Photodissociation Spectra of OCS+ via B2∑+←X2∏ Transitions

In the wavelength range of 231-275 nm, we have studied the mass-resolved dissociation spectra of OCS⁺ via B²∑⁺←X²∏_3/2(000) and B²∑⁺←X²∏_1/2(000, 001) transitions by preparing OCS⁺ ions in the well-defined spin-orbit states. The spectroscopic constants ofυ1(CS stretch)=828.9 (810.4) cm^-1, υ2(bend)=491.3 cm^-1 and υ3(CO stretch)=1887.2 cm^-1 for OCS⁺(B²∑⁺) are deduced. The observed dependence of the υ2(bend) mode excitation of B²∑⁺ on the spin-orbit splitting of X²∏(Ω=1/2, 3/2) in the B²∑⁺←X²∏ transition can be attributed to the K coupling between the (000)²∏_1/2 and (010)²∑⁺_1/2 vibronic levels of X²∏ state, which makes the B²∑⁺(010)←X²∏_1/2(000) transition possible.     

Fe3+/Ba2+/Co2+/Zn2+/Cu2+在NH4HCO3-NH3·H2O和NaOH-Na2CO3体系中的热力学分析

通过对Fe3+/Ba2+/Co2+/Zn2+/Cu2+在NH4HCO3-NH3·H2O和NaOH-Na2CO3体系中的热力学分析,得到各金属离子总浓度(cMe)与pH值的关系,确定了2种体系中5种离子完全共沉淀的pH值范围.结果表明:在NH4HCO3-NH3·H2O体系中,Co2+、Zn2+、Cu2+3种离子和氨的配位能力很强,其中Cu2+与氨的配位能力最强,在相同的pH值条件下,Cu2+沉淀困难,5种金属离子的完全共沉淀区域由Cu2+决定.在NaOH-Na2CO3体系中,随总碳浓度(cc)的增加,Ba、Co、Zn、Cu的溶解度都随之减小,当cc=1.0 mol·L-1时,各金属离子完全共沉淀的pH值范围为7.5～11.在两种体系中,Fe的溶解度都是随pH值的增大而减小,最终达到平衡.以NaOH-Na2CO3 为沉淀剂.在pH=10.0的条件下,采用化学共沉淀法合成出了晶粒细小、粒度均匀的Y型纯相结构的平面六角铁氧体微粉.     

Crystal structure of [MnII (1,10-C12H8N2)3]2+[(B9C2H11)CoIII(B8C2H10)CoIII(B9C2H11)]2?·CH3CN

A novel compound, [MnPhen₃][(B₉C₂H₁₁)Co(B₈C₂H₁₀)Co(B₉C₂H₁₁)]· CH₃CN (Phen = 1,10-phenantroline), comprising a Co(III) dicobaltacarborane cluster anion has been prepared and characterized by single crystal X-ray diffraction. Crystal data are the following: C₄₄H₅₉B₂₆N₇Co₂Mn, M = 1139.84, triclinic, space group , unit cell parameters: a = 13.2465(11) Å, b = 14.521(2) Å, c = 15.2536(15) Å; α = 77.027(9)°, β = 88.500(8)°, γ = 77.274(9)°; V = 2788.5(5) ų, Z = 2, d _calc = 1.358 g/cm³, T = 295 K, F(000) = 1162, μ = 0.853 mm⁻¹. The structure was solved by the direct and Fourier methods and refined anisotropically (isotropically for hydrogen atoms) using the full-matrix technique to final factors R ₁ = 0.0374, wR ₂ = 0.0915 for 7397 I _hkl ≥2σ_I of 9779 I _hkl measured (diffractometer Enraf-Nonius CAD-4, λMoK _α , graphite monochromator, θ/2θ-scanning). The structure is formed from [MnPhen₃]²⁺ cations, [(B₉C₂H₁₁)×Co(B₈C₂H₁₀)Co(B₉C₂H₁₁)]₂₋ anions, and acetonitrile molecules CH₃CN. Central Mn atom in the cation has a distorted octahedral coordination environment formed by six nitrogen atoms of three bi-dentate Phen ligands, average Mn-N bond length being 2.263(2) Å. The anion has a chain-like structure built from three icosahedra sharing common vertices occupied by the cobalt atoms. The central icosahedron including ten light atoms (8B, 2C) provides two vertices for the cobalt atoms shared with the other icosahedra having 11 light atoms (9B, 2C). The arrangement of-C₂-groups in the anion corresponds to a quasi-gauche-configuration of asymmetric sandwich complexes of both cobalt atoms. Original Russian Text Copyright ? 2005 by T. M. Polyanskaya, V. V. Volkov, and M. K. Drozdova __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 46, No. 4, pp.730–740, July–August, 2005.     

