Evaluation of Activation Energies for Pairwise and Non-Pairwise Hydrogen Addition to Propyne Over Pd/Aluminosilicate Fiberglass Catalyst by Parahydrogen-Induced Polarization (PHIP)

Hydrogenation of propyne to propene over Pd/aluminosilicate fiberglass catalyst in the temperature range 175–350 °C was investigated with the use of parahydrogen-induced polarization (PHIP) technique. Activation energies for both pairwise and non-pairwise H₂ addition routes were estimated. It was found that at 175–275 °C the activation energies for hydrogen addition to the triple bond of propyne have similar values (about 60–70 kJ/mol) for both routes of hydrogen addition. At higher temperatures (275–350 °C), the rate constant for pairwise hydrogen addition reaches a maximum value while the rate constant for non-pairwise hydrogen addition continues to increase with increasing temperature.     

第一性原理计算α-ScDx(D=H,He)的弹性常数

本文采用第一性原理方法研究了α相钪氢化合物(α-ScH _x )和α相钪氦化合物(α-ScHe _x )的弹性常数,其中x=0,1/4,1/8,1/32表示H原子和He原子在α-ScD_x(D=H,He)中的浓度.研究结果表明,对于钪,氢和氦对晶体的弹性性质的影响截然不同.钪氢化合物晶体的弹性常数基本上随着晶体中氢的浓度增加而增加,这跟实验测量得出的结论一致;然而,钪氦化合物体系的弹性常数几乎随着氦浓度的 关键词： 第一性原理 弹性常数 x')" href="#">α-ScH _x x')" href="#">α-ScHe _x     

Parahydrogen-Induced Polarization in Heterogeneous Hydrogenations over Silica-Immobilized Rh Complexes

The use of heterogeneous catalysts for parahydrogen-induced polarization (PHIP) of nuclear spins opens new horizons for production of hyperpolarized substances. Immobilization of homogeneous hydrogenation catalysts is a promising approach for designing the efficient heterogeneous catalytic systems capable of PHIP generation. Herein, we study the formation of PHIP in the gas-phase and in the liquid-phase hydrogenations of propyne and propylene catalyzed by silica-immobilized Rh complexes synthesized by the ligand-exchange anchoring of the Wilkinson’s complex RhCl(PPh₃)₃, the binuclear complex Rh₂Cl₂(C₈H₁₂)₂ and the cationic complex [Rh(C₈H₁₂)₂]⁺[BF₄]^? to the phosphine-modified silica gel. We consider the stability and the mechanistic aspects of the hydrogenation over the immobilized Wilkinson’s catalyst in terms of PHIP observation. Using a PASADENA (parahydrogen and synthesis allow dramatically enhanced nuclear alignment) effect, it is found, in particular, that liquid-phase propyne hydrogenation over the immobilized Wilkinsons’s catalyst at 70°C proceeds in a stable regime with a stereoselective cis addition of a hydrogen molecule, while in the gas phase at the same temperature the hydrogenation stereoselectivity is observed only for a short time after the reaction is started, and then the catalyst rapidly loses its activity. The reasons of the catalyst deactivation are discussed based on the literature data, the results of infrared spectroscopy study, and the comparison to the behavior of the immobilized binuclear and cationic Rh complexes. In addition, it is shown that the immobilized Wilkinson’s catalyst is reduced as temperature increases in the range of 90–130°C, as confirmed by X-ray photoelectron spectroscopy.     

Density functional study of uranyl （VI） amidoxime complexes

Uranyl (VI) amidoxime complexes are investigated using relativistic density functional theory. The equilibrium structures, bond orders, and Mulliken populations of the complexes have been systematically investigated under a generalized gradient approximation (GGA). Comparison of (acet) uranyl amidoxime complexes ([UO₂(AO)_n]^2-n, 1 ≤ n ≤ 4) with available experimental data shows an excellent agreement. In addition, the U-O(1), U-O(3), C(1)-N(2), and C(3)-N(4) bond lengths of [UO₂(CH₃AO)₄]^2- are longer than experimental data by about 0.088, 0.05, 0.1, and 0.056 Å. The angles of N(3)-O(3)-U, O(2)-N(1)-C(1), N(3)-C(3)-N(4), N(4)-C(3)-C(4), and C(4)-C(3)-N(3) are different from each other, which are due to existing interaction between oxygen in uranyl and hydrogen in amino group. This interaction is found to be intra-molecular hydrogen bond. Studies on the bond orders, Mulliken charges, and Mulliken populations demonstrate that uranyl oxo group functions as hydrogen-bond acceptors and H atoms in ligands act as hydrogen-bond donors forming hydrogen bands within the complex.     

