A first principles study of methanol decomposition on Pd(111): Mechanisms for O-H bond scission and C-O bond scission

There is some dispute as to whether methanol decomposition occurs by O-H bond scission or C-O bond scission. By carrying out density functional theory calculations, we investigate both scenario of the reaction pathways of methanol decomposition on a Pd(111) surface. It is shown that the O-H bond scission pathway is much more energetically favorable than the C-O bond scission pathway. The high reaction barrier in the latter case is found to be due to the poor bonding abilities of CH3 and OH with the surface at the reaction sites. (C) 2001 American Institute of Physics.

The preparation and properties of coprecipitated Cu-Zr-Y and Cu-Zr-La catalysts used for the steam reforming of methanol

A series of Cu-zirconia catalysts containing various additives (Y2O3, La2O3, Al2O3 and CeO2) have been prepared by coprecipitation and their activities and stabilities under operating conditions have been obtained for the steam reforming of methanol. It has been found that an yttria-promoted catalyst containing 30 mol% Cu and 20 mol% of Y2O3 is not only very active but is also very stable under reaction conditions. The yttria appears to stabilise a high copper surface area and may also have a slight promotional effect on the copper. The results obtained with this material compare very favourably with data for the best catalysts reported in the literature. (C) 2007 Published by Elsevier B.V.

Increased Dispersion of Supported Gold during Methanol Carbonylation Conditions

The active site in supported gold catalysts for the carbonylation of methanol has been identified as dimers/trimers of gold which are formed from large gold particles >10 nm in diameter. Methyl iodide was found to be critical for this dispersion process and to maintain the catalyst in the active form. This study also shows that it may be possible to redisperse gold catalysts, in general, after reaction.

Crystal structure of pyridinium 1,1 '-bis(4-hydroxy-pyrimid-6-on-2-thion-5-yl)-1 ''-(4-nitrophenyl)methane methanol solvate monohydrate, (C5H6N)(C15H10N5O6S2)center dot CH3OH center dot H2O

C21H22N6O8S2, monoclinic, P12(1)/n1 (no. 14), a = 10.1931(8) angstrom, b = 11.9627(7) angstrom, c = 20.299(2) angstrom, beta = 95.131(4)degrees, V = 2465.2 A(3), Z = 4, R-gt(F) = 0.079, wR(ref)(F-2) = 0.229, T = 100 K.

CsF and alumina: A mixed homogeneous-heterogeneous catalytic system for the transesterification of sunflower oil with methanol

The activity and nature (i e heterogeneous and/or homogeneous) of catalysts based on CsF supported on alpha-Al2O3 were investigated for the transesterification of vegetable oil with methanol. The effect of the activation temperature, CsF loading and the reusability in a recirculating reactor were first studied CsF/alpha-Al2O3 exhibited the highest activity for a CsF loading of 0 6 mmol/g and when activated at 120 degrees C An important aspect of this study is the effect of CsF leaching into the reaction mixture, which is attributed to the high solubility of CsF in methanol, leading to a complete loss of activity after one run It was Identified that the activity of the catalyst resulted from a synergy between alumina and dissolved CsF, the presence of both compounds being absolutely necessary to observe any conversion The use of an alumina with a higher surface area resulted in a far greater reaction rate, showing that the concentration of surface site on the oxide (probably surface hydroxyl) was rate-limiting in the case of the experiments using the low surface area alpha-Al2O3 This work emphasizes that combined homogeneous-heterogeneous catalytic systems made from the blending of the respective catalysts can be used to obtain high conversion of vegetable oil to biodiesel. Despite the homogeneous/heterogeneous dual character, such a catalytic system may prove valuable in developing a simple and cost-effective continuous catalytic process for biodiesel production (C) 2010 Elsevier B V All rights reserved

Observational tests of interstellar methanol formation

Context. It has been established that the classical gas-phase production of interstellar methanol (CH3OH) cannot explain observed abundances. Instead it is now generally thought that the main formation path has to be by successive hydrogenation of solid CO on interstellar grain surfaces. Aims. While theoretical models and laboratory experiments show that methanol is efficiently formed from CO on cold grains, our aim is to test this scenario by astronomical observations of gas associated with young stellar objects (YSOs). Methods. We have observed the rotational transition quartets J = 2K – 1K of 12CH3OH and 13CH3OH at 96.7 and 94.4 GHz, respectively, towards a sample of massive YSOs in different stages of evolution. In addition, the J = 1-0 transitions of 12C18O and 13C18O were observed towards some of these sources. We use the 12C/13C ratio to discriminate between gas-phase and grain surface origin: If methanol is formed from CO on grains, the ratios should be similar in CH3OH and CO. If not, the ratio should be higher in CH3OH due to 13C fractionation in cold CO gas. We also estimate the abundance ratios between the nuclear spin types of methanol (E and A). If methanol is formed on grains, this ratio is likely to have been thermalized at the low physical temperature of the grain, and therefore show a relative over-abundance of A-methanol. Results. We show that the 12C/13C isotopic ratio is very similar in gas-phase CH3OH and C18O, on the spatial scale of about 40 arcsec, towards four YSOs. For two of our sources we find an overabundance of A-methanol as compared to E-methanol, corresponding to nuclear spin temperatures of 10 and 16 K. For the remaining five sources, the methanol E/A ratio is less than unity. Conclusions. While the 12C/13C ratio test is consistent with methanol formation from hydrogenation of CO on grain surfaces, the result of the E/A ratio test is inconclusive.

