Density functional theory studies of biomass conversion on metal surfaces: from small to large molecules

Identificador:  TDX:2719

Handle: https://hdl.handle.net/20.500.11797/TDX2719

Autors:  Li, Qiang

Resum:
In this thesis, a series of surface reaction mechanisms related with various biomass derived molecules on slab models have been proposed and computed by using the Vienna Ab initio simulation package (VASP). 1 Multiscale investigation of hydrogen releasing from small molecules of methanol, ethanol, ethylene glycol, and glycerol have been studied. C1 and C2 alcohols’ calculations are performed both on Cu(111) and Ru(0001) surfaces and glycerol is on Ru(0001). Complete intermediates binding geometries were optimized, detailed decomposition, hydrogenation mechanisms related with these species have been proposed. BEP and TSS relationship have been analyzed and ab initio microkinetic simulation under different conditions has been also performed. 2 Glucose and mannose hydrogenation to their sugar alcohols on Ru(0001) surface. Reactions from linear and ring isomers have been calculated and compared between two sugar molecules, and compared with experiment results. The author found that concentrations of different reactant isomers in the liquid phase, different adsorption energies and reaction mechanisms work together to control the overall reaction rates. 3 Levulinic acid hydrogenation to gamma-valerolactone on Ru(0001) and HHDMA decorated Ru(0001) surface. Intramolecular ring formation mechanism on Ru(0001) surface has been outlined. Interfacial acidity and local structures in the HHDMA-Ru(0001) interface which promote the catalysis rate and stability against oxidation have been illuminated. 4 Lignin decomposition and hydrogenation on Ni(111) and Ru doped Ni(111) surfaces. Lignin decomposition mechanisms based on more complicated dimer model have been clarified. Stereocenter effects in its conversions have been discussed and the Ru doping effects on promoting the catalysts behavior is also elucidated.