Reactions of small gold cluster cations with propylene, methane, and hydrogen: permissive and competitive coadsorption effects

Coadsorption effects of molecular hydrogen and small hydrocarbons, CH₄ and C₃H₆, on free Au₃ ⁺ and Au₅ ⁺ were investigated in an octopole ion trap under multi-collision conditions. For hydrogen and methane the observations indicate that both molecules coadsorb on the same adsorption site, i.e., the same atom of the cluster. This type of molecular adsorption on free clusters is termed permissive coadsorption, in contrast to competitive coadsorption, in which two molecules compete for the same adsorption site. The latter case was observed for hydrogen and propylene: already trace amounts of propylene were able to completely saturate the clusters preventing the coadsorption of H₂. The size dependent adsorbate coverage is discussed and implications on the cluster structure are deduced from time and temperature dependent reaction measurements.     

Comparing reaction orders of anthracite chars with bituminous coal chars at high temperature oxidation conditions

The influence of concentration of oxygen on the oxidation rates of 5 anthracite chars is investigated at gas temperatures ranging from 1223 K to 1673 K. Reaction orders and kinetic parameters are determined with a multivariable optimization method in which modeled burnout profiles are fitted to experimental burnout profiles from a 4 m isothermal plug flow reactor operating at industrially realistic heating rates, i.e., 10⁴–10⁵ K/s. The determined reaction orders are compared to reaction orders of 10 bituminous coal chars investigated at similar conditions in a previous study. The results show that the optimized reaction order of the anthracite chars is zero, while the reaction order of the bituminous coal char is one. The difference in the reaction orders cannot be explained by using the two semi-global oxidation reactions: C(O) + O₂ → CO/CO₂ and C(O) → CO. However, by also considering 2C(O) → CO₂ + C as a possible reaction step, the reaction order difference between the anthracite chars and the bituminous coal chars can be explained. In addition, a first attempt to apply the same multivariable optimization method to determine the reaction order for a biomass char is presented.     

Hydrogen gas-sensing properties of Pt/WO<Subscript>3</Subscript> thin film in various measurement conditions

A well-known gasochromic material is Pt particle-dispersed tungsten trioxide (Pt/WO₃). Its optical properties could make it effective as a hydrogen gas sensor. In this study, Pt nanoparticle-dispersed WO₃ thin films were prepared using the sol–gel process, and their optical and electrical properties dependent on the working environment (i.e., temperature, hydrogen gas concentration, oxygen partial pressure, etc.) were investigated. The Pt/WO₃ thin films prepared at 400 °C showed the largest change in optical transmittance and electrical conductivity when exposed to hydrogen gas compared with the films prepared at other temperatures. The optical absorbance and electrical conductivity were found to be dependent on the hydrogen and oxygen gas concentration in the atmosphere because generation and disappearance of W⁵⁺ in the thin films depend on the equilibrium reaction between injection and rejection of H⁺ into and from the thin films. In addition, the equilibrium reaction depends on the hydrogen and oxygen gas concentrations.     

Comparison of VO<Subscript>2</Subscript> thin films prepared by inorganic sol-gel and IBED methods

VO₂ thin films with semiconductor-to-metal phase-transition properties were prepared by inorganic sol-gel and IBED (ion-beam-enhanced deposition) methods on SiO₂/Si substrate. The crystalline phase and the shape and width of the hysteresis curves of these VO₂ films were significantly different. For sol-gel VO₂ films, the transition started at close to 62 °C upon heating. The temperature interval needed to complete the phase transition was 8 °C, the ratio of resistance (R_{20 °C}/R_{80 °C}) reached three orders and the hysteresis width was 6 °C. However, the IBED film post-annealed in Ar at 700 °C underwent a phase transition from 45 °C to 80 °C, the ratio of resistance was more than two orders and the hysteresis width was 2 °C. In addition, the TCR (temperature coefficient of resistance) at 22 °C of the IBED film was 3.5%/K, much larger than the 0.7%/K TCR of the sol-gel film. PACS 73.50.F; 73.66.E; 81.20; 81.05.Z; 81.15     

In situ investigation of the catalytic reaction H2+< ![IGNORE[O2→H2 O with second-harmonic generation

