Methane coupling at low temperatures on Ru(0001) and Ru(11¯20) catalysts

The conversion of methane to higher hydrocarbons on single crystal Ru catalysts has been investigated using combined elevated-pressure kinetic measurements/surface science studies. The reaction consists of activation of methane on Ru(0001) and Ru(11¯20) surfaces to produce carbonaceous intermediates at temperatures between 350 and 700 K and rehydrogenation of these species to ethane and propane at 370 K. It is found that under the reaction conditions employed, the maximum yield in ethane/propane production occurs at 500 K on both surfaces. Influence of the hydrogenation temperature on the production of ethane and propane is also examined. On Ru(0001), the yields of ethane and propane maximize at = 400 K, whereas no maximum yield was observed on Ru(11 0) in the 300–500 K temperature range. Under optimum reaction conditions, hydrocarbon products consist of 16% ethane and 2% propane. High-resolution electron energy-loss spectroscopy (HREELS) has been used to identify various forms of hydrocarbonaceous intermediates following methane decomposition. An effort is made to relate the hydrocarbon intermediates identified by HREELS to the gas phase products observed in the elevated pressure experiments.     

Partial oxidation of methane to synthesis gas via the direct reaction scheme over Ru/TiO2 catalyst

The partial oxidation of methane to synthesis gas has been investigated over various supported metal catalysts. The effects of operational variables on mass and heat transport resistances were investigated for defining the kinetic regime. It is observed that, in the absence of significant mass and heat transfer resistances, high selectivity (up to 65%) to synthesis gas is obtained over Ru/TiO₂ catalysts in the low methane conversion range ( ) whereas only negligibly small selectivity to synthesis gas is observed over all other catalysts investigated under similar conditions. This indicates that the Ru/TiO₂ catalyst possesses unique properties, offering high selectivity to synthesis gas formation via the direct reaction scheme, whereas the other catalysts promote the sequence of total oxidation of methane to CO₂ and H₂O, followed by reforming reactions to synthesis gas. An increase of selectivity to synthesis gas, in the presence of oxygen, is achieved over the Ru/TiO₂ catalyst by multi-feeding oxygen, which is attributed to suppression of deep oxidation of H₂ and CO.     

Diffusion effects in the hydrogenation of 3-methyl crotonaldehyde over zeolite-supported Ru

The activity and selectivity in gas-phase hydrogenation of the unsaturated aldehyde 3-methyl crotonaldehyde (UAL) over zeolite-supported Ru was found to depend markedly on the partial pressures of the two reactants in the gas phase, with the rate increasing as the ratio decreased. Anomalously low apparent activation energies were found compared to the same reaction over Ru/SiO₂, and secondary reactions to produce the totally hydrogenated product occurred much more readily in the zeolite-supported Ru. These observations led to the suggestion that these reactions were under diffusion control.     

The state of Rh during the partial oxidation of methane into synthesis gas

The partial oxidation of methane to synthesis gas over an - and a -supported Rh catalyst has been studied at atmospheric pressure using in situ DRIFTS between 823 and 973 K. A surface intermediate species with IR band at 2000 cm^-1, correlating with the CO formation, was observed during the partial oxidation. DRIFT spectra of adsorbed CO at 323 K were used to study the state of Rh during the partial oxidation. The state of Rh at 973 K is proposed to be a matrix of metallic rhodium with clusters of partially reduced oxide phase with isolated Rh⁺ atoms dispersed on the support. Rh oxide with Rh⁺ cations is the state of Rh during partial oxidation of methane at 823 K. This revised version was published online in July 2006 with corrections to the Cover Date.     

The IR spectroscopy of methane and hydrogen adsorbed on α-chromia

The vibrational perturbations induced in the IR spectra of methane and of dihydrogen by the non-dissociative adsorption on the (01 2) and (11 0) faces of -chromia are illustrated and compared. It is concluded that both molecules are adsorbed on Cr³⁺ sites and that the involved forces are mainly of the electrostatic type. The resulting situation is compared with that found on the more basic MgO. The problems associated with the C–H and H–H bond activations on transition metal oxides are also discussed.     

Correlation between CO frequency and Pt coordination number. A DRIFT study on supported Pt catalysts

The infrared stretching frequencies of linear-bonded carbon monoxide on face, edge and corner atoms have been identified with four platinum catalysts. The metal particles were supported on different absorbentia and each having a different average particle size, ranging from about 10 to 200 Å. The values of the various absorption bands correlate linearly with the number of nearest neighbours of the different surface sites (n in C _n ). Effects of an interaction between Pt clusters and support on the linear-CO stretching frequency have not been observed. This empirical correlation between and C_n, and the advantages ofin situ Diffuse Reflectance Fourier transform Infrared Spectroscopy in combination with derivative spectrometry opens the possibility to monitor the dispersity of supported platinum in a simple and relatively quick way.     

