负载型贵金属催化剂的制备化学－载体等电点对Pd／A1_2O_3催化剂结构与催化性能的影响

本文通过化学修饰的方法改变了γ－Ａｌ_２Ｏ_３载体等电点（ＩＥＰＳ），并用具有不同等电点的Ａｌ_２Ｏ_３作载体，以（ＮＨ_４）_２ＰｄＣｌ４为活性组分前身制备了一系列Ｐｄ／Ａｌ_２Ｏ_３催化剂，在固定床微反色谱装置上考察了其对ＣＯ氧化的催化活性，用Ｈｉ—Ｏ_２滴定、紫外漫反射光谱（ＤＲＳ）、透射电子显微镜（ＴＥＭ）中的能量色散谱（ＥＤＸＳ）等方法对上述催化剂进行了表征，结果表明：Ａｌ_２Ｏ_３的等电点（ＩＥＰＳ）对所得催化剂中金属分散度和浓度分布都有明显影响，ＩＥＰＳ越高。活性组分越靠近外表面，在相同担载量下，其分散度也越高。这主要是由于载体ＩＥＰＳ的改变，导致了（ＮＨ_４）_２ＰｄＣｌ_４在γ－Ａｌ_２Ｏ_３上吸附机理的变化，并使所得催化剂对ＣＯ氧化的催化活性发生了规律性的变化。     

Mn－Ag／γ－Al_2O_3催化剂中氧的性能

本文运用ＴＰＲ、ＴＰＤ－ＭＳ、ＸＲＤ等技术研究了Ｍｎ－Ａｇ／γ－Ａｌ_２Ｏ_３催化剂的还原性能和再氧化能力．结果表明，Ｍｎ－Ａｇ／γ－Ａｌ_２Ｏ_３中银物相由Ａｇ￣０和Ａｇ_２Ｏ组成，锰物相由β－ＭｎＯ_２和Ｍｎ２Ｏ_３组成．Ｍｎ／γ－Ａｌ_２Ｏ_３催化剂的ＴＰＲ有二个还原峰，分别是ＭｎＯ_２和Ｍｎ_２Ｏ_３的还原．Ａｇ促使ＭｎＯ_２和Ｍｎ_２Ｏ_３的还原明显向低温方向移动，而且ＭｎＯ_２和Ｍｎ_２Ｏ_３的还原峰融合成一个还原峰．Ｍｎ－Ａｇ／γ－Ａｌ_２Ｏ_３的ＴＰＤ有三个脱氧峰，随着Ａｇ含量增加，峰Ⅰ向高温方向移动，Ｍｎ￣（４＋）２ｐ３／２的电子结合能增加，并且催化剂的再氧化能力增强．催化剂ＣＯ的氧化活性与催化剂的再氧化能力有很好的对应关系．     

负载型La0.8Sr0.2CoO3燃烧催化剂的载体效应

负载型Ｌａ０．８Ｓｒ０．２ＣｏＯ３／β－Ａ）催化剂,由于钴离子在不太高的温度下易和载体γ－ＡＩ２Ｏ３作用形成ＣｏＡｌ２Ｏ４尖晶石或在尖晶石,因而不能有效地成为ＣＯ、ＨＣ化合物完全氧化的催化剂,采用ＸＲＤ、ＢＥＴ、ＤＴＡ、ＴＧ和二甲苯完全氧化催化活性测试等手段,研究了ＣｏＡｌ２Ｏ４的形成过程,可以认为这是一个放热、释氧而失重的过程,并伴有晶胞的稍微增大,若在γ－ＡＩ２Ｏ３表面涂数一层以ＭｇＡｌ２Ｏ４     

