In situ FTIR spectroscopy on rhodium-exchanged NaX zeolite with different metal dispersion during syngas reaction

In situ FTIR spectroscopy has been applied to study the reason of the different selectivity behaviour of rhodium in the CO hydrogenation reaction in dependence on the different particle size. Several forms of molecularly adsorbed CO are observed, such as linearly- and bridgedbonded CO on metallic rhodium as well as dicarbonyl species with Rh(I) centres formed by oxidation of Rh(0) with protons in presence of CO. Furthermore, non-reactive formate, acetate, and carbonate species are produced as side products of the reaction. The higher selectivity to oxygenates, particularly to methanol, is explained by the existence of multiple-bonded CO present only on small rhodium crystallites. The multiple-bonded CO formed at low temperatures is converted at higher temperatures to the highly reactive formyl species, which is hydrogenated to methanol.     

Behaviour of mesogenic side group polyacrylates in dilute and semidilute regime

The solution behaviour of a new mesogenic side group polyacrylate in tetrahydrofuran and toluene has been investigated by static and dynamic light scattering. In the dilute regime the polymer behaves as typical polydisperse linear chains in good solvent and the dynamics is dominated by a single fast mode. Cluster formation was detected starting at a concentration around 50 g l⁻¹. It seems to be independent of the solvent as well as of polymer molecular weight. In the semidilute regime, the behaviour of the reduced osmotic modulus leads to the conclusion that repulsion between the chains is stronger than in linear macromolecules. The appearance of larger clusters was revealed above a characteristic concentration and is slightly dependent on the polyacrylate molecular weight. The dynamics was generally characterised by a fast mode related to the cooperative diffusion and by a slow mode associated with large clusters. The existence of a network of multiconnected clusters is envisaged with increasing solution concentration.     

Studying the length of trans conformational sequences in polyethylene using Raman spectroscopy: a computational study

The long standing question of how long a trans sequence in a polyethylene needs to be in order to contribute to the all-trans Raman bands at 1060 and 1130 cm⁻¹ is addressed. Various hexadecane, C₁₆H₃₄, conformers were studied using ab initio type calculations revealing vibrational frequencies and intensities. We found that only trans sequences longer than 10 trans bonds reveal Raman intensity primarily selectively at the same frequencies as the C-C stretching modes arising from crystalline polyethylene. Since it is statistically highly unlikely that such long trans sequences occur in the amorphous phase, intensity arising from all-trans sequences not belonging to crystalline structure may only be expected as a consequence of strong non-equilibrium conditions (e.g. shear), or the presence of tie-molecules.     

Nitrogen plasma modification of viscose-based activated carbon fibers

Viscose-based activated carbon fibers (VACFs) were treated by a dielectric-barrier discharge plasma at different conditions. Nitrogen was used as the feed gas to create nitrogen radicals. The textural characteristics were analyzed by SEM, BET and XRD. The surface chemical functional groups were analyzed by XPS. The results show that after nitrogen plasma modification (NPM), the external surface of the VACFs was etched and became rougher, the surface area and pore volume decreased, the average micropore width barely changed, the PSD of the VACF became narrower and the graphitic crystallites of VACF had been destroyed slightly. XPS revealed that NPM could remarkably change the distribution of the oxygen functional groups on the VACFs surface and there were more nitrogen atoms incorporated into the aromatic ring. A tentative explanation for the modification process is proposed.     

DX centers in AlxGa1-xAs bulk alloy,AlAs/GaAs ordered,and disordered superlattices

Properties of theDX centers in Al_0.5Ga_0.5As bulk alloy (b-AL), (AlAs)₂ (GaSa)₂ ordered superlattice (o-SL) and (AlAs) _m (GaAs) _n disordered superlattice (d-SL) (m = 1, 2, 3,n = 1, 2, 3) with the same macroscopic composition were measured and compared. By deconvolution of deep level transient spectroscopy (DLTS) spectrum due to theDX center, we have found a decrease in the number of separate peaks in DLTS spectrum in an intentionally atomic ordered arrangement. Visiting Scholar of the Japan Society for the Promotion of Science. On leave from Department of Electrical Engineering, San Jose State University, San Jose, California 95192-0084, USA.     

