Effects of Calcination Temperature on the Acidity and Catalytic Performances of HZSM-5 Zeolite Catalysts for the Catalytic Cracking of n-Butane

The acidic modulations of a series of HZSM-5 catalysts were successfully made by calcination at different treatment temperatures, i.e. 500, 600, 650, 700 and 800 ℃, respectively. The results indicated that the total acid amounts, their density and the amount of B-type acid of HZSM-5 catalysts rapidly decreased, while the amounts of L-type acid had almost no change and thus the ratio of L/B was obviously enhanced with the increase of calcination temperature (excluding 800 ℃). The catalytic performances of modified HZSM-5 catalysts for the cracking of n-butane were also investigated. The main properties of these catalysts were characterized by means of XRD, N2 adsorption at low temperature, NH3-TPD, FTIR of pyridine adsorption and BET surface area measurements. The results showed that HZSM-5 zeolite pretreated at 800 ℃ had very low catalytic activity for n-butane cracking. In the calcination temperature range of 500-700 ℃, the total selectivity to olefins, propylene and butene were increased with the increase of calcination temperature, while, the selectivity for arene decreased with the calcination temperature.The HZSM-5 zeolite calcined at 700 ℃ produced light olefins with high yield, at the reaction temperature of 650 ℃ the yields of total olefins and ethylene were 52.8% and 29.4%, respectively. Besides, the more important role is that high calcination temperature treatment improved the duration stability of HZSM-5zeolites. The effect of calcination temperature on the physico-chemical properties and catalytic performance of HZSM-5 for cracking of n-butane was explored. It was found that the calcination temperature had large effects on the surface area, crystallinity and acid properties of HZSM-5 catalyst, which further affected the catalytic performance for n-butane cracking.     

Sunlight-activated AlFeO3/TiO2 photocatalyst

A nanocomposite photocatalyst composed of AlFeO₃ and TiO₂ is prepared, and characterized through X-ray diffraction. Application of the nanocomposite for the photodegradations of eosin dye and methyl orange gives an improved photoactivity compared with TiO₂-only nanomaterials. The optimal concentration of AlFeO₃ in the composite is about 1.0 wt% under UV excitation, and 9.0 wt% under sunlight excitation for the improved photoactivity. Furthermore, this nanocomposite is more active for eosin photodegradation if natural sunlight rather than UV is used. This may be due to the reason that adding AlFeO₃ nanoparticles into TiO₂ matrix can promote the separation of photogener-ated charge carriers, and extend the photoresponse of TiO₂ toward visible region, which results in an increase in the solar energy utilization efficiency.     

Synthesis,structure and the e.s.r. spectrum of the mixed-valence molybdovandate Na2(NH4)4[(VIVVV8Mo)O28] · 10H2O

The mixed-valence molybdovanadate compound Na₂(NH₄)₄[V^IVV^V ₈Mo)O₂₈] · 10H₂O [Vanadata(6-)tetradeca--oxotetra-₃-oxodi-₆-oxoheptaoxo(oxomolybdate) nonatetrammonium disodium, decahydrate] has been synthesized from sodium molybdate(VI) dihydrate and sodium metavanadate dihydrate in aqueous solution by adding NH₂OH · HCl. The molecular structure has been determined by X-ray diffraction and is based on the isopolydecavanadate structure. The molybdate atom is crystallographically disordered over 6MO₆ octahedral sites. The e.s.r. spectrum clearly indicates that one vanadium atom has the oxidation number +4.     

High resolution spectral analysis of 13CH3OH in the excited torsional states

In this work, we have extended our previous analysis of the Hamiltonian of 13C substituted methanol to include a large number of spectral lines involving the second excited torsional state using an improved model. The data set consisted of 2529 Fourier transform and microwave transitions with the rotational angular momentum J < or = 10, K < or = 6 and n < or = 2 (with 336 MW lines). The data set was fitted with the new Hamiltonian model to derive the molecular parameters. The results indicate that the model developed for the other methanol species (CH3OH, CH3(18)OH and CH3OD) is also valid for the C-13 substituted species. The results will allow the energy levels of the molecule to be calculated for higher torsional levels above the internal rotational barrier with improved precision and allow the analysis to be carried out for more excited torsional states.     