2 +O₂→H₂ O in the pressure range 0.2 Torr≤p_tot≤10 Torr on Pt(111) surface. At a catalyst temperature of T=700 K the equilibrium oxygen coverage θ_o is determined as a function of hydrogen partial pressure α. The experimentally obtained θ_o is modelled in a two step process considering the mass transport in the gas phase as well as the catalytic reaction on the surface. In this pressure range the mass transport in the gas phase changes from molecular flow conditions to laminar flow, inducing a strong modification of the gas phase present at the catalyst through different diffusivities of the reactants as well as through desorbing reaction products from the catalyst. It is shown that these gas phase alterations have to be taken into account for a proper modelling of the surface mechanism. Simulation calculations allow one to identify the sequential hydrogen addition reaction as the main reaction path for water production in this parameter range. Excellent agreement with previous investigations is obtained for the determined activation energies of the water-producing reaction steps equal to E^f _H2O≥0.7 eV. Received: 20 September 1998 / Revised version: 15 December 1998     

Effect of hydrogen absorption on the magnetic properties of Zr(Fe1−xAlx)2 compounds

Magnetic measurements have been performed on Zr(Fe_0.8Al_0.2)₂ (C15 structure) and on Zr(Fe_0.7Al_0.3)₂ (C14 structure) and their hydrides. These host metal system absorb ≈2 H/formula unit, accompanied by an expansion in volume ranging from 11 to 14%, without change of crystal structure. In both compounds, ferromagnetism is strongly suppressed upon hydrogenation, indicating that Fe-Fe exchange is markedly weakened by hydriding. Hydrogenation converts ferromagnetic Zr(Fe_0.8Al_0.2)₂ and Zr(Fe_0.7Al_0.3)₂ into a super paramagnet and spin-glass, respectively. This suggests a striking change in the electronic 3d band structure due to hydrogen absorption, and in addition the importance of varying local hydrogen concentrations because of varying environments for a given interstitial site.     

Physicochemical characteristics of ZSM-5/SAPO-34 composite catalyst for MTO reaction

SAPO-34 and ZSM-5 are the most well-known catalyst for MTO reaction. A combination of ZSM-5 and SAPO-34 might give rise to optimal catalyst to meet a change of market demand for ethylene, propylene and butadiene. In this study, we have developed ZSM-5/SAPO-34 composite catalysts to control the composition of light olefins in MTO reaction. ZSM-5/SAPO-34 composite catalysts showed very different physicochemical and catalytic properties with respect to ZSM-5 and SAPO-34 synthetic procedure. The physicochemical properties of the composite catalysts have been compared by XRD, SEM, N₂ isotherm, FT-IR and NH₃-TPD. Their catalytic performances were also evaluated for MTO reaction. The series composite catalyst synthesized by successive crystallization of SAPO-34 synthetic gel after ZSM-5 crystallization exhibited relatively high catalytic performance.     

Reaction of OH radical and ozone with methyl salicylate – a DFT study

A theoretical study on the reaction mechanism of methyl salicylate (MeSA), a green leaf volatile organic compound with OH radical and ozone, has been carried out using density functional theory methods using B3LYP, M06‐2X and MPW1K functionals with 6‐311++G(d,p) basis set. The atmospheric degradation pathways of MeSA with OH radical are studied under two different pathways, viz. H‐atom abstraction and electrophilic addition of OH radical. The hydrogen abstraction from –OH group is found to be the dominant reaction channel with small barrier height. Likewise, the electrophilic addition of OH radicals at the para position of MeSA is found to be favourable rather than the ortho and meta positions because of the small barrier height. However, the reaction of MeSA with respect to the addition of O₃ is initiated only through the cycloaddition to the C?C bond, resulting in primary ozonide. The Arrhenius plot for most of the addition reaction shows positive temperature dependence, while for the abstraction reaction, it exhibits negative temperature dependence over the temperature range of 278–350 K. The calculated theoretical rate constants are in good agreement with available experimental data. Overall, the addition of both OH radical and ozone possesses ability to degrade MeSA, but slower when compared with the Cl radical. Copyright © 2015 John Wiley & Sons, Ltd.     

X-ray electron probe microanalysis of the reaction zone of thermally stimulated heterovalent anion substitution in the Ga 2III Se 3VI -GaAs solid-phase system

X-ray electron probe microanalysis (EPMA) was used to study the concentration profiles of the main reaction components in the Ga₂Se₃-GaAs heterojunction obtained as a result of thermally stimulated heterovalent anion substitution. It has been found that the quasi-equilibrium and quasi-steady diffusion modes for delivery of chalcogen to the reaction zone are different with respect to the kinetics of the A₂^IIIC₃^VI layer growth. Independent of this, the concentration profiles of the reaction elements are self-organized with time, which allows heterostuctures with a sharp interphase boundary to be reproduced.     