Droplet size control with methanol-repellent surface in a sampling device for continuous annular electrochromatography

The eluent droplet size defines the number of sampling compartments in a continuously operated annular electrochromatograph and therefore influences separation efficiency. In this work, an assembly of two capillaries, a feeding capillary on the top and a receiving capillary placed under it, has been investigated to control droplet size. The receiving capillary prevents the liquid droplet formation beyond a critical size, which reduces the volume of sampling compartment as compared with the case of the electrolyte flow driven solely by gravity. With a receiving capillary, the electrolyte droplet size was reduced from 1.5 to 0.46 mm. Further decrease of droplet size was not possible due to a so-called droplet jump upwards effect which has been observed on a hydrophilic glass surface with water. A typical electrolyte used in CAEC has high methanol content. In an attempt to improve the methanol-repellent properties of the glass surface, two approaches have been implemented: (i) self-assembled chemisorbed monolayers of an alkylsiloxane and (ii) fabrication of a nano-pin film. The methanol-repellent surface of the feeding capillary suppressed the droplet jump upwards effect. The surface remained methanol repellent in different solutions with lower polarity than that of water.

Selective homogeneous snythesis of dimethyl ether from methanol

Selected Bronsted acidic ionic liquids were tested as homogeneous catalysts for the dehydration of methanol to dimethyl ether. Ionic liquids incorporating an alkanesulfonic acid as a part of the cation, a complex acidic anion, [A(2)H](-), or both, proved to be good catalysts for this process, providing high conversions and selectivities. Homogeneous catalysis in the liquid state represents a novel approach to dimethyl ether synthesis.

Tetrahexahedral Pt Nanocrystal Catalysts Decorated with Ru Adatoms and Their Enhanced Activity in Methanol Electrooxidation

Tetrahexahedral Pt nanocrystals (THH Pt NCs) bound by well-defined high index crystal planes offer exceptional electrocatalytic activity, owing to a high density of low-coordination surface Pt sites. We report, herein, on methanol electrooxidation at THH Pt NC electrodes studied by a combination of electrochemical techniques and in situ FTIR spectroscopy. Pure THH Pt NC surfaces readily facilitate the dissociative chemisorption of methanol leading to poisoning by strongly adsorbed CO. Decoration of the stepped surfaces by Ru adatoms increases the tolerance to poisoning and thereby reduces the onset potential for methanol oxidation by over 100 mV. The Ru modified THH Pt NCs exhibit greatly superior catalytic currents and CO2 yields in the low potential range, when compared with a commercial PtRu alloy nanoparticle catalyst. These results are of fundamental importance in terms of model nanoparticle electrocatalytic systems of stepped surfaces and also have practical significance in the development of surface tailored, direct methanol fuel cell catalysts.

Synthesis of mesoporous tungsten carbide-supported platinum and its electrocatalytic activity for methanol oxidation

High activity and stability during oxidation of methanol under the relatively anode environment are two main evaluation criterias for an effective anode electrocatalyst in direct methanol fuel cell (DMFC). Mesoporous WC samples with hollow structure were prepared by gas-solid reaction at the atmosphere of CH(4)/H(2) by using airflow spray dried ammonium metatungstate (AMT). The platinum supported on this material by impregnation-vapor phase deoxidation method served as a less expensive electro anode catalyst. XRD and SEM results showed that Pt particles were well dispersed on the surface of WC. The results showed that the Pt/WC-PME exhibited an attractive catalytic activity, and methanol oxidation process in Pt/WC-PME is affected by liquid-phase mass transfer. The results also indicated that the oxidation can be improved by raising temperatures.

Effect of precursor on the performance of alumina for the dehydration of methanol to dimethyl ether

Dimethyl ether (DME) is amongst one of the most promising alternative, renewable and clean fuels being considered as a future energy carrier. In this study, the comparative catalytic performance of γ-Al2O3 prepared from two common precursors (aluminum nitrate (AN) and aluminum chloride (AC)) is presented. The impact of calcination temperature was evaluated in order to optimize both the precursor and pre-treatment conditions for the production of DME from methanol in a fixed bed reactor. The catalysts were characterized by TGA, XRD, BET and TPD-pyridine. Under reaction conditions where the temperature ranged from 180 °C to 300 °C with a WHSV = 12.1 h−1 it was found that all the catalysts prepared from AN(η-Al2O3) showed higher activity, at all calcination temperatures, than those prepared from AC(γ-Al2O3). In this study the optimum catalyst was produced from AN and calcined at 550 °C. This catalyst showed a high degree of stability and had double the activity of the commercial γ-Al2O3 or 87% of the activity of commercial ZSM-5(80) at 250 °C.