A multi-faceted structural, thermodynamic, and spectroscopic approach for investigating ethanol dehydration over transition phase aluminas.

Understanding the role that the surface of a material plays in the mediation of a chemical reaction at the atomic level is paramount to the optimization and improvement of catalytic materials. While this area of research has matured over several decades, few techniques are sensitive enough to directly examine and differentiate the behavior of molecular adsorbates during the course of the chemical reaction with a substrate. In this study, a combined approach which involves structural characterization techniques, volumetric adsorption, temperature programmed desorption, and inelastic neutron scattering (INS) was used to investigate the mechanism of ethanol dehydration on the surface of transition phase aluminas. The alumina samples employed were extensively characterized using X-ray diffraction, solid-state 27Al nuclear magnetic resonance spectroscopy, and thermogravimetric analysis with differential scanning calorimetry. A high-precision volumetric adsorption apparatus was used to characterize the surface area and to controllably dose ethanol onto the surface of the aluminas. A modified temperature programmed desorption (TPD) method which samples the molecular composition of the vapor at discrete temperatures in a closed cell is described. INS results were used to confirm adsorption of ethanol on γ- and θ-alumina and show the reaction of ethanol and subsequent formation of ethylene as a function of temperature. The TPD and INS results affirm that the dehydration reaction and subsequent formation of ethylene on both γ- and θ-aluminas occur rapidly at 300 °C, though ethanol is still observed on θ-alumina indicating fewer active sites. These results demonstrate the value of a multi-faceted characterization approach, featuring INS, towards providing a detailed understanding of the ethanol dehydration mechanism on θ-alumina and further provide the basis for extending this approach to other systems in heterogeneous catalysis and areas where molecule-substrate interactions are poorly understood.

Investigation of the behavior of ethylene molecular films using high resolution adsorption isotherms and neutron scattering.

The wetting behavior of ethylene adsorbed on MgO(100) was investigated from 83-135 K using high resolution volumetric adsorption isotherms. The results are compared to ethylene adsorption on graphite, a prototype adsorption system, in an effort to gain further insight into the forces that drive the observed film growth. Layering transitions for ethylene on MgO(100) are observed below the bulk triple point of ethylene (T = 104.0 K). The formation of three discrete adlayers is observed on the MgO(100) surface; onset of the second and third layers occurs at 79.2 +/- 1.3 K and 98.3 +/- 0.9 K, respectively. Thermodynamic quantities such as differential enthalpy and entropy, heat of adsorption, and isosteric heat of adsorption are determined and compared to the previously published values for ethylene on graphite. The average area occupied by a ethylene molecule on MgO(100) is 22.6 +/- 1.1 A2 molecule(-1). The locations of two phase transitions are identified (i.e., layer critical temperatures at T(c2)(n=1) at 108.6 +/- 1.7 K and T(c2)(n=2) at 116.5 +/- 1.2 K) and a phase diagram is proposed. Preliminary neutron diffraction measurements reveal evidence of a monolayer solid with a lattice constant of approximately 4.2 A. High resolution INS measurements show that the onset to dynamical motion and monolayer melting take place at approximately 35 K and approximately 65 K, respectively. The data reported here exhibit a striking similarity to ethylene on graphite which suggests that molecule-molecule interactions play an important role in determining the physical properties and growth of molecularly thin ethylene films.

Neutron investigations of rotational motions in monolayer and multilayer films at the interface of MgO and graphite surfaces.

Recent experimental investigations of the rotational motion of methane and molecular hydrogen using inelastic neutron scattering (INS) measurements in combination with thermodynamic techniques have provided a unique view of the evolution of the interaction of these two molecules with the MgO (100) surface and graphite basal plane. Despite significant differences in the chemical and physical properties and surface symmetry of these two adsorbents, the dynamical behavior of the adsorbed films is remarkably similar. The interaction of a CH4 monolayer solid with MgO and graphite, as monitored by the behavior of the J = 0 --> J = 1 free rotor transition, is so strong that there is no evidence for unhindered rotation of the molecule below 20 K. Using this same transition as a probe, H2 monolayer solids exhibit nearly free or significantly hindered motion on graphite and MgO (100) surfaces, respectively. Investigations of CH4 and H2 multilayer films on MgO find that once the film thickness exceeds approximately 3 layers, the molecule-molecule interactions predominantly determine the dynamical properties of the molecular film furthest from the surface. INS signals indicate that the dynamical motion in thicker films is closely related to that observed in the bulk system. The results of these studies serve as a valuable pathway for developing a qualitatively accurate description of the potential energy surfaces that govern the microscopic properties of these systems.

