混合金属络合物羟基镍铝交联蒙托土的合成

用取代法和共聚法合成了一系列羟基镍铝交联蒙托土。(27)~Al-NMR,UV谱表明两种合成方法都可以得到具有Kessin结构的羟基镍铝柱。取代法合成的交联蒙托土具有均一的(001)面衍射(d_(001)约1.80nm),而共聚法的样品有两种羟基镍铝柱支撑着层间,分别在1.80nm和1.55nm附近产生复合(001)面衍射。用高温老化处理可改善交联蒙托土的热稳定性。经过处理的样品在700℃焙烧后仍可保持稳定,与不经处理的样品相比,热稳定性提高200℃以上。     

混合金属络合物羟基铬铝交联蒙托土的合成

用取代法和共聚法合成了不向Cr/Al比的混合金属络合物羟基铬铝交联蒙托土,用XRD、DTA考察了其热稳定性,用~(27)Al-NMR、UV、ESR等技术对柱化溶液中铬和铝的状态进行了研究。结果表明,两种方法均合成出结构相近且底面间距d(001)为1.90～2.49nm的羟基铬铝交联蒙托土。发现Cr/Al比对羟基铬铝聚合物的结构、d(001)值、比表面热稳定性均有较大影响;随Cr/Al比的增加,d(001)逐渐增加,热稳定性下降,但在惰性气氛下热稳定性较好(>500℃)。     

部份层无序铝交联蒙脱土结构的研究

应用非完整晶体的XRD衍射及阳离子交换量的测定等实验数据, 得出了铝交联蒙脱土的三维结构模型. 结构中Al(III)多数以十三聚体形式进入层间, 层间距为1.97 nm, 几率为0.65, 少数以六聚体形式进入层间, 层间距为1.5 nm, 几率为0.25, 其余10%的层间仅为水分子. 并给出了交联柱子在层间的分布与层单元之间的连接方式. 目前通用的以Bragg公式计算所得的d_(001)值来表征交联浆脱土的层间距是不确切的.     

高层间距的羟基硅铝交联蒙托土的合成与表征

采用溶胶分散法合成了一系列高层间距(2.6nm)的羟基硅铝交联蒙托土(SiAl-CLM),并用~(27)Al NMR、XRD、DTA、XPS、吡啶吸附-IR、正丁胺吸附-TPD等技术进行了表征,用脉冲反应技术考察了其催化活性。结果表明:SiAl-CLM层间存在氧化硅胶团与羟基铝聚体形成的复合Si-Al柱.SiAl-CLM的热稳定性较好,对异丙苯的裂解活性(76.8％)较高。Si的引入增加了交联蒙托土的表面酸性,尤其增加了Bronsted酸性。     

羟基铝离子柱撑蒙脱石材料的制备与结构表征

采用水洗过滤提纯蒙脱石原矿,以NaCl作为钠化改型剂对提纯后的蒙脱石原矿进行了钠化改型,以NaOH水解AlC13溶液制备了铝柱化剂,并采用离子交换法使铝柱化剂柱撑进入钠基蒙脱石层间得到羟基铝离子柱撑蒙脱石。采用XRF,XRD,SEM等方法对铝柱撑蒙脱石载体的结构进行了表征。柱撑前后样品的测试结果表明,羟基铝离子通过离子交换反应进入蒙脱石层间。     

羟基硅铝交联粘土的合成和热稳定性研究

羟基硅铝交联粘土的合成和热稳定性研究孙来生，李栋藩，陶龙骧（中国科学院大连化学物理研究所，大连１１６０２３）关键词蒙脱土，硅铝柱，热稳定性，~（２７）Ａｌ　ＮＭＲ交联粘土作为一种新型催化材料出现以来，其热稳定性一直是重要研究课题，对影响交联粘土热稳定?..     