Copper recovery from dilute solutions in the Falling-Film cell

The removal of copper from dilute solutions is examined in electrochemical reactors where the electrolyte flows as a thin film in an inclined channel between a plane plate and a sheet of expanded metal (Falling-Film cell). Copper is recovered as a thin sheet from the plane plate. The results are compared with a known simplified model and the variations of the faradaic yield with the operating conditions are discussed.Nomenclature A _e electrode surface area - b width of inclined channel - C(t) copper concentration at timet - C ₀ initial copper concentration - d interelectrode distance - overall current density - overall limiting current density - overall mass transfer coefficient - L length of the channel - Q _v volumetric flow rate - Q _vl volumetric flow rate per unit of channel width (=Q _v/b) - t time - t _s residence time in the reactor, defined by Equation 1 - mean flow velocity of the liquid film, defined by Equation 2 - V volume of electrolyte in the circuit - V _R reactor volume - v _sn normalized space velocity, defined by Equation 9 - inclination angle with respect to the horizontal - instantaneous faradaic yield - time-averaged faradaic yield - v _e number of electrons exchanged in the electrochemical reaction     

Dilute acid-hydrolized cotton cellulose An electron diffraction study

Summary A comparative morphological investigation by electron diffraction analysis was carried out on samples of cotton cellulose from different stages of dilute-acid-catalysed hydrolytic degradation reactions. Within the range from 13000 (native material) to 500 only a gentle decrease of the relative crystallinity was observed. For below 500 the crystallinity decreases much faster, together with a simultaneous marked increase in paracrystalline lattice distortion and the show up of crystallographic evidence for a new cellulose phase which became better defined as degradation proceeded. A clearly defined parallel can be established between the different kinetic stages of the degradation reaction and the degree-of-polymerization dependence of the morphological features. The resulting evidence is at odds with the traditionally held views about the effects of acid hydrolysis of cellulose on its morphological fine structure.     

Activity and selectivity of PtNi/TiO2 catalysts for hydrogenation of crotonaldehyde

The hydrogenation of crotonaldehyde over a series of titania supported PtNi catalysts was investigated. Pt/TiO₂ had the highest activity to hydrogenate the bond of crotonaldehyde. With the addition of Ni to Pt the activity for carbonyl group hydrogenation decreased, while that for the bond hydrogenation increased. Two different types of sites were established to be active for bond hydrogenation, located at (i) the Pt-TiO₂ interface and (ii) the PtNi bimetallic phase. For the Pt-TiO₂ interface the presence of accessible Ti ^x+ cations in close distance to Pt and for the PtNi phase a slightly positively charged Ni on the surface of these alloy particles were concluded to be responsible for the enhanced selectivity to crotylalcohol. The hydrogenation of the bond occurs mainly on the clean metal surfaces of Ni and Pt.     

Synthesis gas formation by direct oxidation of methane over Rh monoliths

The production of H₂ and CO by catalytic partial oxidation of CH₄ in air or O₂ at atmospheric pressure has been examined over Rh-coated monoliths at residence times between 10^–4 and 10^–2 s and compared to previously reported results for Pt-coated monoliths. Using O₂, selectivities for H₂ ( ) as high as 90% and CO selectivities (S _CO) of 96% can be obtained with Rh catalysts. With room temperature feeds using air, Rh catalysts give of about 70% compared to only about 40% for Pt catalysts. The optimal selectivities for either Pt or Rh can be improved by increasing the adiabatic reaction temperature by preheating the reactant gases or using O₂ instead of air. The superiority of Rh over Pt for H₂ generation can be explained by a methane pyrolysis surface reaction mechanism of oxidation at high temperatures on these noble metals. Because of the higher activation energy for OH formation on Rh (20 kcal/mol) than on Pt (2.5 kcal/mol), H adatoms are more likely to combine and desorb as H₂ than on Pt, on which the O+ H OH reaction is much faster.This research was partially supported by DOE under Grant No. DE-FG02-88ER13878-AO2.     