硫化态K－MoO_3／γ－Al_2O_3催化剂表面物种的XPS研究

采用Ｘ光光电子能谱（ＸＰＳ）及曲线拟合手段对硫化态Ｋ－ＭｏＯ_３／Ａｌ_２Ｏ_３合成醇催化剂进行了研究，分别考察负载量及硫化前不同条件预处理对催化剂表面的Ｓ、Ｍｏ组分的物种形式及各物种相对含量的影响，以及表面不同组分的相对组成。结果表明，根据其电子结合能变化，Ｓ组分可区分为ＳＯ_４￣（２－）、ＳＯ_３、Ｓ￣０、Ｓ_２￣（２－）、ＭｏＳ_２、ＭｏＳ_（２－ｘ）等六种存在形式不同的物种；Ｍｏ组分可区分为Ｍｏ￣（６＋）、Ｍｏ￣（５＋）、ＭｏＳ_（２＋ｘ）、ＭＯＳ_２、ＭＯＳ_（２－ｘ）等五种存在形式不同的物种。ＭｏＯ_３／Ａｌ_２Ｏ_３．重量比为０．０３的样品，Ｍｏ组分硫化还原不完全，表面Ｓ、Ｍｏ组分均以多种物种形式并存，ＭｏＯ_３／Ａｌ_２Ｏ_３比增加至０．０８和０．２４后，表面Ｓ、Ｍｏ组分中ＭＯＳ_２物种形式所占比例有所增加，样品的硫化还原也较彻底，但负载量增加至ＭｏＯ_３／Ａｌ_２Ｏ_３比为０．３５后，表面存在较多的Ｓ￣（６＋）物种和Ｍｏ￣（６＋）、Ｍｏ（５＋）物种，同时Ｋ组分在表面富集。对ＭｏＯ_３／Ａｌ_２Ｏ_３比为０．２４，样品硫化前不同条件预处理的研究表明，该样品与水蒸汽接触对其表面结构影响很大，与水蒸汽接触后再硫化，其表     

Ag／γ－Al_2O_3催化剂的TPR和TPD研究

本文运用ＴＰＤ－ＭＳ、ＴＰＲ等方法研究了Ａｇ／γ－Ａｌ_２Ｏ_３催化剂的氧脱附和还原性能。结果表明，Ａｇ／γ－Ａｌ_２Ｏ_３催化剂表面银物相由Ａｇ０和Ａｇ＋（Ａｇ２Ｏ）组成，其中Ａｇ＋所占比例随负载量增加而减少。Ａｇ／γ－Ａｌ_２Ｏ_３催化剂有三个脱氧峰，并且随着Ａｇ负载量的增加，脱氧峰从高温向低温依次出现。低温脱氧峰（３７０℃）归属为结晶态Ａｇ２Ｏ的分解，高温脱氧峰（６５０和８００℃）为分散在γ－Ａｌ_２Ｏ_３表面并且与Ａｌ_２Ｏ_３发生相互作用的Ａｇ_２Ｏ的分解。ＴＰＲ有三个还原峰；高温峰（２３０℃）为结晶态Ａｇ_２Ｏ的还原，低温峰（１００和１２０℃）为分散在γ－Ａｌ_２Ｏ_３表面的Ａｇ_２Ｏ的还原。     

CuO／γ－Al_2O_3中热稳定助剂作用的探讨

用等量共浸法和分浸法制备了含Ｃａ、Ｓｒ、Ｂａ、Ｍｇ、Ｚｒ和Ｌａ助剂的ＣｕＯ／γ－Ａｌ_２Ｏ_３催化剂（ＣｕＯ／Ａｌ_２Ｏ_３＝８ｗｔ％，Ｍ／Ｃｕ（原子比）＝０．１５，Ｌａ／Ｃｕ＝０．３５）．用ＸＲＤ和ＸＰＳ等考察了在高温７５０℃、９５０℃和１０５０℃老化后的相结构和ＣＯ氧化活性，实验表明所有助剂均有不同程度的抗烧结和抗相变作用。其中Ｌａ、Ｃａ和Ｚｒ的效果最好。分浸法比共浸法好。在９５０℃老化后，ＣｕＡｌ_２Ｏ_４和α－Ａｌ_２Ｏ_３同步产生；随老化温度增高，ＣＯ氧化活性有所下降。分浸法制备的含Ｚｒ样品在９５０℃老化后活性最高。从γ－Ａｌ_２Ｏ_３缺陷尖晶石特征及高温脱结构水过程，探讨了助剂抑制α－Ａｌ_２Ｏ_３生成的原因。     