Die Reaktion zwischen Thioglykols?ure (TGA) und Zn2+, Hg2+, Cd2+, Pb2+ und Ag+

Ohne Zusammenfassung     

N2O+经由B2Пi←X2П跃迁的光解离机理研究

在超声分子束条件下,利用360.50 nm的电离激光使N₂O分子经由[3+1]共振增强多光子电离（REMPI）产生纯净的N₂O⁺（X²Π（000））分子离子,用另一束解离激光在230-275 nm范围扫描获得N₂O⁺经由B²П_i←X²Π跃迁产生的光解碎片（NO⁺和N₂⁺）激发（PHOFEX）谱. 获得的光解碎片激发谱可以归属为B²П_i（00n）←X²Π（000）序列跃迁. 我们分别将线性三原子分子离子N₂O⁺中N―N伸缩振动简化成NO和N之间的简谐振动,N―O伸缩振动简化成N₂和O之间的简谐振动,用谐振子的简谐势能曲线和波函数对N₂O⁺分子离子X²Π和B²П_i电子态振动能级间跃迁的Franck-Condon因子进行计算,和实验得到的碎片离子增强谱实验强度进行比较,对前人给出的分子数据（分子平衡核间距）进行验证,讨论了N₂O⁺经由B²П_i（00n）←X²Π（000）电子态跃迁的光解离机理和碎片离子的分支比.     

Ionophoretische Trennung von ReCl62?, ReBr62? und ReO4?

Zusammenfassung Es wurde die ionophoretische Trennung von ReCl₆ ^2–, ReBr₆ ^2– und ReO₄ ^– unter Verwendung verschiedener Papiersorten untersucht. Am geeignetsten erwies sich das Papier 2045 b Gl von Schl. & Sch.

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Summary The ionophoretic separation of ReCl₆ ^2–, ReBr₆ ^2–, and ReO₄ ^– has been examined using different kinds of paper. Best results have been obtained with the paper 2045 b Gl from Schleicher & Schüll.

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Herrn Prof. G. Brauer danke ich für Förderung. Für die Überlassung von Rheniumverbindungen bin ich der Fa. W. C. Heraeus, Hanau, verpflichtet. Die Neutronenaktivierung wurde freundlicherweise von den Herren Dr. Marth und Dr. Köhler von der Reaktorstation in Garching bei München vorgenommen. Das Bundesministerium für Atomkernenergie und Wasserwirtschaft unterstützte die Untersuchung durch eine Sachbeihilfe.     

Rotational Analysis of A2Πu-X2Σ+g System of 14N2+

The absorption spectrum of N₂⁺ has been studied using optical-heterodyne velocity mod-ulation spectroscopy in the near-infrared region. The observed spectral lines were assigned to the (3,1), (4,2), (5,3), (8,5) bands of the A²Π_u-X²Σ⁺_g system and the line lists were provided. The (5,3) band was studied for the first time. Fourteen rotational-resolved bands in literatures were fitted together with our observed bands and the molecular constants were obtained for υ_A=0-9 and υ_X=0-5.     

