Desolvation and dehydrogenation of solvated magnesium salts of dodecahydrododecaborate: relationship between structure and thermal decomposition.

Attempts to synthesize solvent-free MgB12H12 by heating various solvated forms (H2O, NH3, and CH3OH) of the salt failed because of the competition between desolvation and dehydrogenation. This competition has been studied by thermogravimetric analysis (TGA) and temperature-programmed desorption (TPD). Products were characterized by IR, solution- and solid-state NMR spectroscopy, elemental analysis, and single-crystal or powder X-ray diffraction analysis. For hydrated salts, thermal decomposition proceeded in three stages, loss of water to form first hexahydrated then trihydrated, and finally loss of water and hydrogen to form polyhydroxylated complexes. For partially ammoniated salts, two stages of thermal decomposition were observed as ammonia and hydrogen were released with weight loss first of 14 % and then 5.5 %. Thermal decomposition of methanolated salts proceeded through a single step with a total weight loss of 32 % with the release of methanol, methane, and hydrogen. All the gaseous products of thermal decomposition were characterized by using mass spectrometry. Residual solid materials were characterized by solid-state (11)B magic-angle spinning (MAS) NMR spectroscopy and X-ray powder diffraction analysis by which the molecular structures of hexahydrated and trihydrated complexes were solved. Both hydrogen and dihydrogen bonds were observed in structures of [Mg(H2O)6B12H12]⋅6 H2O and [Mg(CH3OH)6B12H12]⋅6 CH3OH, which were determined by single-crystal X-ray diffraction analysis. The structural factors influencing thermal decomposition behavior are identified and discussed. The dependence of dehydrogenation on the formation of dihydrogen bonds may be an important consideration in the design of solid-state hydrogen storage materials.

Incident-angle dependent operando XAS cell design: investigation of the electrochemical cells under operating conditions at various incidence angles.

An operando characterization of electrode materials under electrochemical reaction conditions is important for their further development. X-ray absorption spectroscopy (XAS) presents a unique opportunity in this regard as the absence of a vacuum chamber in this technique makes it possible to collect spectroscopy data using user-designed operando cells. In the current study, the design and performance of an operando XAS cell are evaluated for characterizing solid oxide electrolysis cell working electrodes under a reaction environment that mimics high-temperature ammonia production conditions from H2O and N2. Sr2FeMoO6-x N x (SFMON)-type double perovskite oxides were used as the cathode materials in these experiments. The operando cell contained a sample stage with a turnable head so that XAS data can be collected at different angles between the electrode and the X-ray beam with an accuracy of 0.5°. The mechanism to adjust the angle of incidence of the beam on the sample allows control over the depth of penetration of the X-ray photons into the electrode. At low angles, it becomes possible to collect surface sensitive data, which is of great importance as the electrochemical processes are believed to take place on the surface of the electrodes. Sr K-edge and Fe K-edge XAS collected at 2° and 45° angles showed that these the oxidation state changes occurring in these elements are different in the near-surface region compared to the bulk of the electrode. Such an ability to distinguish between the surface and bulk properties of the electrode during real reaction environment will help to understand the underlying phenomena better, which will enable electrode design targeted towards the reactions of interest.

Changing the oxygen mobility in Co/ceria catalysts by Ca incorporation: implications for ethanol steam reforming.

The effect of calcium doping on the performance of Co/CeO(2) catalysts in ethanol steam reforming was examined using various characterization techniques including CO temperature-programmed reduction, O(2) and CO pulse chemisorption, laser Raman spectroscopy, X-ray diffraction, isotopically labeled oxygen exchange, and diffuse reflectance infrared Fourier transform spectroscopy. Characterization results showed Ca incorporation to lead to oxygen vacancies and unit cell expansion in the ceria lattice. The creation of oxygen vacancies, in turn, enhanced the oxygen mobility in ceria-supported Co catalysts. Steady-state reaction studies showed increased TOF and higher H(2) yields over Co catalysts supported on Ca-doped ceria in ethanol steam reforming.

Oxygen reduction reaction catalysts prepared from acetonitrile pyrolysis over alumina-supported metal particles.