介孔铁铝/蒙脱土复合材料：解离柱撑制备、结构及催化羟基化性能

利用极稀悬浮液中蒙脱土的解离作用并结合柱化技术过程，制备了介孔结构的铝铁/蒙脱土复合材料(Fe-Al/mmt)；并采用粉末X射线衍射、氮等温吸脱附、傅立叶红外光谱、紫外可见光漫反射光谱及苯酚催化羟基化反应表征了其结构和性能。结果显示，铁铝聚合前驱液中铁/铝比影响复合材料中蒙脱土的解离程度，且仅当低铁/铝比时(即Fe/(Fe+Al)物质的量的比介于0.05～0.3)，嵌入解离的蒙脱土片层间的混合铁铝物种呈现能耐温350 ℃的热稳定性；氮等温吸脱附分析反映出这种解离的蒙脱土堆积结构呈现介孔特征，孔径分布窄，介于2.0～2.3 nm；红外分析表明材料表面具有L酸和B酸位，并且L酸位量与嵌入解离的蒙脱土结构中的混合铁铝物种相关；由于结构中混合铁铝物种的存在及相应的Si-O → Fe、Al-O → Fe间的电子跃迁，Fe-Al/mmt材料在紫外区呈现宽泛的能量吸收特征。这些结果说明，由于混合铁铝物种嵌入于解离的蒙脱土片层堆积结构中，形成了“卡片屋”式介孔结构。实验条件下，Fe/(Fe+Al)物质的量的比为0.3的Fe-Al/mmt呈现较佳的催化羟基化性能，苯酚转化率为36.7%，二酚产物选择性32.3%；并且初步表明铝掺杂后，通过铁铝比和表面酸性的调整，材料的部分选择氧化性能可以得到改善。     

改性蒙脱土催化剂制备及催化低浓度乙醇脱水制乙烯研究

采用硫酸将蒙脱土层间杂质溶出、板层发生层离后,基于它的"记忆效应",通过离子交换的方式引入聚羟基铝,再在其表面负载磷钨酸,从而得到不同改性的蒙脱土催化剂.运用氮气吸脱附分析、X射线衍射(XRD)、傅里叶红外光谱(FT-IR)、热重分析(TG)和NH_3-程序升温脱附(NH_3-TPD)表征手段对催化剂的结构变化进行了分析,通过微反固定床反应器评价不同催化剂在低浓度乙醇脱水制乙烯反应中的催化性能.结果表明:经改性后,蒙脱土比表面积增加,孔容增大,酸含量和分布优化,在低浓度乙醇脱水反应中表现出优异的催化性能,在使用PW-Al-MMT催化剂质量空速为0.65 h~(-1),乙醇体积分数为20%,反应温度为300℃时,反应时间为12 h,乙醇的转化率为95.7%,乙烯的选择性达98.6%以上.     

含过渡金属离子的交联蒙托土交联柱中Keggin结构的作用

利用Keggin结构可以发生同晶取代的性质,合成了含过渡金属离子铬、镍的羟基铝交联蒙托土,并运用XRD、~(27)Al-NMR、UV-DRS、XPS、TPR等方法研究了Keggin结构的作用。结果表明,铬、镍都可以和铝生成具有Keggin骨架结构的羟基共聚体,并以此作柱子支撑着蒙托土的层间。铬的取代反应比镍容易发生。共聚法合成出的羟基镍铝交联蒙托土中镍存在两种状态;过量的金属离子对Keggin结构有较大地破坏;Keggin结构的存在增加了交联蒙托土的热稳定性。     

铈铝柱撑蒙脱土的制备及其负载钴催化剂的费托反应性能

以钠化改型后的内蒙古兴和县蒙脱土为原料, 按照不同的Ce/Al摩尔比合成柱化液,制备铈铝柱撑蒙脱土. 使用XRD, BET, TGA-DTA, ICP和FTIR等方法对柱撑后的蒙脱土进行了表征, 结果表明, 所制备的铈铝柱撑蒙脱土具有高热稳定性, 较大的层间距和高比表面积. 以铈铝柱撑蒙脱土为载体, 使用浸渍法制备了负载钴的柱撑蒙脱土催化剂, 用于费托反应性能评价. 实验结果表明, 交联柱中Ce的引入改变了柱撑蒙托土负载的钴催化剂的性质, 提高了催化活性, 催化剂具有优良的费托合成性能.     

Homogeneous forced hydrolysis of aluminum through the thermal decomposition of urea

Homogeneous hydrolysis of aluminum by decomposition of urea in solution was achieved because the urea coordinates to the Al3+ in solution, forming [Al(H2O)5 (urea)]3+ and to a lesser extent [Al(H2O)4 (urea)2]3+. Upon hydrolysis more hydrolyzed monomeric species, [Al(H2O)5 (OH)]2+, [Al(H2O)4 (OH)2]+, [Al(H2O)4 (urea)(OH)]2+, and [Al(H2O)3 (urea)(OH)2]+, were formed, followed by trimeric species and the Al13 Keggin complex [AlO4Al12(OH)24(H2O)12]7+. The 27Al NMR spectra indicated the formation of other complexes in addition to the Al13 at the end of the hydrolysis reaction.     