Zum schnellen Nachweis der Kationen Cu++, Ni++, Co++, Fe++ und Mn++, der AnionenSCN?,OCN?,CN?,S2O82?,J?und Br? sowie tert.aliphatischer Amine und Pyridine

Ohne Zusammenfassung     

Die halbquantitative Bestimmung von Cl?, Br?, J?, SCN?, AsO43?, Cr2O72? und [Fe(CN)6]3?

Ohne Zusammenfassung     

近紫外激发Sm3+与Sr2+,Ba2+,Bi3+共掺杂的La1/3NbO3的发光性质

通过高温固相反应合成了La1/3NbO3∶Sm3+荧光粉.样品的荧光光谱表明,La1/3NbO3∶Sm3+荧光粉最强的激发带在406 nm,对应于Sm3+的6H5/2→4K11/2跃迁,属于近紫外区(365～410 nm).当激发波长为406nm时,样品的最强发射峰位于596 nm,是由Sm3+的4G5/2→6H7/2跃迁而产生的.因此,La1/3NbO3∶Sm3+可以作为基于近紫外激发的白光发光二极管(LED)的红光材料.而且,La位共掺杂Sr2+,Ba2+和Bi3+使样品的荧光强度大大增加,在最佳掺杂浓度时的量子产率分别为5.4%,7.5%和5.3%.     

稀土固体超强酸SO42-/TiO2/La3+催化合成丁酸异戊酯

丁酸异戊酯是无色至淡黄色透明油状液体,有近似生梨和香蕉香甜气。天然品存在于椰子油、可可豆、苹果、香蕉、葡萄、草莓等中,是我国ＧＢ２７６０－８６规定允许使用的食用香料,主要用以配制香蕉、菠萝、杏、樱桃和杂锦水果等型香精;也可用作提取天然香料的溶剂、乙酸纤维素的溶剂及增塑剂。通常它是在硫酸催化下由丁酸和异戊醉酯化反应而得［１,２］,反应时间长,副反应多,对设备腐蚀严重,废水排放量大,后处理工艺复杂。为此,本实验选用稀土固体超强酸ＳＯ４２－／ＴｉＯ２／Ｌａ３＋作为催化剂进行某些酸与异戊醇的酯化反应。 …     

SO42-/SnO2-硅藻土型固体酸的制备及其对正丁酸与异戊醇的催化酯化

采用质量比为1∶3的SnCl₄·5H₂O和硅藻土制备的硅藻土Sn(OH)₄溶胶,70 ℃老化12 h,90 ℃干燥12 h、3.0 mol/L硫酸浸渍3 h、550 ℃焙烧3.5 h,制备了SO₄^2-/SnO₂硅藻土型固体酸催化剂。 利用IR、 XRD、TG测试技术表征了催化剂的理化性质。 用于催化正丁酸与异戊醇的酯化反应,当n（异戊醇）∶n（正丁酸）=1.4∶1、催化剂用量为反应物总质量的2.5%、10 mL苯、反应时间70 min时,酯收率为97.7％。 结果表明,该催化剂兼具多元氧化物型固体酸和硫酸酸化改性天然粘土固体酸催化剂的优点,催化活性高,成本低廉、制备方法简单并可适当回收循环使用。     

Synthesis of butyrate using a heterogeneous catalyst based on polyvinylpolypyrrolidone

A heterogeneous polyvinylpolypyrrolidone supported Brønsted acidic catalyst ([PVPP-BS]HSO₄) was used to synthesize butyrate in this paper. The prepared catalysts were characterized by FT-IR, TG, and FESEM and their catalytic activity in butyric acid esterification with benzyl alcohol was investigated. The influencing factors such as the amount of catalyst, reaction temperature, and reaction time were carefully studied. Under the optimized condition with the butyric acid to benzyl alcohol mole ratio of 1: 1.2 and the reaction temperature of 130°C, the yield of benzyl butyrate reached 96.8 % within 4 h in the presence of 8 mass % of catalyst. Moreover, the catalyst could be reused six times without noticeable drop in activity. This catalyst was also used to synthesize other kinds of butyrates achieving the butyrate yield above 90 %.     