NiMoNx/γ-Al2O3催化剂的制备及加氢脱氮性能

采用程度升温氮化（ＴＰＮ）的方法制备了ＮｉＭｏＮｘ／γ－Ａｌ２Ｏ３催化剂，考察了它对吡啶加氢脱氮（ＨＤＮ）反应的催化活性。结果表明，ＮｉＭｏＮｘ／γ－Ａｌ２Ｏ３催化剂的活性远远高于ＮｉＭｏＳｘ／γ－Ａｌ２Ｏ３催化剂和工业硫化态催化剂。对于ＮｉＭｏＺｘ／γ－Ａｌ２Ｏ３催化剂，助剂Ｎｉ的作用与硫化物体系中的Ｎｉ不同，它不仅是活化氢中心，同时也是脱氮中之心一，ＮｉＭｏＮｘ／γ－Ａｌ２Ｏ３催化剂的ＨＤＮ活     

（四甲基二硅撑）双（3－三甲硅基环戊二烯基）－四羰基二铁的反应性

标题化合物（Ｍｅ_２ＳｉＳｉＭｅ_２）［η￣５－（３－Ｍｅ_３ＳｉＣ_５Ｈ_３）Ｆｅ（ＣＯ）_２］_２／（μ－ＣＯ）_２（Ａ）分子中的Ｆｅ－Ｆｅ键被钠汞齐还原断裂，生成相应的双铁负离子，分别与ＭｅＣＯＣｌ、ＰｈＣＯＣｌ、ＰｈＣＨ_２Ｃｌ、ＣｌＣＨ_２ＣＯＯＣ_２Ｈ_５和Ｐｈ_３ＳｎＣｌ进行亲核取代反应，生成在铁原子上引入相应取代基的产物（Ｍｅ_２ＳｉＳｉＭｅ_２）［η￣５－（３－Ｍｅ_３ＳｉＣ_５Ｈ_３）Ｆｅ（ＣＯ）_２Ｒ］_２（Ｒ：ＭｅＣＯ（１），ＰｈＣＯ（２），ＰｈＣＨ_２（３），ＣＨ_２ＣＯＯＣ_２Ｈ_５（４），Ｐｈ_３Ｓｎ（５），Ｉ（６））。Ａ在氯仿中与碘反应，得到Ｆｅ－Ｆｅ断裂的双铁碘化物，但在苯中与过量碘反应，则得到Ｆｅ－Ｉ－Ｆｅ桥联的离子型化合物（Ｍｅ_２ＳｉＳｉＭｅ_２）［η￣５－（３－Ｍｅ_３ＳｉＣ_５Ｈ_３）Ｆｅ（ＣＯ）_２］_２Ｉ·Ｉ（７）。化合物６的晶体和分子结构经Ｘ射线衍射测定，６属单斜晶系，Ｐ２１／ｃ空间群，ａ＝１．７２１７（４）ｎｍ，ｂ＝０．７７５３（２）ｎｍ，Ｃ＝１．３６２９（７）ｎｍ，β＝１０３．８０（３）°，Ｖ＝１．７６７（２）ｎｍ３，Ｚ＝４，Ｄｃ＝１．６２９９·ｃｍ－１，最终偏差因子Ｒ＝０．０５４。     

