碱土金属氧化物催化氧化异丙苯反应研究

考察了碱土金属氧化物CaO、MgO和SrO在催化氧化异丙苯合成过氧化氢异丙苯 (CHP)反应中的性能。3种催化剂的活性顺序为 :CaO >MgO >SrO。采用Hammett指示剂分别表征了碱土金属氧化物的碱强度。碱强度H-=15 0～ 18 4的碱性中心有利于异丙苯过氧化合成CHP反应。采用红外光谱分析了异丙苯在MgO、CaO催化剂表面的吸附态。异丙苯通过异丙基叔碳原子上的氢原子与CaO催化剂表面碱中心发生化学吸附 ,弱化了异丙基叔碳原子上的C—H键 ,从而有利于催化异丙苯氧化合成CHP的反应。MgO与异丙苯的异丙基叔碳上的氢原子的相互作用弱于CaO与异丙苯的异丙基叔碳上的氢原子的相互作用 ,使MgO催化异丙苯氧化的反应活性低于CaO催化异丙苯氧化的反应活性     

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.     

Evaluation of different coating systems by electrochemical methods

Corrosion protection of organic coated steel is determined by free corrosion potential measurements and impedance spectroscopy. The results are classified by means of very basic considerations and evaluation figures are developed. These electrochemical data are correlated with the extent of the corrosion for each coating system. The evaluation figures are used for ranking coating systems and this ranking is correlated with the ranking with reference to the results of standardized and exposure tests.     

The origin of the band at 1462 cm−1 generally appearing upon desorption of pyridine from acidic solids. Steps towards a more comprehensive understanding

The pyridine adsorption-desorption method, followed by IR spectroscopy, is generally applied for acidity determination of solid catalysts. A peculiar band at 1462 cm^–1 was observed by several authors upon pyridine desorption at higher temperatures and was interpreted in various ways. A new complex between Lewis framework acid sites and pyridine is proposed and several evidences are reported.     

THz-TDS signal analysis and substance identification via the conformal split

A terahertz time-domain spectroscopy(THz-TDS)imaging system can obtain high-dimensional signals with substance fingerprint information.By introducing geometric algebra,a novel signal analysis approach to THz-TDS signals is developed based on an optical physical mechanism.Using this approach,signals are represented with vectors in the high-dimensional real vector space.Geometric distribution properties and algebraic relationships of THz-TDS signals are deduced.It is proved that every complex refractive index of substances relates to a unique 2-blade,the vectors corresponding to the samples of the same substance are collinear and belong to the intrinsic 2-blade of the substance.When decomposed through the conformal split with respect to a 2-blade,THz-TDS signals of high dimensionality can be related to vectors in a 2-dimensional subspace.Based on the conformal split properties we deduced,two criteria for substance identification on the basis of THz-TDS signals are proposed.Accordingly,a novel substance identification method via the conformal split is presented.In the method,the 2-blade related to each "known" substance is calculated with two vectors corresponding to THz-TDS signals measured from samples of the substance but with dierent thicknesses.Using the conformal split with respect to those 2-blades,an identified vector corresponding to a THz-TDS signal is linearly related to the vector in a 2-dimensional subspace.The substance of a sample can be identified using criteria on the projected vectors in the subspaces.This method can contribute to accurate classification and identification.Finally,two experiments are presented that show the feasibility and accuracy of this method.