Shape-Controlled Pathways in the Hydrogen Production from Ethanol Steam Reforming over Ceria Nanoparticles.

The ethanol surface reaction over CeO2 nanooctahedra (NO) and nanocubes (NC), which mainly expose (111) and (100) surfaces, respectively, was studied by means of infrared spectroscopy (TPSR-IR), mass spectrometry (TPSR-MS), and density functional theory (DFT) calculations. TPSR-MS results show that the production of H2 is 2.4 times higher on CeO2-NC than on CeO2-NO, which is rationalized starting from the different types of adsorbed ethoxy species controlled by the shape of the ceria particles. Over the CeO2(111) surface, monodentate type I and II ethoxy species with the alkyl chain perpendicular or parallel to the surface, respectively, were identified. Meanwhile, on the CeO2(100) surface, bidentate and monodentate type III ethoxy species on the checkerboard O-terminated surface and on a pyramid of the reconstructed (100) surface, respectively, are found. The more labile surface ethoxy species on each ceria nanoshape, which are the monodentate type I or III ethoxy on CeO2-NO and CeO2-NC, respectively, react on the surface to give acetate species that decompose to CO2 and CH4, while H2 is formed via the recombination of hydroxyl species. In addition, the more stable monodentate type II and bidentate ethoxy species on CeO2-NO and CeO2-NC, respectively, give an ethylenedioxy intermediate, the binding of which is facet-dependent. On the (111) facet, the less strongly bound ethylenedioxy desorbs as ethylene, whereas on the (100) facet, the more strongly bound intermediate also produces CO2 and H2 via formate species. Thus, on the (100) facet, an additional pathway toward H2 formation is found. ESR activity measurements show an enhanced H2 production on the nanocubes.

Operando DRIFTS and DFT Study of Propane Dehydrogenation over Solid- and Liquid-Supported Ga x Pt y Catalysts.

Supported catalytically active liquid metal solutions (SCALMS) represent a class of catalytic materials that have only recently been developed, but have already proven to be highly active, e.g., for dehydrogenation reactions. Previous studies attributed the catalytic activity to isolated noble metal atoms at the surface of a liquid and inert Ga matrix. In this study, we apply diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) with CO as a probe molecule to Ga/Al2O3, Pt/Al2O3, and Ga37Pt/Al2O3 catalysts, to investigate in detail the nature of the active Pt species. Comparison of CO adsorption on Pt/Al2O3 and Ga37Pt/Al2O3 shows that isolated Pt atoms are, indeed, present at the surface of the liquid SCALMS. Combining DRIFTS with online gas chromatography (GC), we investigated the Ga/Al2O3, Pt/Al2O3, and Ga37Pt/Al2O3 systems under operando conditions during propane dehydrogenation in CO/propane and in Ar/propane. We find that the Pt/Al2O3 sample is rapidly poisoned by CO adsorption and coke, whereas propane dehydrogenation over Ga37Pt/Al2O3 SCALMS leads to higher conversion with no indication of poisoning effects. We show under operando conditions that isolated Pt atoms are present at the surface of SCALMS during the dehydrogenation reaction. IR spectra and density-functional theory (DFT) suggest that both the Ga matrix and the presence of coadsorbates alter the electronic properties of the surface Pt species.

Interaction of Ester-Functionalized Ionic Liquids with Atomically-Defined Cobalt Oxides Surfaces: Adsorption, Reaction and Thermal Stability.

Hybrid materials consisting of ionic liquid (ILs) films on supported oxides hold a great potential for applications in electronic and energy materials. In this work, we have performed surface science model studies scrutinizing the interaction of ester-functionalized ILs with atomically defined Co3 O4 (111) and CoO(100) surfaces. Both supports are prepared under ultra-high vacuum (UHV) conditions in form of thin films on Ir(100) single crystals. Subsequently, thin films of three ILs, 3-butyl-1-methyl imidazolium bis(trifluoromethyl-sulfonyl) imide ([BMIM][NTf2 ]), 3-(4-methoxyl-4-oxobutyl)-1-methylimidazolium bis(trifluoromethyl-sulfonyl) imide ([MBMIM][NTf2 ]), and 3-(4-isopropoxy-4-oxobutyl)-1-methylimidazolium bis(trifluoromethyl-sulfonyl) imide ([IPBMIM][NTf2 ]), were deposited on these surfaces by physical vapor deposition (PVD). Time-resolved and temperature-programmed infrared reflection absorption spectroscopy (TR-IRAS, TP-IRAS) were applied to monitor in situ the adsorption, film growth, and thermally induced desorption. By TP-IRAS, we determined the multilayer desorption temperature of [BMIM][NTf2 ] (360±5 K), [MBMIM][NTf2 ] (380 K) and [IPBMIM][NTf2 ] (380 K). Upon deposition below the multilayer desorption temperature, all three ILs physisorb on both cobalt oxide surfaces. However, strong orientation effects are observed in the first monolayer, where the [NTf2 ]- ion interacts with the surface through the SO2 groups and the CF3 groups point towards the vacuum. For the two functionalized ILs, the [MBMIM]+ and [IPBMIM]+ interact with the surface Co2+ ions of both surfaces via the CO group of their ester function. A very different behavior is found, if the ILs are deposited above the multilayer desorption temperature (400 K). While for [BMIM][NTf2 ] and [MBMIM][NTf2 ] a molecularly adsorbed monolayer film is formed, [IPBMIM][NTf2 ] undergoes a chemical transformation on the CoO(100) surface. Here, the ester group is cleaved and the cation is chemically linked to the surface by formation of a surface carboxylate. The IL-derived species in the monolayer desorb at temperatures around 500 to 550 K.