Effects of concentrated NaCl and KCl solutions on the behaviour of aqueous peptide bond environment: single-particle dynamics and H-bond structural relaxation

The effects of salt concentrations on the structure, dynamics and hydrogen bond structural relaxation properties of ～1.10 M aqueous N-methylacetamide (NMA) solution at 308 K are studied by classical molecular dynamics simulations. We have considered the concentration range of salts solution from 0.222 to 3.756 M to investigate the behaviour of aqueous environment of peptide bonds in the presence of concentrated NaCl and KCl solution. It is found that the addition of salt solution facilitates the structural breaking of aqueous NMA hydrogen bonds, as a result the number of hydrogen bonds per NMA molecule and their stability decreases. The water and NMA molecule shows slower translational and rotational dynamics with increasing salt concentrations due to additional ion atmospheric friction. Our result shows that the cation–O_NMA radial distribution function decreases whereas the Cl^?─H_NMA radial distribution function increases with ion concentration. On the other hand, the cation–O_water and Cl^?─H_water radial distribution function shows very negligible change with respect to ion concentration. We have also calculated NMA–water and water–water hydrogen bond structural relaxation times. It is observed that the hydrogen bond structural relaxation of O_NMA─H_water is comparatively slower than the H_NMA─O_water hydrogen bond, which can be attributed to higher number and greater stability of the former hydrogen bond than the latter. The change of the dynamical quantities observed here is more prominent in addition of NaCl rather than the KCl solution.     

Dielectric behaviour of propylene glycol-water mixtures studied by time domain reflectometry

Dielectric relaxation measurements on water mixtures of propylene glycol across the entire concentration range were carried out using time domain reflectometry at 25°C over the frequency range from 10 MHz to 4 GHz. For all the mixtures, only one dielectric loss peak was observed in this frequency range. The relaxation in these mixtures can be described by a single relaxation time using the Debye model. A plot of the calculated relaxation time of the mixtures gives a straight line against the mole fraction of water, X_w. It is reasoned that the diameter of the water cluster is nearly the same as the length of propylene glycol. Further, a plot of the dielectric relaxation strength δ? against X_w suggests that there is a changing pattern of dielectric behaviour from below X_w = 0.5 to higher values of X_w. The excess permittivity, the excess inverse relaxation time and the activation free energy have been determined, to confirm the formation of hydrogen bonded homogeneous and heterogeneous cooperative domains, the dynamics of solute-solvent interaction and the hindrance to molecular rotation in the hydrogen bonded glass forming propylene glycol-water system.     

The early oxynitridation stages of hydrogen-terminated (100) silicon after exposure to N2:N2O. III. Initial conditions

The structure and thermal stability in N₂ of hydrogen-terminated (100) silicon has been studied by X-ray photoemission spectroscopy, transmission electron microscopy, atomic force microscopy, thermal programmed desorption, and reflection high energy electron diffraction. Device-quality surfaces were prepared in an open-chamber reactor by exposing single crystalline, (100) oriented silicon to H₂ at high temperature (850 °C or 1100 °C) for durations on the order of 10² s. The observed stability with respect to N₂ at 850 °C is inconsistent with the reported desorption kinetics and may be accounted for in terms of either physico-chemical properties of the system (e.g., the presence of a buried layer of H₂ or of hydrogen-decorated vacancies whose out-diffusion restores the hydrogen terminations on the surface) or the reactor (persistence of hydrogen in the atmosphere even after switching it off). The nitridation by N₂ of hydrogen-terminated silicon is less efficient (per unit exposure) than that by N₂O by 4 orders of magnitude. PACS 68.35.Dv; 68.35.Fx; 82.65.Dp; 79.60.Jv; 81.60.Cp     

The adsorption of hydrogen and the reaction of hydrogen with oxygen on Pt (100)

The adsorption of hydrogen on Pt (100) was investigated by utilizing LEED, Auger electron spectroscopy and flash desorption mass spectrometry. No new LEED structures were found during the adsorption of hydrogen. One desorption peak was detected by flash desorption with a desorption maximum at 160 °C. Quantitative evaluation of the flash desorption spectra yields a saturation coverage of 4.6 × 10¹⁴ atoms/cm² at room temperature with an initial sticking probability of 0.17. Second order desorption kinetics was observed and a desorption energy of 15–16 kcal/mole has been deduced. The shapes of the flash desorption spectra are discussed in terms of lateral interactions in the adsorbate and of the existence of two substates at the surface. The reaction between hydrogen and oxygen on Pt (100) has been investigated by monitoring the reaction product H₂O in a mass spectrometer. The temperature dependence of the reaction proved to be complex and different reaction mechanisms might be dominant at different temperatures. Oxygen excess in the gas phase inhibits the reaction by blocking reactive surface sites. At least two adsorption states of H₂O have to be considered on Pt (100). Desorption from the prevailing low energy state occurs below room temperature. Flash desorption spectra of strongly bound H₂O coadsorbed with hydrogen and oxygen have been obtained with desorption maxima at 190 °C and 340 °C.     