Characterization of aluminum species with nitrate, perchlorate and sulfate ions in the positive and negative ion mode by electrospray ionization mass spectrometry

The application of electrospray ionization mass spectrometry (ESI-MS) for aluminum speciation in the positive and negative ion modes was discussed. Aluminum nitrate, perchlorate and sulfate solutions were measured by ESI-MS. In the positive ion mode, aluminum species containing anions (Al-L; L=NO3, ClO4 and SO4) were identified, while [Al(OH)2(H2O)n]+ (n=2-4) were the main species. The affinity of the anions with Al3+ estimated by ESI-MS was consistent with the hardness of the anions (hard and soft acids and bases principle) and the results from 27Al nuclear magnetic resonance studies. This indicates that the results observed from the positive ion mode preserved the chemical state of aluminum in the solution. In the negative ion mode, [Al(OH)4-nLn]- (n=0-2, L=NO3, ClO4) were the main species, which were considered to be converted from positive aluminum species, [Al(OH)(H2O)n]+ (n=2-4), by the successive addition of anions. Anions did not only attach to one aluminum ion but also bridged two aluminum ions. In Al2(SO4)3 solution, the behavior of SO4(2-) in the negative ion mode differed from that of NO3- and ClO4-. This may reflect the affinity of SO4(2-) with Al3+ in the solution or in the mass spectrometer or in both. Finally, detection mechanisms for the aluminum species in the solution are proposed for both the positive and negative ion modes. It is shown that ESI-MS can be used to observe the interaction between Al3+ and anions. We show the importance of the interpretation of the results by ESI-MS for obtaining new information of the metal species in the solution.     

Characteristics and formation of [AlO_4Al_(12)(OH)_(24)(H_2O)_(12)]~(7+) in electrolysis process

[AlO4Al12(OH)24(H2O)12] + (Al13) formation in electrolysis process is studied. The results detected by27Al NMR spectroscopy show that high content of Al13 polymer is formed in the partially hydrolyzed aluminum solution prepared by controlled electrolysis process. In the produced electrolyte of total Al concentration ([AlT]) 2.0 mol · L-1 with a basicity (B = OH/Al molar ratios) of 2.0, the content of Al13 polymer is over 60% of total Al. Dynamic light scattering shows that the size distribution of the final electrolyte solutions ([AlT] = 2.0 mol · L-1) is trimodal with B = 2.0 and bimodal with B = 2.5. The aggregates of Al13 complexes increase the particle size of partially hydrolyzed aluminum solution.     

Polyoxometalate-supported transition metal complexes and their charge complementarity: synthesis and characterization of [M(OH)6Mo6O18[Cu(Phen)(H2O)2]2][M(OH)6Mo6O18[Cu(Phen)(H2O)Cl]2].5H2O (M = Al(+, Cr3+)

Two Anderson-type heteropolyanion-supported copper phenanthroline complexes, [Al(OH)6Mo6O18[Cu(phen)(H2O)2]2]1+ (1c) and [Al(OH)6Mo6O18[Cu(phen)(H2O)Cl]2]1- (1a) complement their charges in one of the title compounds [Al(OH)6Mo6O18[Cu(phen)(H2O)2]2][Al(OH)6Mo6O18[Cu(phen)(H2O)Cl]2].5H2O [1c][1a].5 H2O 1. Similar charge complementarity exists in the chromium analogue, [Cr(OH)6Mo6O18[Cu(phen)(H2O)2]2][Cr(OH)6Mo6O18[Cu(phen)(H2O)Cl]2].5 H2O [2c][2a].5 H2O 2. The chloride coordination to copper centers of 1a and 2a makes the charge difference. In both compounds, the geometries around copper centers are distorted square pyramidal and those around aluminum/chromium centers are distorted octahedral. Three lattice waters, from the formation of intermolecular O-H.....O hydrogen bonds, have been shown to self-assemble into an "acyclic water trimer" in the crystals of both 1 and 2. The title compounds have been synthesized in a simple one pot aqueous wet-synthesis consisting of aluminum/chromium chloride, sodium molybdate, copper nitrate, phenanthroline, and hydrochloric acid, and characterized by elemental analyses, EDAX, IR, diffuse reflectance, EPR, TGA, and single-crystal X-ray diffraction. Both compounds crystallize in the triclinic space group P. Crystal data for 1: a = 10.7618(6), b = 15.0238(8), c = 15.6648(8) angstroms, alpha = 65.4570(10), beta = 83.4420(10), gamma = 71.3230(10), V = 2182.1(2) angstroms3. Crystal data for 2: a = 10.8867(5), b = 15.2504(7), c = 15.7022(7) angstroms, alpha = 64.9850(10), beta = 83.0430(10), gamma = 71.1570(10), V = 2235.47(18) angstroms3. In the electronic reflectance spectra, compounds 1 and 2 exhibit a broad d-d band at approximately 700 nm, which is a considerable shift with respect to the value of 650-660 nm for a square-pyramidal [Cu(phen)2L] complex, indicating the coordination of [M(OH)6Mo6O18]3- POM anions (as a ligand) to the monophenanthroline copper complexes to form POM-supported copper complexes 1c, 1a, 2c, and 2a. The ESR spectrum of compound 1 shows a typical axial signal for a Cu2+ (d9) system, and that of compound 2, containing both chromium(III) and copper(II) ions, may reveal a zero-field-splitting of the central Cr3+ ion of the Anderson anion, [Cr(OH)6Mo6O18]3-, with an intense peak for the Cu2+ ion.     