天然气和二氧化碳转化制合成气的研究Ⅵ Ni／Al_2O_3催化剂再生的疏活机理

采用γ－Ａｌ_２Ｏ_３为载体，以硝酸镍、硝酸镁和稀土硝酸盐为原料，按常规浸渍法制备镍负载型催化剂，其中Ｎｉ含量为９．１７％，助剂ＲＥ_２Ｏ_３和Ｍｇ含量分别为５．１８％和１．８０％，该催化剂简称为Ｎ－５－ＲＭ。催化反应评价采用双套管石英反应器，在多功能固定床流动反应装置上进行，以天然气和二氧化碳转化为探针反应，采用连续反应法评价催化剂性能。以反应尾气中合成气摩尔百分数表征催化剂活性。采用理光Ｄ／ｍａｘ－ｒ－Ｂ型Ｘ射线衍射仪测定催化剂晶相。实验发现，催化剂长期使用失活的主要原因是由于活性中心Ｎｉ￣０与载体Ａｌ_２Ｏ_３间形成难还原的ＮｉＡｌ_２Ｏ_４物种，以及活性中心Ｎｉ￣０聚集形成晶相，从而降低了催化剂表面活性中心数。ＴＰＲ结果指出，ＮｉＡｌ_２Ｏ_４物种在高温下通氢气可以得到充分还原。然而，此时催化剂活性仍明显低于新鲜催化剂活性。ＸＲＤ结果表明，此时催化剂存在很强的Ｎｉ￣０衍射峰，说明尽管高温还原已使形成ＮｉＡｌ_２Ｏ_４的Ｎｉ￣（２＋）还原为Ｎｉ￣０，但高温还原又进一步使活性Ｎｉ￣０聚集成晶相，因而降低了催化剂表面活性中心数。这说明，对ＮｉＡｌ_２Ｏ_４的活化仅通过常规高温还原是不够的。２０％过氧化氢水溶液（以下简称     

Al_2（SO_4）_3／γ－Al_2O_3单层分散状态及其对丁烯齐聚反应活性的

用ＸＲＤ、ＴＧ、热重氨吸附法等手段，测定了Ａｌ_２（ＳＯ_４）_３／γ－Ａｌ_２Ｏ_３中单层分散相与Ａｌ_２（ＳＯ_４）_３担载量之间的关系，测定了表面单层最大分散量一阈值。其与用密置单层模型计算所得值接近，这为Ａｌ_２（ＳＯ_４）_３在γ－Ａｌ_２Ｏ_３上单层分散行为提供了证据，且将该催化剂的表面行为与其对丁烯齐聚反应活性进行了关联。     

Organotransition-Metal Complexes of Multidentate Ligands 3. The Unexpected Derivatives of Bis(3,5-Dimethylpyrazol-1-YL)Methanetetracarbonylmolybdenlim(0) and-Tungsten(0) Complexes

Thermolysis of (H₂CPz′₂)M(CO)₄ (H₂CPz′₂ = bis(3,5-dimethylpyrazol-1-yl)methane; M=Mo, W) in 1,2-dimethoxyethane did not give the expected 16-electron complexes, (H₂CPz′₂)M(CO)₃, but gave dinuclear compounds, [(H₂CPz′₂)M(CO)₃]₂, probably containing two linear carbonyl bridges and no metal-metal interactions. The dimers reacted with CH₃CN to give mononuclear compounds, (H₂CPz′₂)M(CO)₃(NCCH₃), identical to the substitution products between (H₂CPz′₂)M(CO)₄ and CH₃CN.     

Synthesis of Derivatives of (4-Methyl-2-Quinolylthio)acetic and (4-Methyl-2-Quinolylthio)propionic Acids

An efficient synthesis has been developed for derivatives of (4-methyl-2-quinolylthio)acetic and (4-methyl-2-quinolylthio)propionic acids by the reaction of 4-methyl-2-thioxoquinoline with methyl methacrylate, the amide of methacrylic acid, acrylonitrile, ethyl bromoacetate, and ethyl acrylate. The hydrolysis of the resultant intermediates by (quinolylthio)acetic and (quinolylthio)propionic acids gave the corresponding acid products, which are also formed in the reaction of 4-methyl-2-thioxoquinoline with chloroacetic and acrylic acids. The reaction of 4-methyl-2-thioxoquinoline with allyl bromide was studied. The potassium permanganate oxidation of the resultant 2-allylthio-4-methylquinoline led to (4-methyl-2-quinolylthio)acetic acid.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 403–406, April, 2005.     