Electrical properties of A′Ca2Nb3O10 (A′=K, Rb, Cs) layered perovskite ceramics

The electrical conductivity properties of Dion-Jacobson type layered perovskites A′Ca₂Nb₃O₁₀ (A′=K, Rb, Cs) was investigated under different gas atmospheres. An increase in the electrical conductivity by about 2–5 orders in magnitude in both ammonia and hydrogen atmospheres is observed compared to air. Among the members of the series, the compound with the smallest size of the alkali ion, i.e. KCa₂Nb₃O₁₀, exhibits the highest conductivity. In air and hydrogen, a single activation energy value in the range 0.25 – 0.80 eV is observed, while in ammonia a sharp increase in the electrical conductivity is found at about 500 °C. The activation energy at low-temperatures (300–500 °C) is attributed to ionic motion and at higher temperatures (500–700 °C) to both defect formation and ionic motion. The unusual electrical conductivity behavior in ammonia is explained on the basis of the model developed for alkali halides. EMF measurements reveal that the layered perovskites are ionic (proton) conductors. The electrical conductivity changes as a function of the ammonia gas concentration; accordingly, layered perovskites appear to be useful solid electrolytes in galvanic cells for practical applications, e.g. for gas sensors. Paper presented at the 7th Euroconference on Ionics, Calcatoggio, Corsica, France, Oct. 1–7, 2000.     

Surface characterization study of a Pd/Co3O4 methane oxidation catalyst

A surface characterization study using X-ray photoelectron spectroscopy (XPS) and ion scattering spectroscopy (ISS) has been performed on a 5 wt.% Pd/Co₃O₄ methane oxidation catalyst before and after exposure to a mixture of CH₄ and O₂ in N₂ at 250 °C for a period of 6 days. The primary peaks observed in the XPS survey spectra are the Co 2p, Pd 3d, O 1s and C 1s, along with Co, Pd and O Auger peaks. High-resolution Pd 3d spectra reveal that Pd exists on the surface predominantly as PdO, with no apparent change in chemical state during reaction. High-resolution XPS Co 2p and O 1s spectra reveal an accumulation of CoOOH and a depletion of CoO in the near-surface region during reaction. ISS analysis with intermittent 1-keV Ar⁺ sputtering was used to obtain depth profiles from the catalyst before and after reaction. The results indicate that the Pd/Co concentration ratio decreases with sputtering and that this ratio is larger for the as-prepared catalyst indicating that morphological changes occur during reaction. The ISS depth profile spectra obtained from the catalyst after reaction indicates the presence of an oxyhydroxide layer throughout the near-surface region. This observation is consistent with the XPS data indicating accumulation of hydroxide and oxyhydroxide species at the surface during reaction.Based on these data and the results of related studies, a reaction mechanism is proposed. In this mechanism, methane dissociatively chemisorbs to form a surface methoxy species and CoOOH. The remaining hydrogen atoms are stripped from the methoxy species leaving an active adsorbed C species which reacts with surface oxygen and a hydroxyl group to form an adsorbed bicarbonate ion which then decomposes to form CO₂ and a surface hydroxyl group. These hydroxyl groups also react to form H₂O and then more O₂ adsorbs dissociatively at the vacant sites.     

Insight into the reaction mechanism of ethanol steam reforming catalysed by Co–Mo6S8

The production of hydrogen via steam reforming of ethanol (SRE) is favourable for the use of hydrogen as an alternative fuel. Co–Mo₆S₈ possesses high activity and stability for SRE to sustainably produce hydrogen. The competition among reaction pathways related to C–H, O–H, C–C, C–O cleavage and H₂ formation was studied. The adsorption and reaction of related intermediates in the ESR reaction pathway are described. The results indicated that the most feasible route for the decomposition of ethanol catalysed by Co–Mo₆S₈ is CH₃CH₂OH*→CH₃CH₂O*→CH₃CHO*→CH₂CHO*→CHCHO*→CHCO*→CH*+CO*. The CH* can be decomposed into C*+H*, and CO* can be oxidised via the redox mechanism of the water gas shift (WGS) reaction. Thus the final products are CO₂ and H₂. The present result may help people to design an SRE catalyst, which has the ability to break C–C to form CO and H₂, then CO react with H₂O in the WGS reaction generating CO₂ and H₂.