过饱和铝酸钠溶液中氢氧化铝自发成核动力学规律的研究

用电导法和吸光光度法首次对苛性比相同的不同浓度过饱和铝酸钠溶液自发分解过程进行了实时跟踪研究,获得铝酸钠溶解氢氧化铝自发成核动力学方程,探索了H₂O和Na⁺对氢氧化铝自发成核过程的影响.结果表明,过饱和铝酸钠溶液分解为氢氧化铝属化学反应控制过程;H₂O参与了溶液分解过程控制步骤的反应;K⁺和Na⁺等阳离子参与了溶液的重构,但对溶液分解的控制步骤影响不大.     

Potentiometric Study of the Effect of Sodium Dodecylsulfate and Dioxane on the Hydrolysis of the Aluminum(III) Ion

Hydrolytic equilibria of the aluminum(III) ion were studied in the presence of a surfactant, sodium n-dodecylsulfate (SDS) and, separately, in mixed water + dioxane and water + dioxane + surfactant media at 298.15 K, by using potentiometric measurements with a glass electrode. The concentration of SDS was between 1.25 and 25.0 mmol-dm⁻³, whereas the volume percent of dioxane was varied from 10 to 50. The supporting strong electrolyte was 0.1 mol-dm⁻³ LiCl. A general least-squares treatment of the data indicates the formation of mononuclear hydrolytic complexes of the form Al(OH)_m^{3 − m} (m = 1–3) at all studied compositions. At lower concentrations of SDS (≤ 12.5 mmol-dm⁻³) it was necessary to include polynuclear hydrolytic complexes in the hydrolytic model. On increasing the concentration of SDS, the formation of polynuclear complexes is suppressed, and at the SDS concentration of 25.0 mmol-dm⁻³, only Al(OH)²⁺ and Al(OH)₂⁺ are observed in solution. At lower volume percentages of dioxane, the speciation involved polynuclear complexes in addition to mononuclear complexes. At dioxane concentrations higher than 20 vol% only mononuclear complexes are formed. The simultaneous presence of the SDS and dioxane as ionic medium modifiers produces only the mononuclear complexes Al(OH)²⁺ and Al(OH)₂⁺, which have significantly higher stability constants than in the pure ionic medium.     

Lead hydro sodalite [Pb2(OH)(H2O)3]2[Al3Si3O12]2: synthesis and structure determination by combining X-ray rietveld refinement, 1H MAS NMR FTIR and XANES spectroscopy

Ion exchange of the sodium hydro sodalites [Na3(H2O)4]2-[Al3Si3O12]2 [Na4(H3O2)]2[Al3Si3O12]2 and [Na4(OH)]2[Al3Si3O12]2 with aqueous Pb(NO3)2 solutions yielded, whichever reactant sodalite phase was used, the same lead hydro sodalite, [Pb2(OH)-(H2O)3]2[Al3Si3O12]2. Thus, in the case of the non-basic reactant [Na3(H2O)4]2-[Al3Si3O12]2 an overexchange occurs with respect to the number of nonframework cationic charges. Rietveld structure refinement of the lead hydro sodalite based on powder X-ray diffraction data (cubic, a = 9.070 A, room temperature, space group P43n) revealed that the two lead cations within each polyhedral sodalite cage form an orientationally disordered dinuclear [Pb2(micro-OH)(micro-H2O)(H2O)2]3+ complex. Due to additional lead framework oxygen bonds the coordination environment of each metal cation (CN 3+3) is approximately spherical, and clearly the lead 6s electron lone pair is stereochemically inactive. This is also suggested by the absence of a small peak at 13.025 keV, attributed in other Pb2+-O compounds to an electronic 2p-6s transition, in the PbL3 edge XANES spectrum. 1H MAS NMR and FTIR spectra show that the hydrogen atoms of the aqua hydroxo complex (which could not be determined in the Rietveld analysis) are involved in hydrogen bonds of various strengths.     