Esterification activity and stability of Candida rugosa lipase immobilized into chitosan

Microbial lipase from Candida rugosa immobilized into porous chitosan beads was tested for esterification selectivity with butanol and different organic acids (C2–C12), and butyric acid and different aliphatic alcohols (C2–C10). After 24 h, the acids tested achieved conversions of about 40–45%. Acetic acid was the only exception, and in this case butanol was not consumed. Different alcohols led to butyric acid conversions >40%, except for ethanol, in which case butyric acid was converted only 26%. The system’s butanol and butyric acid were selected for a detailed study by employing an experimental design. The influence of temperature, initial catalyst concentration, and acid:alcohol molar ratio on the formation of butyl butyrate was simultaneously investigated, employing a 2³ full factorial design. The range studied was 37–50°C for temperature (X₁), 1.25–2.5% (w/v) for the catalyst concentration (X₂), and 1 and 2 for the acid:alcohol molar ratio (X₃). Catalyst concentration (X₂) was found to be the most significant factor and its influence was positive. Maximum ester yield (83%) could be obtained when working at the lowest level for temperature (37°C), highest level for lipase concentration (2.5% [w/v]), and center level of acid:alcohol molar ratio (1.5). The immobilized lipase was also used repeatedly in batch esterification reactions of butanol with butyric acid, revealing a half-life of 86 h.     

Biodiesel Production from Waste Cooking Oil over Mesoporous SO42-/Zr-SBA-15

Biodiesel production from waste cooking oils over SO₄^2-/Zr-SBA-15 catalyst was successfully carried out and investigated. SO₄^2-/Zr-SBA-15 catalyst was prepared by one-step process using anhydrous zirconium nitrate as zirconium resource, and endowed with the strong Lewis acid sites formed by supporting the zirconium species onto the SBA-15 surface. The asprepared SO₄^2-/Zr-SBA-15 showed excellent triglyceride conversion efficiency of 92.3% and fatty acid methyl esters (FAME) yield of 91.7% for the transesteriffication of waste cooking oil with methanol under the optimized reaction conditions: the methanol/oil molar ratio of 30, the reaction temperature of 160 oC, the reaction time of 12 h and 10wt% of catalyst. It was noticed that the as-prepared SO₄^2-/Zr-SBA-15 materials with the higher area surface of mesoporous framework and the surface acidity displayed excellent stability and reusability, maintaining high FAME yield of (74±1)% after seven runs of reaction.     

SO42-/SnO2-Fe2O3固体酸催化下的环酮Baeyer-Villiger氧化反应及缩合反应

采用共沉淀的方法制备了不同Fe 掺杂量的SO₄^2-/SnO₂-Fe₂O₃固体超强酸催化剂. 利用傅里叶变换红外(FTIR)光谱, 粉末X射线衍射(XRD), N₂吸附-脱附实验(BET), 热重(TG)分析和扫描电镜(SEM)等方法对样品进行了表征. 考察了所得催化剂对4-叔丁基环己酮与乙二醇缩合反应的催化性能. 实验结果表明, 与未经过掺杂改性的SO₄^2-/SnO₂固体酸催化剂相比, 改性后催化剂的催化性能得到了改善. 研究了以Fe/Sn 摩尔比为0.5的SO₄^2-/SnO₂-Fe₂O₃固体酸为催化剂, 部分醛酮类化合物与乙二醇及1,2-丙二醇的缩合反应. 考察了反应时间、催化剂用量等因素对反应的影响. 同时, 将所得催化剂应用于环酮Baeyer-Villiger 氧化反应中, 催化剂表现出良好的催化活性, 且催化剂具有一定的循环使用性.     