Noble-metal-free active catalysts for the oxygen reduction reaction (ORR) in an acidic environment were prepared from the pyrolysis of acetonitrile at 900 degrees C over alumina and metal-doped alumina. This work includes analyses of the nitrogen-doped carbon preparation process, characterization of the carbon materials formed, and activity testing for the ORR. The nitrogen-containing carbon nanostructures that formed during the pyrolysis of acetonitrile could be purified by washing the product with hydrofluoric acid. A wide range of techniques were used to characterize the solid carbon products of the acetonitrile decomposition. While the samples have many similar physical properties, X-ray photoelectron spectroscopy and transmission electron microscopy showed evidence that differences in the nanostructure and surface functional groups of the samples are likely to account for observed differences in oxygen reduction activity. The most active catalysts were prepared over alumina impregnated with up to 2 wt % Fe, although the catalysts that were prepared by acetonitrile pyrolysis over alumina with no metal doping still had significant activity. In comparison to a 20 wt % platinum on Vulcan carbon catalyst, the most active samples only have an additional 100 mV overpotential. The selectivity of the catalysts for complete oxygen reduction to water followed a trend similar to activity. The best selectivity to water versus peroxide obtained was 99%, or equivalently, an n of 3.98 (i.e., 3.98 electrons transferred out of a maximum of 4 electrons per mole of oxygen that is reduced), as determined by rotating ring-disk electrode testing.

Characterization of active sites over reduced Ni-Mo/Al(2)O(3) catalysts for hydrogenation of linear aldehydes.

Reduced Ni-Mo/Al(2)O(3) catalysts exhibit a behavior analogous to that of sulfided Ni-Mo/Al(2)O(3) catalysts in hydrogenation of linear aldehydes to alcohols. Similar to what has been previously reported for sulfided catalysts, NO and CO(2) can be used over the reduced Ni-Mo catalysts as probe molecules for the active sites responsible for two competing reactions -- aldehyde hydrogenation to alcohols and condensation reactions to heavy products, respectively. Reduced catalysts have a higher aldehyde conversion activity and alcohol selectivity than their sulfided counterparts. The reduction temperature has a strong effect on the surface density of anion vacancies, which are responsible for alcohol formation. Reduction temperature also plays a role in determining the abundance of OH groups on the alumina surface. The effect of reduction temperature also manifests itself through the differences seen in the oxidation states of Mo and Ni species.

A computational exploration of the oxygen reduction reaction over a carbon catalyst containing a phosphinate functional group.

Oxygen reduction reaction (ORR) over a carbonaceous catalyst (1) with a phosphinate (>P(=O)OH) moiety was explored computationally. Under the acidic environment of a fuel cell, 1 could be active for ORR and be converted to 2 with a >P(OH)(2) moiety. An edge phosphinate could be active for both 2- and 4-electron ORR.

Spectroscopic and structural characterization of chlorine loading effects on Mo/Si:Ti catalysts in oxidative dehydrogenation of ethane.

The structural changes induced in a silica-titania mixed-oxide support (1:1 molar ratio) by chlorine addition at different loading levels, their relation to the structural characteristics of supported MoOx species over the support, and their correlation with ethane oxidative dehydrogenation (ODH) activity have been examined. The molybdenum and chlorine precursors are incorporated into the Si/Ti support network as it forms during gelation by using a "one-pot" modified sol-gel/coprecipitation technique. In situ X-ray diffraction during calcination shows the Si/Ti 1:1 mixed-oxide support is in a state of nanodispersed anatase titania over amorphous silica. With the addition of molybdenum and chlorine modifier, this anatase feature becomes more pronounced, indicating a decreased dispersion of titania. The effective titania surface area on the chlorine-doped Si:Ti support obtained from 2-propanol temperature-programmed reaction supports this observation. Raman spectra of dehydrated samples point to an enhanced interaction of MoOx species with silica at the expense of titania. X-ray photoelectron spectroscopic results show that, without forming a molybdenum chloride, the presence of chlorine significantly alters the relative surface concentration of Si vs Ti, the electronic structure of the surface MoOx species, and the oxygen environment around supported MoOx species in the Si/Ti network. Secondary ion mass spectrometry detected the existence of SiCl fragments from the mass spectra, which provides molecular insight into the location of chlorine in Mo/Si:Ti catalysts. The observed increase in ethane ODH selectivity with chlorine modification may be ascribed to the MoOx species sharing more complex ligands with silica and titania with the indirect participation of chlorine. Steady-state isotopic transient kinetic analysis (SSITKA) is used to to examine the oxygen insertion and exchange mechanisms. The catalysts show very little oxygen exchange with the gas phase in the absence of a reaction medium. During the steady-state ODH reaction, lattice oxygen appears to be the primary source of oxygen in the formation of water and CO2.