手性二噁唑啉吡啶铁和镍配合物的制备与表征

Tridentate bis(oxazolinylpyridine)(1) reacted with nickel chloride or ferrous chloride in anhydrous ethanol to form bis(oxazolinylpyridine) Nickel(Ⅱ) and Iron(Ⅱ) complexes. The stable solid complexes were characterized with IR， UV， MS， XPS and elemental analysis. No stable complexes were formed with bidentate bis(oxazoline)(2) ins- tead of bis(oxazolinylpyridine).     

Asymmetric Synthesis of (R)-and (S)-Moprolol

A simple and effective procedure for the enantioselective synthesis of (R)-and (S)-moprolol was described.The key step was the asymmetric synthesis of enantiopure (R)-and (S)-guaifenesin,which were synthesized from enantioenriched (R)-3-chloro-1,2-propanediol and (S)-epichlorohydrin via kinetics of hydrolysis resolution of racemic epichlorohydrin by chiral Salen-CoIIII complex.The e.e.values of both the optical compounds were above 98%,and the chemical structures of the target compounds were confirmed by 1H NMR,13C NMR,IR,and MS.     

Preparation of Palladium(II) and Platinum(II) Phosphine Complexes Promoted by Phase-Transfer Catalysts

The synthesis of M(PR₃)₂Cl₂ (M = Pd and Pt, R = alkyl or aryl) front K₂MCl₄ (in H₂O) and PR₃ (in CH₂Cl₂) was promoted by the addition of phase-transfer catalysts (PTC). The greater the amount of PTC used, the more quickly the reaction completed. ³¹P NMR spectra of some M(PR₃)₂Cl₂ in the presence of free PR₃ were measured; these NMR resulls were used to explain problems encountered during the preparations.     

Separation of Ga(III) from Cu(II), Ni(II) and Zn(II) in aqueous solution using synthetic polymeric resins

Poly (acrylamide-acrylic acid-dimethylaminoethylmethacrylate), p(AM-AA-DMAEM) and Poly(acrylamide-acrylic acid)-ethylenediaminetetracetic acid disodium, p(AM-AA)-EDTANa₂ were prepared by gamma radiation-induced template polymerization technique and used for the separation of Ga (III) from Cu (II), Ni (II), and Zn (II) in aqueous media. The effect of pH and contact time on the separation process was studied. The optimum pH value for the separation process is 3–3.5. The result shows that Ga (III) is first extracted while Cu (II), Ni (II) and Zn(II) are slightly extracted at this pH value. The recovery of metals using HCl, HNO₃ and H₂SO₄ has been studied. The resins may be regenerated using 2M HCl solutions.      

(Phosphine)gold(I) Complexes of Benzenedithioles. Crystal structures of 1,2-benzenedithiolato-bis[triphenyl-phosphinegold(I)] and bis(triethylphosphine)gold(I) bis(1,2-benzenedithiolato)gold(III)