The influence of total monomer concentration on the “reactivity” of ω-(p-vinylbenzyl ether) macromonomers of poly(2,6-dimethyl-1,4-phenylene oxide) determined from radiacal copolymerization experiments with butyl methacrylate

Summary The influence of the total monomer concentration on the radical reactivity ratio r₁ of butyl methacrylate (BMA) (M₁)--(p-vinylbenzyl ether) macromonomer of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO-VBE) (M₂) monomer pair was investigated. For two different molecular weights of the PPO-VBE macromonomer ( , and ), the determined reactivity ratio r₁ decreases with the increase of the macromonomer concentration. Therefore, the reactivity of the macromonomer, 1/r₁, follows the opposite trend. This dependence is due to micelles formation during copolymerization. This microsegregation process partitionates the comonomer concentrations between the bulk of solvent and around the growing chain and therefore, the experimental r₁ is actually a product of the true reactivity ratio r₁ ⁰ and a partition coefficient k.     

Catalytic activity and XPS surface determination of tungsten carbide for hydrocarbon reforming. Influence of the oxygen

The influence of oxygen on the catalytic properties of tungsten carbide has been studied for the reforming reaction of 2-methylpentane in a great excess of hydrogen . The oxygen surface concentration has been measured by the ratio of the signal area of the O_1s and the W_4f levels as determined by X-ray photoelectron spectroscopy. Two kinds of processes are observed: cracking and isomerization reactions. The introduction of oxygen at T=350°C leads to a deep decrease of the cracking reaction kinetics; about two orders of magnitude. The tungsten carbide, strongly selective for cracking reactions in absence of oxygen, becomes very selective for isomer production in the presence of oxygen.     

Surface characterization of zirconium titanate (ZrTiO4) powder by measurements of electrical photoconductance and photoassisted oxygen isotope exchange

The photosensitivity of a ZrTiO₄ sample (33 m²/g) prepared by a sol-gel method has been assessed in the presence of O₂ by both photoconductance and oxygen isotope exchange (OIE) measurements at room temperature at wavelengths > 290 nm. For oxygen pressures < ca. 13.3 Pa, the steady-state photoconductance of ZrTiO₄ was unaffected by , which indicated that the direct recombination of the photoproduced charges played the dominant role. At higher pressures, varied as the reciprocal of , which was consistent with the fact that the electronic equilibrium was then governed by O₂ + e^– O ₂ ^– . OIE over ZrTiO₄ occurred predominantly via the overall mechanism which involves the exchange of two surface oxygen atoms for each exchange act. It was very slow as compared with OIE over photocatalytically active anatase samples which, in addition, occurs via another mechanism. These results allow one to predict that this ZrTiO₄ sample is a poorly active photocatalyst for oxidations involving gaseous oxygen, and further illustrate the interest of and OIE measurements to evaluate the photosensitivity of semiconductor oxide samples.     

Polymerization of substituted acetylenes by (mesitylene)M(CO)3 (M=W,Mo)

Summary Phenylacetylene could be polymerized by (mesitylene)W(CO)₃ in CCl₄ to give a polymer with 12,000 in ca. 80% yield. UV irradiation was unnecessary unlike the W(CO)₆–CCl₄-h catalyst. The present polymerization did not proceed in toluene. The (mesitylene)W(CO)₃ catalyst afforded high molecular weight polymers from phenylacetylenes bearing bulky substituents (e.g., Me₃Si and CF₃) at the ortho position. The Mo counterpart, (mesitylene)Mo(CO)₃, catalyzed the polymerization of 1-chloro-2-phenylacetylene and 1-chloro-1-octyne to provide high molecular weight polymers . Catalytic amounts of Lewis acids accelerated the polymerization of phenylacetylene by (mesitylene)W(CO)₃, but decreased the polymer molecular weight; this polymerization proceeded not only in CCl₄ but also in toluene.     

X-Ray absorption studies of the Ni environment in Ni-Mo-S

The local environment of the Ni atoms in the Ni-Mo-S phase has been elucidated by Ni K-edge EXAFS and XANES measurements of carbon-supported sulfided Ni-Mo catalysts. The results show that the Ni atoms have a low sulfur coordination number (less than six). This is contrary to recent reports in which an octahedral-like sulfur coordination have been suggested. It is proposed that the Ni atoms in Ni-Mo-S are located at the edges of the MoS₂ structure in square and tetragonal pyramidal type sites. These two types of sites can easily interconvert during sulfur addition/extraction and may as such be involved in the catalytic cycle.     