金属表面柴油机油沉积物的反射红外光谱法研究

利用镜反射红外光谱法研究了ＣＣ级柴油机油中添加剂对成漆板板面漆膜组成的影响：考察了成漆板漆膜组成与Ｃａｔ．１Ｈ２活塞环台漆膜组成的相关性。试验结果对柴油机油的研制和应用有一定指导作用。     

In Situ FTIR Study of the Formation of an Organosilane Layer at the Silica/Solution Interface

An FTIR experiment especially designed to study the growth of an organosilane layer at the interface between a solution and a flat silica surface is presented. High sensitivity is achieved by using the attenuated total reflection (ATR) technique in a liquid flow cell. The ATR crystal, either silicon or germanium, is covered with a very thin silica layer. Chemical reactions of a mono-and a di-hydrolyzable silane with the silica substrate have been investigated. The grafting of a submonolayer of the first reagent has been monitored by following the C-H and SiO-H vibrations. The density of grafted molecules has been estimated and information on the nature of the chemical bonding has been achieved. Evidence for the chain-polymerization of the dihydrolyzable silane at the substrate/solution interface has been inferred from the appearance of a Si-O-Si absorption band.     

An infrared spectroscopic study of the mechanism of chloromethane conversion to higher hydrocarbons on HZSM5 catalyst

Investigation of the reaction mechanism of chloromethane on ZSM5 is a new topic. In this work an in situ FTIR technique was employed to study the conversion processes of chloromethane, the active sites on HZSM5, and the desorption state of surface species. The catalytic conversion of chloromethane to higher hydrocarbons was also studied. It is demonstrated that chloromethane can be reversibly adsorbed on acidic sites of HZSM5 at room temperature. At 100°C chloromethane is irreversibly and dissociatively adsorbed on the strong acidic sites of HZSM5, on which surface methoxyl is formed as proved by infrared characteristic C-H stretchings of-CH₃ at 2960 and 2870 cm^–1. Alkoxyls are produced and adsorbed on the catalyst surface as characterized by the infrared absorption bands of -CH₂-groups at 1460 and 2930 cm^–1. At 100°C the adsorbed methoxyl and alkoxyls are the main surface species, and a small amount of aromatics might exist as detected by a characteristic absorption band at 1510 cm^–1. Between 100 and 200°C the adsorbed surface methoxyl and alkoxyls are converted to aromatics, and the occupied OH groups partially appear. At temperature higher than 300°C the adsorbed aromatics are thermally desorbed into the gas phase. Aromatics and alkanes are the main products in catalytic conversion. These results reveal that the formation of aromatics from methoxyl and alkoxyls is easier than the desorption of aromatics from HZSM5 catalyst. An alkoxyl mechanism is proposed for the conversion of chloromethane on HZSM5 based upon the experimental results and the three assumptions: (a) The primary C-C bond is formed from surface methoxyl groups via the methoxyl group polarization and C-H bond weakening, (b) The adsorbed alkoxyls are converted to aromatics via hydrogen transfer and bond rearrangement similar to the conventional carbenium ion mechanism for the aromatization of olefins and alkanes on HZSM5. The hydrogen atoms from the aromatization stimulate the desorption of alkoxyls to alkanes. (c) At temperature higher than 300°C surface reactions and desorption of adsorbed species take place simultaneously, determining the product distribution in the catalytic conversion.     

Direct Spectroscopic Determination of Europium(Ⅱ) Concentration During Europium(Ⅲ) Electro-Reduction in Hydrochloric Acid Medium

UV-Vis spectroscopy was used to directly determine the concentration of Eu(Ⅱ) during electroreduction of Eu(Ⅲ) in hydrochloric acid medium. Electroreduction was carried out in a flow type electrolyzer with glassy carbon cathode at the constant potential of -800 mV vs. Ag/AgCl. The effects of oxygen and concentration of hydrochloric acid on the system were investigated. For 0.01 mol·L-1 hydrochloric acid, calibration curves for Eu(Ⅱ) absorption bands at 248 and 320 nm were constructed. Molar absorption coefficients were estimated to be 2016 and 648 L·mol-1·cm-1, respectively. The absorbance strongly decreased with decrease in pH of the solution, whereas concentration of chloride had only a negligible effect.     

Progress in near-field photothermal infra-red microspectroscopy

Near‐field photothermal Fourier transform infra‐red microspectroscopy, which utilizes atomic force microscopy (AFM)‐type temperature sensors, is being developed with the aim of achieving a spatial resolution higher than the diffraction limit. Here we report on a new implementation of the technique. Sensitivity of the technique is assessed by recording infra‐red spectra from small quantities of analytes and thin films. A photothermomechanical approach, which utilizes conventional AFM probes as temperature sensors, is also discussed based on preliminary results. Early indication suggests that the photothermal approach is more sensitive than the thermomechanical one.