygens). To facilitate both reactions, efficient multi-function catalysts need to be developed. An ideal catalyst would be a bimetallic nanoparticle catalyst supported on a high surface area material, in which one metal acts as an oxophilic acid to reduce the polar bond and the other metal is being a base to help produce dissociated hydrogen. Potential catalysts include Au/Fe3O4 and Au/ZnO nanoparticles, as well as Pt or Pd metal nanoparticles-zeolite catalysts. The catalytic properties will be measured by reaction energetic. Current: undetermined amount Justification: Requested: 200000 A specific reason has been given: The transition states of the reactions in zeolites are difficult to locate using the NEB calculations of VASP program, and more CPU hours are needed. This needs to be approved and the final allocation amount decided upon. Thank You, The LCRC Accounts System