David D. Hibbitts

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The selective oxidation of alcohols in aqueous phase over supported metal catalysts is facilitated by high-pH conditions. We have studied the mechanism of ethanol and glycerol oxidation to acids over various supported gold and platinum catalysts. Labeling experiments with (18)O(2) and H(2)(18)O demonstrate that oxygen atoms originating from hydroxide ions(More)
A ReO(x)-promoted Rh/C catalyst is shown to be selective in the hydrogenolysis of secondary C-O bonds for a broad range of cyclic ethers and polyols, these being important classes of compounds in biomass-derived feedstocks. Experimentally observed reactivity trends, NH(3) temperature-programmed desorption (TPD) profiles, and results from theoretical(More)
We present a computational screening study of ternary metal borohydrides for reversible hydrogen storage based on density functional theory. We investigate the stability and decomposition of alloys containing 1 alkali metal atom, Li, Na, or K (M(1)); and 1 alkali, alkaline earth or 3d/4d transition metal atom (M(2)) plus two to five (BH(4))(-) groups, i.e.,(More)
Ethane hydrogenolysis involves C–C bond rupture in unsaturated species in quasi-equilibrium with gaseous reactants and H 2 on metal clusters, because C–C bonds weaken as C-atoms replace hydrogen with exposed metal atoms from catalyst surfaces. The nature and reactivity of such adsorbed species are probed here using kinetic data and density functional theory(More)
Kinetic and isotopic data on Pt clusters and activation free energy barriers from density functional theory (DFT) on Pt(111) are used to assess the elementary steps involved in NO–H2 reactions. Pt clusters 1–10 nm in diameter gave similar turnover rates, indicating that these elementary steps are insensitive to surface-atom coordination. N–O cleavage occurs(More)
Controlling the charge transfer between a semiconducting catalyst carrier and the supported transition metal active phase represents an elite strategy for fine turning the electronic structure of the catalytic centers, hence their activity and selectivity. These phenomena have been theoretically and experimentally elucidated for oxide supports but remain(More)
This study combines theory and experiment to determine the kinetically relevant steps and site requirements for deoxygenation of alkanols and alkanals. These reactants deoxygenate predominantly via decarbonylation (C-C cleavage) instead of C-O hydrogenolysis on Ir, Pt, and Ru, leading to strong inhibition effects by chemisorbed CO (CO*). C-C cleavage occurs(More)
The kinetic relevance and rates of elementary steps involved in C−C bond hydrogenolysis for isobutane, neopentane, and 2,3-dimethylbutane reactants were systematically probed using activation enthalpies and free energies derived from density functional theory. Previous studies showed that C−C cleavage in alkanes occurs via unsaturated species formed in fast(More)
High CO* coverages lead to rates much higher than Langmuirian treatments predict because co-adsorbate interactions destabilize relevant transition states less than their bound precursors. This is shown here by kinetic and spectroscopic data-interpreted by rate equations modified for thermodynamically nonideal surfaces-and by DFT treatments of CO-covered Ru(More)