Direct observation of H2 binding to a metal oxide surface.

Inelastic neutron scattering is used to probe the dynamical response of H2 films adsorbed on MgO(100) as a function of film thickness. Concomitant diffraction measurements and a reduced-dimensionality quantum dynamical model provide insight into the molecule-surface interaction potential. At monolayer thickness, the rotational motion is strongly influenced by the surface, so that the molecules behave like quasiplanar rotors. These findings have a direct impact on understanding how molecular hydrogen binds to the surface of materials used in catalytic and storage applications.

Thermodynamic investigation of n-hexane thin films adsorbed on magnesium oxide.

The thermodynamic properties of n-hexane adsorption on MgO(100) were determined using high-resolution volumetric adsorption isotherms in the temperature range 195-255 K. Two distinct layering transitions are observed in the isotherms. The isotherms are used to calculate the two-dimensional compressibility, the differential enthalpy and entropy, the heat of adsorption, and the isosteric heat of adsorption. Neutron Diffraction is used to identify where melting of the n-hexane monolayer takes place.

Thermodynamic investigation of thin films of ethane adsorbed on magnesium oxide.

The layering properties of ethane on MgO(100) were measured between 91 and 144 K using high-resolution adsorption isotherms. In contrast to previous studies, the results demonstrate that only three layers are formed. The thermodynamic functions derived from the data (isosteric heat, differential enthalpy, and entropy of adsorption) compare well with literature values and show a steady trend toward the bulk properties as the number of layers increased. Phase transitions for two of the layers were identified by monitoring the changes in the two-dimensional isothermal compressibility as a function of chemical potential. Both of these phase transitions occur at approximately 127 K and within 1 K of each other. Through the use of neutron diffraction, it is possible to identify at least one solid surface phase that melts at approximately 75 K. The transition at 127 K is therefore a transition between a liquidlike phase and a hyper-critical fluid. A comparison is made between the present data and our recent study of methane on MgO.

Tracking the evolution of interatomic potentials with high resolution inelastic neutron spectroscopy.

High resolution inelastic neutron scattering has been used to characterize the low temperature rotational dynamics of methane ( CH4) films on MgO(100) surfaces as a function of layer thickness. At low temperatures the films grow layer-by-layer similar to the (100) planes of bulk solid CH4. We observe a crossover in the CH4 tunneling spectrum from one characteristic of the 2D solid at monolayer coverages into one that is bulklike (i.e., 3D) when the film is six layers thick. These findings place significant constraints on the microscopic models used to describe CH4-CH4 and CH4-MgO interactions.

Transition state structure of purine nucleoside phosphorylase and principles of atomic motion in enzymatic catalysis.

Immucillin-H [ImmH; (1S)-1-(9-deazahypoxanthin-9-yl)-1,4-dideoxy-1,4-imino-D-ribitol] is a 23 pM inhibitor of bovine purine nucleoside phosphorylase (PNP) specifically designed as a transition state mimic [Miles, R. W., Tyler, P. C., Furneaux, R. H., Bagdassarian, C. K., and Schramm, V. L. (1998) Biochemistry 37, 8615-8621]. Cocrystals of PNP and the inhibitor are used to provide structural information for each step through the reaction coordinate of PNP. The X-ray crystal structure of free ImmH was solved at 0.9 A resolution, and a complex of PNP.ImmH.PO(4) was solved at 1.5 A resolution. These structures are compared to previously reported complexes of PNP with substrate and product analogues in the catalytic sites and with the experimentally determined transition state structure. Upon binding, ImmH is distorted to a conformation favoring ribosyl oxocarbenium ion formation. Ribosyl destabilization and transition state stabilization of the ribosyl oxocarbenium ion occur from neighboring group interactions with the phosphate anion and the 5'-hydroxyl of the ribosyl group. Leaving group activation of hypoxanthine involves hydrogen bonds to O6, N1, and N7 of the purine ring. Ordered water molecules provide a proton transfer bridge to O6 and N7 and permit reversible formation of these hydrogen bonds. Contacts between PNP and catalytic site ligands are shorter in the transition state analogue complex of PNP.ImmH.PO(4) than in the Michaelis complexes of PNP.inosine.SO(4) or PNP.hypoxanthine.ribose 1-PO(4). Reaction coordinate motion is dominated by translation of the carbon 1' of ribose between relatively fixed phosphate and purine groups. Purine and pyrimidine phosphoribosyltransferases and nucleoside N-ribosyl hydrolases appear to operate by a similar mechanism.