Intercalating lithium into the lattice of silver nanoparticles boosts catalytic hydrogenation of carbon–oxygen bonds

Coinage metal nanoparticles with high dispersion can serve as highly efficient heterogeneous catalysts. However, owing to their low melting point, poor thermal stability remains a major obstacle towards their application under reaction conditions. It is a common practice to use porous inorganic templates such as mesoporous silica SBA-15 to disperse Ag nanoparticles (NPs) against aggregation but their stability is far from satisfactory. Here, we show that the catalytic activity for hydrogenation of dimethyl oxalate (DMO) to methyl glycolate (MG) over Ag NPs dispersed on SBA-15 silica can be further promoted by incorporation of alkali metal ions at small loading, which follows the inverse order of their cationic size: Li⁺ > Na⁺ > K⁺ > Rb⁺. Among these, 5Ag₁–Li_0.05/SBA-15 can double the MG yield compared to pristine 5Ag/SBA-15 under identical conditions with superior thermal stability. Akin to the effect of an ionic surfactant on stabilization of a micro-emulsion, the cationic charge of an alkali metal ion can maintain dispersion and modulate the surface valence of Ag NPs. Interstitial Li in the octahedral holes of the face center packed Ag lattice is for the first time confirmed by X-ray pair distribution function and electron ptychography. It is believed that this interstitial-stabilization of coinage metal nanoparticles could be broadly applicable to multi-metallic nanomaterials for a broad range of C–O bond activating catalytic reactions of esters.

Coinage metal nanoparticles with high dispersion can serve as highly efficient heterogeneous catalysts.     

Cr/MCM-41催化剂上的乙烯聚合行为

以纯硅ＭＣＭ４１为载体，负载Ｐｈｉｌｉｐｓ烯烃聚合催化剂活性组分Ｃｒ．ＸＲＤ及ＴＥＭ表征结果表明，所得到的Ｃｒ／ＭＣＭ４１催化剂具有良好的晶体结构和较理想的长程有序一维孔道．ＦＴＩＲ和Ｒａｍａｎ光谱表征结果表明，Ｃｒ／ＭＣＭ４１上不仅可发生乙烯聚合过程，而且形成的聚乙烯以结晶和无定形两种形态存在．乙烯聚合活性不仅与反应参数有关，而且与Ｃｒ的负载量密切相关．用于乙烯聚合后，Ｃｒ／ＭＣＭ４１催化剂仍保持其特征的晶体结构和一维孔道结构．     

连续一级反应的热动力学研究

本文把时间比法引入热动力学研究,建立了连续一级反应的热动力学研究法,并用来研究了一个连续反应体系的热动力学,验证了该方法的正确性.     

单柱离子色谱法测定茶叶中草酸根和硫酸根的研究

本文研究单柱离子色谱分离测定茶叶中微量草酸根和硫酸根的方法。样品水浸泡，酸化液。上ＳｈｉｍＰａｒｓｋＩＣ－Ａ＿２柱分离，用２．０ｍｍｏｌ·Ｌ￣（－１）Ｈ－２Ｃ＿８Ｏ＿４／１．９ｍｍｏｌ·Ｌ￣（－１）Ｔｒｉ淋洗液洗脱，电导检测器检测，检测灵敏度为１．６Ｓ／ｃｍ，最低检出限０．０５μｇ／ｍＬ；线性范围Ｌ；相对标准偏差１．０６％；平均回收车９８．７２％９７．８８／。该法简便、快速、准确、灵敏、选择性好。     

catena‐Poly­[[tetra­aqua­iron(II)]‐μ‐succinato‐κ2O:O′]

The title complex, {[Fe(C₄H₄O₄)(H₂O)₄]}_n, is an infinite poly­meric compound bridged by the succinate dianion. Two carboxyl­ate groups coordinate in a monodentate manner to the Fe^II atom, in a trans fashion, with an O—Fe—O bond angle of 175.72 (6)° and Fe—O distances of 2.0886 (14) and 2.1008 (15) Å. One of the uncoordinated carboxyl­ate O atom forms an intramolecular hydrogen bond with a coordinated water mol­ecule. Extensive hydrogen bonding between parallel poly­meric complex chains results in a three‐dimensional supramolecular structure.     

Single electron emission from the closed-tips of single-walled carbon nanotubes

The single electron emission behaviors and characteristics from the well-defined quantized energy levels, corresponding to localized electronic states at the dome-structure tips, in single-walled carbon nanotubes (SWNTs) are investigated and illuminated by use of the energy level emission model in combination with the first-principles calculations on the electronic structures. Under the external electric field, the confined electrons are emitted simultaneously from each quantized energy level by virtue of the resonant tunneling effects. With increasing applied voltage, the emission current increases monotonically and exponentially up to the first peak value, and then steps into the increasing and decreasing "sawtoothlike" variations in sequence. The negative differential resistance or conductivity and the maximum current for SWNTs are simulated. The influences of localized electronic states and curvatures of the different closed tips on the single electron emission behaviors of SWNTs are evaluated and discussed. Also a few issues and applications relevant to electron emission of carbon nanotubes are addressed.