Simon G. Podkolzin

Identification of molybdenum oxide nanostructures on zeolites for natural gas conversion

Waste not, want not Natural gas often escapes or is deliberately burned at remote exploration sites because there is no economical way to transport it to markets. One route proposed for converting its main component, methane, into a more readily transported liquid is conversion to benzene over zeolites containing molybdenum (Mo). However, this method suffers from low conversion efficiency. Gao et al. identified the active Mo nanostructures as well as deactivated carbide species that form during this reaction. They were also able to recover and even enhance the zeolite catalytic activity after oxygen treatments. Science, this issue p. 686 Catalytically active isolated molybdenum nanostructures on a zeolite can be recovered after reaction through oxygen treatment. Direct methane conversion into aromatic hydrocarbons over catalysts with molybdenum (Mo) nanostructures supported on shape-selective zeolites is a promising technology for natural gas liquefaction. We determined the identity and anchoring sites of the initial Mo structures in such catalysts as isolated oxide species with a single Mo atom on aluminum sites in the zeolite framework and on silicon sites on the zeolite external surface. During the reaction, the initial isolated Mo oxide species agglomerate and convert into carbided Mo nanoparticles. This process is reversible, and the initial isolated Mo oxide species can be restored by a treatment with gas-phase oxygen. Furthermore, the distribution of the Mo nanostructures can be controlled and catalytic performance can be fully restored, even enhanced, by adjusting the oxygen treatment.

Microcalorimetric studies of interactions of ethene, isobutene, and isobutane with silica-supported Pd, Pt, and PtSn

Microcalorimetric measurements were made of the interaction of hydrogen, ethene, isobutene and isobutane at 300 K with silica- supported Pt, Pd, and PtSn catalysts. The initial heats of hydrogen adsorption on silica-supported Pd and Pt are 104 and 95 kJ/mol, respectively. The presence of Sn decreases the saturation uptake of hydrogen on the PtSn sample. The initial heats of ethene interaction with Pd/silica and Pt/silica are 170 and 145 kJ/mol, respectively. The presence of Sn decreases the initial heat to 115 kJ/mol on the PtSn sample. The initial heats of isobutene interaction with silica-supported Pd and Pt are 160 and 190 kJ/mol, respectively. The presence of Sn decreases the initial heat to 125 kJ/mol on the PtSn sample. It appears that ethene and isobutene adsorb dissociatively on silica-supported Pd and Pt to form alkylidyne species at 300 K, with an average strength of carbon-metal bonds for these species near 230 kJ/mol. Ethene and isobutene adsorb on silica-supported PtSn to form di- σ- and π-bonded alkene species at 300 K, with an average strength of carbon-metal bonds for these species near 190 and 130 kJ/mol, respectively. Isobutane appears to adsorb dissociatively on a small number of sites on silica-supported Pd and Pt, and this dissociation is also inhibited by Sn on PtSn samples.

Ethylene adsorption on Pt/Au/SiO2 catalysts

Ethylene adsorption on a Pt/Au/SiO2 catalyst (2 wt% Pt; Au/Pt atomic ratio of 10) was studied using adsorption microcalorimetry and FTIR spectroscopy. Ethylene adsorption at 300 K on Pt/Au/SiO2 produced π‐bonded, di‐σ‐bonded, and ethylidyne species with an initial heat of 140 kJ/mol, compared to a heat of 157 kJ/mol for Pt/SiO2 on which only ethylidyne species formed. At 203 and 263 K, ethylene adsorbed on Pt as well as on Au surface atoms for the Pt/Au/SiO2 catalyst. Quantum chemical, DFT calculations indicate that Au exerts a significantly smaller electronic effect on Pt than does addition of Sn to Pt.

