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.     

Accurate measurement of capture cross sections in deep level transient spectroscopy: Application to EL2 in GaAs

A rigorous formulation of capacitance changes during trap filling processes is presented and used to accurately determine the electron capture cross section of EL2 in GaAs at a particular temperature, 377K, in this case. The value, σ_n (377K) = 2.7 × 10⁻¹⁶ cm², is compared with that predicted from the emission dependence.     

Argon I Lines Produced in a Hollow Cathode Source, 332 nm to 5865 nm

We report precision measurements by Fourier transform spectroscopy of the vacuum wavenumber, line width, and relative signal strength of 928 lines in the Ar I spectrum. Wavelength in air and classification of the transition are supplied for each line. A comparison of our results with other precision measurements illustrates the sensitivity of Ar I wavelengths to conditions in the light source.     

Adsorption and decomposition of NO on carbon and carbon-supported catalysts

The interactions of NO with carbon and carbon-supported catalysts have been investigated by means Fourier transform infrared spectroscopy. Nitric oxide direct decomposition over carbon-supported catalysts (Cu, Pt) was studied in a temperature ranging from 473 to 623 K. NO conversion increased with increasing reaction temperature in the whole temperature range. The carbon-supported Pt catalyst has a very high activity for the decomposition of NO in the absence of oxygen. As a result of NO chemisorption isocyanate (-NCO) species on the surface of carbon containing Cu were observed. When the reaction temperature was increased, the -NCO band at 2229 cm⁻¹ became more intense.     

Structure of carbon nanotubes probed by local and global probes

A review is proposed of different techniques available today for the characterization of the atomic structure of carbon nanotubes. This review covers the electron microscopies, various diffraction techniques, scanning probe microscopies, and optical spectroscopies, including Raman scattering. The advantages and limitations of the characterization techniques are discussed.     

Dual reaction capacity of hydrogenated nanodiamond

High temperature hydrogen stream treatment of nanodiamond was shown to produce nanodiamond with bifunctional surface. OH- and different CH-groups were shown to be the main functional groups on the surface. In this article we proposed two main strategies for further chemical modification of hydrogenated nanodiamond. OH-groups were shown to react with different types of acylating agents: anhydrides and chloranhydrides. Chlorination of hydrogenated nanodiamond with molecular chlorine and its subsequent treatment with alkyllithium reagents resulted in formation of alkyl-nanodiamonds. Chlorination was shown to reduce the size of nanodiamonds aggregates. We have also applied suspension-state NMR-H1 spectroscopy to study suspensions of alkyl-nanodiamonds for the first time.     

Vanadium species in new catalysts for the selective oxidation of methane to formaldehyde: Activation of the catalytic sites

New vanadium oxide supported on mesoporous silica catalysts for the oxidation of methane to formaldehyde were investigated by infrared and Raman spectroscopies to identify and characterize the molecular structure of the most active and selective catalytic sites. In situ and operando experiments have been conducted in order to understand the redox and hydroxylation/dehydroxylation processes of the vanadium species. (SiO)₂VO(OH) species were identified in these catalysts in reaction conditions and shown to undergo a deprotonation at 580 °C under vacuum, leading to a site giving a photoluminescence band at 550 nm attributed to reverse radiative decay from the excited triplet state:

(V⁴⁺–O⁻)^*  (V⁵⁺O²⁻). An activation mechanism of vanadium monomeric species with electrophilic oxygen species is proposed.