The reaction of 1,2- and 1,3-benzenedithiol C₆H₄(SH)₂ with chloro(phosphine)gold(I) complexes R₃PAuCl (R = Et, Ph) in the presence of triethylamine in tetrahydrofuran gives stable gold(I) complexes 1,2-C₆H₄(SAuPR₃)₂ [R = Et ( 1 ) and Ph ( 2 )] or 1,3-C₆H₄(SAuPPh₃)₂ ( 3 ), respectively, in high yield. The compounds have been characterized by analytical and NMR spectroscopic data. From the reaction of 1,2-C₆H(SH)₂ with Et₃P? AuCl a by-product [(Et₃P)₂Au]⁺ [Au(1,2? C₆H₄S₂)₂]^? ( 4 ) has also been isolated in low yield. The crystal structures of compounds 2 and 4 have been determined by single crystal X-ray diffraction. The gold(I) atoms in complex 2 are two-coordinate with bond angles S? Au? P of 175.2(1) and 159.5(1)°, Au? S bond distances of 2.304(1) and 2.321(1) å, and a short Au…?Au contact of 3.145(1) Å. The gold(I) atom in the cation of complex 4 is also linearly two-coordinate with a P? Au? P angle of 170.1(1) Å and Au? P distances of 2.296(3) and 2.298(3) Å. The geometry of the anion in 4 shows a square-planar coordination of gold(III) by two chelating 1,2-benzenedithiolate ligands with Au? S distances between 2.299(3) and 2.312(3) Å (for two crystallographically independent, centrosymmetrical anions in the unit cell).     

Crystal structure of bis(l-arginine)copper(II) hexachlorodimercurate, [Cu(l-Arg)2]Hg2Cl6

By means of X-ray diffraction the chain structure of [Cu(l-Arg)₂]Hg₂Cl₆ (monoclinic, a = 10.2348(9) Å, b = 9.1386(7) Å, c = 14.8521(14) Å, β = 97.455(11)°, space group P2₁) is established. The chains are formed by square-planar [Cu(l-Arg)₂]²⁺ cations of the type trans-[Cu(N)₂(O)₂] (l-Arg is the zwitter-ion of arginine; Cu-N 1.992 Å and 1.938(6) Å, Cu-O 1.953 Å and 1.967(4) Å) that are bonded to two adjacent binuclear [Cl₂Hg(μ-Cl)₂HgCl₂]^2? ions through its clorine atoms Cl (Hg-Cl bonds are within 2.34–2.78 Å). With these two additional Cu…Cl contacts Cu adopts the geometry of an elongated octahedron with two apical Cl (Cu-Cl 2.961 Å and 3.064(3) Å).     

Rhodium(III), palladium(II) and platinum(II) complexes of Bis(o-aminobenzenesulfonyl)ethylenediamine

New complexes of the formulae K₃[RhL ₃]·2 H₂O, [PdL]·H₂O and [M(LH₂)Cl₂] [whereM = Pd, Pt andLH₂ = bis(o-aminobenzenesulfonyl)ethylenediamine] have been prepared and characterized by conductivity measurements, thermogravimetric analysis, X-ray powder patterns and IR, Ligand Field and¹H-NMR spectroscopy.

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Rhodium(III), Palladium(II)- und Platin(II)-Komplexe mit Bis(o-aminobenzolosulfonyl)ethylendiamin (Kurze Mitteilung)

Zusammenfassung Neue Komplexe der allgemeinen Formeln K₃[RhL ₃]·2H₂O, [PdL]·H₂O und [M(LH₂)Cl₂] mitM = Pd, Pt undLH₂ = Bis(o-aminobenzolosulfonyl)ethylendiamin wurden dargestellt und mit Konduktionsmessungen, thermogravimetrischen Analysen, Röntgenstrukturanalysen, IR, Ligandfeld- und¹H-NMR-Spektroskopie charakterisiert.

     

Mechanism and kinetics of thermal decomposition of nickel(II) sulfate(VI) hexahydrate

This work presents results of research on thermal decomposition of nickel(II) sulfate(VI) hexahydrate in air and in helium atmosphere. On the base of TG and XRD results a mechanism of thermal decomposition of NiSO₄ hydrate was established. For calculations of kinetic parameters of the Arrhenius equation, the Coats-Redfern approximation was applied. Choice of g(a) function and thus of a mechanism best describing given stage of decomposition was performed by testing 12 kinetic models. This revised version was published online in July 2006 with corrections to the Cover Date.