（TEAH）nH3-nPW12O40催化苯甲醇选择氧化及其反应机理

以Keggin结构的磷钨酸和三乙胺（TEA）为原料,通过简单的酸碱反应合成了磷钨酸的TEA盐.并以它们为催化剂,考察了以H₂O₂为氧化剂、以水为溶剂的体系中苯甲醇选择氧化制备苯甲醛的反应性能.结果表明,（TEAH）_nH_3-nPW₁₂O₄₀（n=1,2,3）系列催化剂对苯甲醇的选择氧化反应有很高的活性和选择性,且可被分离和循环使用.在适宜的反应条件下,最佳催化剂（TEAH）H₂PW₁₂O₄₀上,苯甲醇的转化率可达99.6%,苯甲醛的选择性为100%.还采用IR,³¹PNMR谱和元素分析技术,对催化剂和反应过程中催化剂物种的转化和分布进行了考察,进而导出了反应机理.在这个水--油两相反应中,（PW₁₂O₄₀）^3-首先在H₂O₂的作用下,氧化降解为溶于水的小分子过氧物种（PO₄（WO（O₂）₂）₄）^3-和自由W物种.（PO₄（WO（O₂）₂）₄）^3-是真正的活性物种,可将部份溶于水层的苯甲醇氧化为苯甲醛,自身转变为失去活性氧的反应后物种（SAR）.而SAR又可与自由W物种一起聚合为前驱体状态的（PW₁₂O₄₀）^3-,完成催化循环.     

微波辐射下Zr(SO4)2•4H2O/SiO2催化合成芳香磺酰亚胺

微波辐射无溶剂条件下, 以Zr(SO₄)₂•4H₂O/SiO₂固体酸为催化剂, 芳香醛与芳香磺酰胺反应合成了一系列芳香磺酰亚胺化合物. 此方法具有操作简便, 催化剂价廉易得、活性高、可回收重复使用、对环境友好等优点.     

Al含量对Pt-SO2-4 /ZrO2-Al2O3固体超强酸催化

通过向SO^2-₄ /ZrO₂催化剂中同时引入适量的Pt和Al₂O₃, 制备出了具有较高催化性能和稳定性的Pt-SO^2-₄ /ZrO₂-Al₂O₃型固体超强酸催化剂. 以正戊烷异构化反应为探针, 考察了Al含量对催化剂性能的影响; 并采用X射线衍射(XRD)、比表面积测定(BET)、红外(IR)光谱、程序升温还原(TPR)、热重-差热分析(TG-DTA)和氨-程序升温脱附(NH₃-TPD)手段对催化剂进行了表征. 结果表明, Al能够提高ZrO₂的晶化温度, 抑制硫的分解, 增加催化剂的比表面积, 增强硫氧键的结合, 提高催化剂的还原性能, 增加催化剂的酸强度和酸总量. 当Al₂O₃含量(质量分数, w)为5.0%时, Pt-SO^2-₄ /ZrO₂-Al₂O₃固体超强酸催化剂的催化活性最好, 在100 h内异戊烷收率可稳定在52.0%以上, 选择性在98.2%以上.     

制备方法对Al2O3掺杂Pt/WO3-ZrO2催化剂上正庚烷异构化反应的影响

采用恒pH法和非恒pH法制备了Al₂O₃掺杂的Pt/WO₃/ZrO₂催化剂,并用N₂吸附-脱附、X射线衍射、紫外-可见漫反射、CO化学吸附、X射线光电子能谱、²⁷Al魔角旋转核磁共振和吡啶吸附红外等技术对催化剂进行了表征.结果表明,相比于非恒pH法制备的催化剂,恒pH法制备的催化剂具有较高的比表面积和Pt分散度,在H₂气氛中产生更多的B酸位,从而表现出更高的催化正庚烷临氢异构化反应活性; 在200℃和质量空速0.9h^-1的反应条件下,正庚烷转化率达70.0%,明显高于非恒pH法制备的催化剂(43.5%).