Gluing Ionic Liquids to Oxide Surfaces: Chemical Anchoring of Functionalized Ionic Liquids by Vapor Deposition onto Cobalt(II) Oxide.

Ionic liquids (IL) hold a great potential as novel electrolytes for applications in electronic materials and energy technology. The functionality of ILs in these applications relies on their interface to semiconducting nanomaterials. Therefore, methods to control the chemistry and structure of this interface are the key to assemble new IL-based electronic and electrochemical materials. Here, we present a new method to prepare a chemically well-defined interface between an oxide and an IL film. An imidazolium-based IL, which is carrying an ester group, is deposited onto cobalt oxide surface by evaporation. The IL binds covalently to the surface by thermally activated cleavage of the ester group and formation of a bridging carboxylate. The anchoring reaction shows high structure sensitivity, which implies that the IL film can be adhered selectively to specific oxide surfaces.

Molecular structure and thermal stability of the oxide-supported phosphotungstic Wells-Dawson heteropolyacid.

We present, for the first time in the literature, a systematic study of the molecular structure of the Wells-Dawson heteropolyacid H6P2W18O62·24H2O (HPA) dispersed on TiO2, SiO2, ZrO2 and Al2O3. The heteropolyacid-based materials were synthesized through a conventional impregnation method (in aqueous and ethanol media) at a loading that corresponds to the theoretical "monolayer" coverage (dispersion limit loading). The combination of Raman and infrared studies demonstrates the presence of crystals of HPA (regardless of the nature of the medium used during the synthesis) suggesting that the dispersion limit loading was greatly exceeded. In situ temperature programmed spectroscopy analyses demonstrated that the Raman shift of the distinctive W[double bond, length as m-dash]O Raman mode of the phosphotungstic Wells-Dawson heteropolyacid is sensitive to the local environment, that is, the amount of water molecules associated with the structure. Moreover, the aqueous based species associated with such structures are recognizable through infrared spectroscopy.

Methanol adsorption on the beta-Ga2O3 surface with oxygen vacancies: theoretical and experimental approach.

Methanol adsorption on beta-Ga2O3 surface has been studied by Fourier transform infrared spectroscopy (FTIR) and by means of density functional theory (DFT) cluster model calculations. Adsorption sites of tetrahedral and octahedral gallium ions with different numbers of oxygen vacancies have been compared. The electronic properties of the adsorbed molecules have been monitored by computing adsorption energies, optimized geometry parameters, overlap populations, atomic charges, and vibrational frequencies. The gallia-methanol interaction has different behaviors according to the local surface chemical composition. The calculations show that methanol can react in three different ways with the gallia surface giving rise to a nondissociative adsorption, a dissociative adsorption, and an oxidative decomposition. The surface without oxygen vacancies is very reactive and produces the methanol molecule decomposition. The molecule is nondissociatively adsorbed by means of a hydrogen bond between the alcoholic hydrogen atom and a surface oxygen atom and a bond between the alcoholic oxygen atom and a surface gallium atom. Two neighbor oxygen vacancies on tetrahedral gallium sites produce the dissociation of the methanol molecule and the formation of a bridge bond between two surface gallium atoms and the methoxy group.

Infrared spectroscopic study of the carbon dioxide adsorption on the surface of Ga2O3 polymorphs.

