RESUMEN
NiO/ceria-zirconia (CZ) is a promising catalyst for the selective oxidation of benzene, as the Lewis-acidic NiO clusters can activate C-H bonds and the redox-active CZ support can activate O2 and supply active oxygen species for the reaction. In this study, we used transmission in situ infrared (IR) spectroscopy to examine surface species formed from benzene, water, oxygen, phenol, and catechol on a NiO/CZ catalyst. The formation of surface species from benzene and phenol was compared at different temperatures in the range of 50-200 °C in the presence and absence of water vapor. We also examined the role of the NiO clusters and the CZ support during benzene activation by comparing the surface species formed on NiO-CZ with those formed on a Ni-free CZ support and on a NiO/SiO2 catalyst. The spectrum of surface species from dosing benzene at 180 °C provides evidence for C-H bond activation. Specifically, the observation of C-O stretching vibrations indicates the formation of phenolate species. Introduction of water enhances these IR signals and introduces several additional peaks, indicating that a variety of different surface species are formed. These results show that NiO/CZ could catalyze direct conversion of benzene to phenol.
RESUMEN
Strong adsorption of ketone and diketone byproducts and their fragmentation products during the aqueous phase reforming of biomass derived oxygenates is believed to be responsible for the deactivation of supported Pt catalysts. This study involves a combined experimental and theoretical approach to demonstrate the interactions of several model di/ketone poisons with Pt/γ-Al2O3 catalysts. Particular di/ketones were selected to reveal the effects of hydroxyl groups (acetone, hydroxyacetone), conjugation with C=C bonds (mesityl oxide), intramolecular distance between carbonyls in diketones (2,3-butanedione, 2,4-pentanedione), and length of terminal alkyl chains (3,4-hexanedione). The formation of adsorbed carbon monoxide (1900-2100 cm-1) as a decarbonylation product was probed using infrared spectroscopy and to calculate the extent of poisoning during subsequent methanol dehydrogenation based on the reduction of the ν(C≡O) band integral relative to experiments in which only methanol was dosed. Small Pt particles appeared less active in decarbonylation and were perhaps poisoned by strongly adsorbed di/ketones on undercoordinated metal sites and bulky conjugated species formed on the γ-Al2O3 support from aldol self-condensation. Larger Pt particles were more resistant to di/ketone poisoning due to higher decarbonylation activity yet still fell short of the expected yield of adsorbed CO from subsequent methanol activity. Vibrational spectra acquired using inelastic neutron scattering showed evidence for strongly binding methyl and acyl groups resulting from di/ketone decarbonylation on a Pt sponge at 250 °C. Adsorption energies and molecular configurations were obtained for di/ketones on a Pt(111) slab using density functional theory, revealing potential descriptors for predicting decarbonylation activity on highly coordinated metal sites. Calculated reaction energies suggest it is energetically favorable to reform surface methyl groups into adsorbed CO and H. However, the rate of this surface reaction is limited by a high activation barrier indicating that either improved APR catalyst designs or regeneration procedures may be necessary.
RESUMEN
A prominent role of water in aqueous-phase heterogeneous catalysis is to modify free energies; however, intuition about how is based largely on pure metal surfaces or even homogeneous solutions. Using multiscale modeling with explicit liquid water molecules, we show that the influence of water on the free energies of adsorbates at metal/support interfaces is different than that on pure metal surfaces. We specifically compute free energies of solvation for methanol and its constituents on a Pt/Al2O3 catalyst and compare the results to analogous values calculated on a pure Pt catalyst. We find that the more hydrophilic Pt/Al2O3 interface leads to smaller (more positive) free energies of solvation due to an increased entropy penalty resulting from the additional work necessary to disrupt the interfacial water structure and accommodate the interfacial species. The results will be of interest in other fields, including adsorption and proteins.