On the determination of oxygen potentials and O/M ratios in mixed U-Pu oxides by means of solid state galvanic cells

Measurements of oxygen potential on uranium-plutonium mixed oxides by means of solid state galvanic cells are discussed and compared with precedent data. Discrepancies in the values at low temperature (1000 K) as well as in the versusT slopes are found, which disappear when the samples are thermally cycled. An analysis is performed of this effect, showing that the absence of a good homogeneization of the sample in oxygen and/or in plutonium content can give rise to mixed potentials and hence to erroneous results.     

Multi-arm star polyisobutylenes

Summary The first synthesis of a multi-arm radial-star polyisobutylene (*-PIB) is described. The synthesis occurred by the addition of excess divinylbenzene (DVB) linking reagent to a living polyisobutylene (PIB) charge i.e., by the arm first method under specific conditions. The radial structure of the *-PIB was proven by determining the molecular weight of a sample by light scattering, then selectively destroying the aromatic polydivinylbenzene (PDVB) core, and finally determining the molecular weight of the surviving alphatic PIB arms. The synthesis strategy, kinetic observations during synthesis, and procedures leading to a representative *-PIB are described. This product whose g/mole with , contained 90.3 mole% (78 wt.%) PIB arms and 9.7 mole% (22 wt.%) aromatic core; thus the number of PIB arms emanating from the core was (number average number of arms)=56 or (weight average number of arms)=110.     

High pressure FIR-spectroscopy on polyethylene at elevated temperature

Summary The temperature and pressure dependence of the translational B_1u-lattice vibration has been determined in the pressure range of 7 kbar and a temperature range of almost 200 K from room temperature upwards. For some pressure values the Grüneisen Parameter has been evaluated as a function of temperature. A detailed discussion is given for a step in the (T)-curves at elevated pressure.     

n‐butane isomerization on sulfated zirconia: isotopic transient kinetic analysis of reaction at the site level

By using SSITKA (steady‐state isotopic transient kinetic analysis), n‐butane (n‐C₄) isomerization on sulfated zirconia (SZ) has been studied for the first time at the site level. Accurate measures of the average residence time and the concentration of the most active surface intermediates leading to isobutane (iso‐C₄) were able to be determined. As has previously been observed, a fast initial deactivation of the catalyst followed by a slow steady‐state deactivation was observed over 400 min time‐on‐stream (TOS). It was shown that even though a large amount (∼100 μmol/g) of n‐C₄ was adsorbed on the catalyst, the concentration of active surface intermediates leading to iso‐C₄ was only ∼10 μmol/g at 30 min TOS. The continuous decrease in indicated that the decrease in catalytic activity was due to loss of active sites. An increase in the average residence time of active surface intermediates leading to iso‐C₄ was observed only between 30 and 100 min TOS. This suggests a possible presence of two types of active sites for n‐C₄ isomerization on SZ under the reaction condition studied. It is suggested that the more‐active sites contributed to the high initial activity, while the majority of active sites after 100 min TOS were the less active sites. This revised version was published online in July 2006 with corrections to the Cover Date.     

Studies on nonisothermal solid state galvanic cells — effect of gradients on EMF

An expression for the EMF of a nonisothermal galvanic cell, with gradients in both temperature and chemical potential across a solid electrolyte, is derived based on the phenomenological equations of irreversible thermodynamics. The EMF of the nonisothermal cell can be written as a sum of the contributions from the chemical potential gradient and the EMF of a thermocell operating in the same temperature gradient but at unit activity of the neutral form of the migrating species. The validity of the derived equation is confirmed experimentally by imposing nonlinear gradients of temperature and chemical potential across galvanic cells constructed using fully stabilized zirconia as the electrolyte. The nature of the gradient has no effect on the EMF.Nomenclature J _i flux of speciesi - X _i generalized forces - L _ij Onsagar coefficient - ₁ electrochemical potential of ions - ₂ electrochemical potential of electrons - T absolute temperature - U ₁ ^* total energy of transfer of the ion - partial molar enthalpy of the ion - Q ₁ ^* heat of transport of the ion - Z ₁ charge on the ion - F Faraday constant - electrostatic potential - ₂ chemical potential of the electron - ₁ chemical potential of the ion - partial entropy of the ion - E _SE EMF developed across the solid electrolyte - E _Pt EMF developed across the platinum lead - ( ₂)_Pt chemical potential of electrons in platinum - partial entropy of electrons in platinum - (Q ₂ ^* )_Pt heat of transport of electrons in platinum - E _cell EMF developed across the whole cell - chemical potential of oxygen - chemical potential of oxygen in its standard state - R universal gas constant - partial pressure of oxygen - relative chemical potential of oxygen - _M relative chemical potential of metal M - a _M activity of metal M