The adsorption of CO(2) over a set of gallium (III) oxide polymorphs with different crystallographic phases (alpha, beta, and gamma) and surface areas (12-105 m(2) g(-1)) was studied by in situ infrared spectroscopy. On the bare surface of the activated gallias (i.e., partially dehydroxylated under O(2) and D(2) (H(2)) at 723 K), several IR signals of the O-D (O-H) stretching mode were assigned to mono-, di- and tricoordinated OD (OH) groups bonded to gallium cations in tetrahedral and/or octahedral positions. After exposing the surface of the polymorphs to CO(2) at 323 K, a variety of (bi)carbonate species emerged. The more basic hydroxyl groups were able to react with CO(2), to yield two types of bicarbonate species: mono- (m-) and bidentate (b-) [nu(as)(CO(3)) = 1630 cm(-1); nu(s)(CO(3)) = 1431 or 1455 cm(-1) (for m- or b-); delta(OH) = 1225 cm(-1)]. Together with the bicarbonate groups, IR bands assigned to carboxylate [nu(as)(CO(2)) = 1750 cm(-1); nu(s)(CO(2)) = 1170 cm(-1)], bridge carbonate [nu(as)(CO(3)) = 1680 cm(-1); nu(s)(CO(3)) = 1280 cm(-1)], bidentate carbonate [nu(as)(CO(3)) = 1587 cm(-1); nu(s)(CO(3)) = 1325 cm(-1)], and polydentate carbonate [nu(as)(CO(3)) = 1460 cm(-1); nu(s)(CO(3)) = 1406 cm(-1)] species developed, up to approximately 600 Torr of CO(2). However, only the bi- and polydentate carbonate groups still remained on the surface upon outgassing the samples at 323 K. The total amount of adsorbed CO(2), measured by volumetric adsorption (323 K), was approximately 2.0 micromol m(-2) over any of the polymorphs, congruent with an integrated absorbance of (bi)carbonate species proportional to the surface area of the materials. Upon heating under flowing CO(2) (760 Torr), most of the (bi)carbonate species vanished a T > 550 K, but polydentate groups remained on the surface up to the highest temperature used (723 K). A thorough discussion of the more probable surface sites involved in the adsorption of CO(2) is made.

Thermal stabilization of tellurium in mineral acids solutions: use of permanent modifiers for its determination in sulfur by GFAAS.

The aim of this work is the study of the best conditions for thermal stabilization of tellurium in graphite furnaces under different experimental conditions, including highly concentrated nitric and hydrochloric acids solutions as those resulting of drastic dissolution procedures. The influence of different noble metals used as matrix modifiers in solution or as permanent layers on the graphite furnace will be assessed. Amongst the assayed matrix modifiers, iridium used as permanent has shown the best performance in high concentrations of mineral acids. The mass employed was 20 microg (for 1 ng of Te), with a maximal attainable pyrolysis temperature of 1400 degrees C without losses of the analyte or sensitivity (height, area and form of the atomization peak), being mo=20 pg. Some speculations on the mechanisms of thermal stabilization of tellurium in graphite furnaces will be discussed. The potentiality of ETAAS for tellurium determination in technical grade sulfur will be evaluated. Results involving characteristics mass, limit of detection and percentage of recovery of tellurium in a mineralized sulfur sample will be compared with those obtained through a working curve in absence of interferences.

Hydrogen chemisorption on gallium oxide polymorphs.

The chemisorption of H(2) over a set of gallia polymorphs (alpha-, beta-, and gamma-Ga(2)O(3)) has been studied by temperature-programmed adsorption equilibrium and desorption (TPA and TPD, respectively) experiments, using in situ transmission infrared spectroscopy. Upon heating the gallium oxides above 500 K in 101.3 kPa of H(2), two overlapped infrared signals developed. The 2003- and 1980-cm(-1) bands were assigned to the stretching frequencies of H bonded to coordinatively unsaturated (cus) gallium cations in tetrahedral and octahedral positions [nu(Ga(t)-H) and nu(Ga(o)-H), respectively]. Irrespective to the gallium cation geometrical environment, (i) a linear relationship between the integrated intensity of the whole nu(Ga-H) infrared band versus the Brunauer-Emmett-Teller surface area of the gallia was found and (ii) TPA and TPD results revealed that molecular hydrogen is dissociatively chemisorbed on any bulk gallium oxide polymorph following two reaction pathways. An endothermal, homolytic dissociation occurs over surface cus-gallium sites at T > 450 K, giving rise to Ga-H(I) bonds. The heat and entropy of this type I hydrogen adsorption were determined by the Langmuir's adsorption model as Deltah(I) = 155 +/- 25 kJ mol(-1) and Deltas(I) = 0.27 +/- 0.11 kJ mol(-1) K(-1). In addition, another exothermic, heterolytic adsorption sets in already in the low-temperature region. This type of hydrogen chemisorption involves surface Ga-O-Ga species, originating GaO-H and Ga-H(II) bonds which can only be removed from the gallia surface after heating under evacuation at T > 650 K. The measured desorption energy of this last, second-order process was equal to 77 +/- 10 kJ mol(-1). The potential of the H(2) chemisorption as a tool to measure or estimate the specific surface area of gallia and to discern the nature and proportion of gallium cation coordination sites on the surface of bulk gallium oxides is also analyzed.