Convenient synthesis of aluminum and gallium phosphonate cages

The reactions of AlCl 3.6H 2O and GaCl 3 with 2-pyridylphosphonic acid (2PypoH 2) and 4-pyridylphosphonic acid (4PypoH 2) afford cyclic aluminum and gallium phosphonate structures of [(2PypoH) 4Al 4(OH 2) 12]Cl 8.6H 2O ( 1), [(4PypoH) 4Al 4(OH 2) 12]Cl 8.11H 2O ( 2), [(2PypoH) 4Al 4(OH 2) 12](NO 3) 8.7H 2O ( 3), [(2PypoH) 2(2Pypo) 4Ga 8Cl 12(OH 2) 4(thf) 2](GaCl 4) 2..8thf ( 4), and [(2PypoH) 2(2Pypo) 4Ga 8Cl 12(OH 2) 4(thf) 2](NO 3) 2.9thf ( 5). Structures 1- 3 feature four aluminum atoms bridged by oxygen atoms from the phosphonate moiety and show structural resemblance to the secondary building units found in zeolites and aluminum phosphates. The gallium complexes, 4 and 5, have eight gallium atoms bridged by phosphonate moieties with two GaCl 4 (-) counterions present in 4 and nitrate ions in 5. The cage structures 1- 3 are interlinked by strong hydrogen bonds, forming polymeric chains that, for aluminum, are thermally robust. Exchange of the phosphonic acid for the more flexible 4PyCH 2PO 3H 2 afforded a coordination polymer with a 1:1 Ga:P ratio, {[(4PyCH 2PO 3H)Ga(OH 2) 3](NO 3) 2.0.5H 2O} x ( 6). Complexes 1- 6 were characterized by single-crystal X-ray diffraction, NMR, and mass spectrometry and studied by TGA.     

Hybrid organic-inorganic 1D and 2D frameworks with epsilon-Keggin polyoxomolybdates as building blocks

Organic-inorganic hybrid materials based on polyoxometalate building blocks with capping La3+ ions and bidentate oxygenated ligands have been obtained by reaction at room temperature of the [epsilon-PMo12O36(OH)4[La(H2O)4]]5+ polyoxocation with glutarate (C5H6O(2)(2-)) and squarate (C4O(4)(2-)) organic ligands. [epsilon-PMo12O37(OH)3[La(H2O)4(C5H6O4)0.5]4].21 H2O (1) and [epsilon-PMo12O39(OH)[La(H2O)6]2-[La(H2O)5(C4O4)0.5]2].17 H2O (2) form unprecedented 1D chains built from alternating polyoxocations and organic ligands connected through LaO links. The structures of these materials are compared to the 2D hybrid organic-inorganic framework [NC4H12]2-[Mo22O52(OH)18[La(H2O)4]2[La(CH3CO2)2]4].8H2O (3) isolated from the hydrothermal reaction of elemental precursors (MoO(4)(2-), Mo, La3+) in acetate buffer. Compound 3 is built from previously undescribed polyoxometalate units with twenty-two MoV centers capped by six La3+ ions, four of which are bridged by acetate ligands.     

Absorption spectra of caffeic acid, caffeate and their 1:1 complex with Al(III): density functional theory and time-dependent density functional theory investigations

The UV-visible absorption spectra of caffeic acid, caffeate and of the predominant complex obtained in the presence of aluminum ion (1:1 stoichiometry) have been simulated by using the time-dependent density functional theory (TD-DFT) technique, taking into account solvent effects. Whereas the use of the B3LYP hybrid XC functional with the 6-31+G(d,p) basis set allows us to reproduce fairly well the essential features of the experimental spectra of caffeic acid and caffeate, it is necessary to introduce an effective core potential to properly describe the aluminum ion and its environment and to obtain a good agreement between theoretical and experimental spectra of the 1:1 complex. The ligand presents two potential complexing sites in competition. The results of our calculations show that the aluminum ion coordinates preferentially at the level of the catecholate group, and the [Al(H(2)O)(4)(CA)], [Al(H(2)O)(3)(OH)(CA)](-) and [Al(H(2)O)(4)(HCA)](+) complexed forms could coexist in aqueous solution at pH = 5.