Geometric Requirements for Hydrocarbon Catalytic Sites on Platinum Surfaces

Vibrational spectroscopic measurements and density functional calculations were used to identify a preferential catalytic mechanism for the transformation of acetylene, HC-CH, to vinylidene, C-CH2, on surfaces of Pt-Sn ordered alloys. In this mechanism, two adjacent Pt atoms adsorb an acetylene molecule and a third neighboring Pt atom is required for stabilizing the reacting H atom during the transformation. Therefore, unlike a direct H shift along the C-C bond in organometallic compounds with a single transition-metal atom, this mechanism has a geometric site requirement of three adjacent Pt atoms in the form of a three-fold site. The same geometric site requirement is identified for preferential C-H bond cleavage of acetylene with the formation of adsorbed C-CH and H species. In the absence of three-fold Pt sites, the reaction mechanism changes, and reactions of H transfer and C-H bond cleavage are suppressed.

Catalytic hydrogen-chlorine exchange between chlorinated hydrocarbons under oxygen-free conditions

Chlorinated hydrocarbons (CHCs) remain important industrial chemical intermediates and solvents, especially for the exploration of the potential of La-based materials for the conversion of chlorinated waste compounds.[1] The production of industrially important CHCs frequently occurs with concurrent formation of less desirable side-products. For example, mixtures of chlorinated C1 and C2 hydrocarbons are still formed as by-products in industrial processes such as the production of vinyl chloride monomer (VCM).[2, 3] Another example is carbon tetrachloride (CCl4) formation in the production of chloroform (CHCl3) and other chlorinated methanes. The United States Clean Air Act and the Montreal Protocol limit the production and sale of CCl4,[4,5] therefore methods to effectively recycle chlorinated side-products, in particular CCl4, would be advantageous. The hydrogen– chlorine exchange of CCl4 with other CHCs, such as CH2Cl2, for the recycling of less desirable compounds into valuable products would be of particular interest.

Adsorption and decomposition of cyclohexanone (C6H10O) on Pt(111) and the (2 × 2) and (√3 × √3)r30°-Sn/Pt(111) surface alloys.

Adsorption and decomposition of cyclohexanone (C(6)H(10)O) on Pt(111) and on two ordered Pt-Sn surface alloys, (2 × 2)-Sn/Pt(111) and (√3 × √3)R30°-Sn/Pt(111), formed by vapor deposition of Sn on the Pt(111) single crystal surface were studied with TPD, HREELS, AES, LEED, and DFT calculations with vibrational analyses. Saturation coverage of C(6)H(10)O was found to be 0.25 ML, independent of the Sn surface concentration. The Pt(111) surface was reactive toward cyclohexanone, with the adsorption in the monolayer being about 70% irreversible. C(6)H(10)O decomposed to yield CO, H(2)O, H(2), and CH(4). Some C-O bond breaking occurred, yielding H(2)O and leaving some carbon on the surface after TPD. HREELS data showed that cyclohexanone decomposition in the monolayer began by 200 K. Intermediates from cyclohexanone decomposition were also relatively unstable on Pt(111), since coadsorbed CO and H were formed below 250 K. Surface Sn allowed for some cyclohexanone to adsorb reversibly. C(6)H(10)O dissociated on the (2 × 2) surface to form CO and H(2)O at low coverages, and methane and H(2) in smaller amounts than on Pt(111). Adsorption of cyclohexanone on (√3 × √3)R30°-Sn/Pt(111) at 90 K was mostly reversible. DFT calculations suggest that C(6)H(10)O adsorbs on Pt(111) in two configurations: by bonding weakly through oxygen to an atop Pt site and more strongly through simultaneously oxygen and carbon of the carbonyl to a bridged Pt-Pt site. In contrast, on alloy surfaces, C(6)H(10)O bonds preferentially to Sn. The presence of Sn, furthermore, is predicted to make the formation of the strongly bound C(6)H(10)O species bonding through O and C, which is a likely decomposition precursor, thermodynamically unfavorable. Alloying with Sn, thus, is shown to moderate adsorptive and reactive activity of Pt(111).