Synthesis and characterization of molybdenum incorporated mesoporous aluminophosphate

A synthesis of molybdenum incorporated mesoporous aluminophosphate with long-chain n-alkylamine as template material had been prepared under non-aqueous condition. These materials were extensively characterized by using X-ray diffraction (XRD), nitrogen sorption isotherms, nuclear magnetic resonance of ²⁷Al and ³¹P (NMR), inductive coupled plasma (ICP), electron spin resonance (ESR), Fourier transform infrared (FTIR) and thermogravimetric-differential thermal analysis (TG-DTA). Morphology of the materials had been observed by using transmission electron microscope (TEM) that revealed the mesoporous materials possessed wormhole-like structures. Alkaline solvent extraction using n-butylamine/ethanol had been efficiently removed the n-alkylamine from the mesoporous samples which yielded BET surface areas around 550-730 m²/g. BJH analysis showed a narrow pore size distribution which increased with increasing of the carbon chain length of alkylamine (template). Valence state and coordination of the molybdenum in the obtained samples were investigated by using ESR and FTIR where it was found that Mo⁴⁺ and Mo⁶⁺ molybdenum species existed in the molybdenum incorporated mesoporous aluminophosphate in tetrahedral coordination.     

Synthesis of molecular sieve AlPO4-12

A member of the novel family of crystalline microporous aluminophosphates, AlPO₄-12, was synthesized by hydrothermal crystallization using different aluminum-containing compounds. Three new crystalline phases were obtained by varying the composition of the reaction mixture. The effect of the synthesis conditions on the hudrothermal process and the kinetics of crystallization are discussed. The apparent activation energies obtained for AlPO₄-12 are 20.9 and 14.6 kcal/mol for nucleation and crystallization, respectively. The adsorption isotherms of one AlPO₄-12 product were measured.     

Ethylene polymerization over supported MAO/(nBuCp)2ZrCl2 catalysts: Influence of support properties

The catalytic system methylaluminoxane (MAO) and bis(n-butylcyclopentadienyl)zirconium dichloride ((nBuCp)₂ZrCl₂) was immobilized on commercial silica, silica-alumina and aluminophosphate calcined at different temperatures. The properties of the supports were determined by using N₂ adsorption-desorption isotherms at 77 K, FT-IR spectroscopy and SEM. After aluminium and zirconium impregnation, the catalysts were analyzed by ICP-AES, FT-IR and UV-vis spectroscopy. Ethylene polymerizations were carried out in a Schlenk tube at 70 °C and 1.2 bar of ethylene pressure. The polyethylene obtained was characterized by GPC, DSC and SEM.Catalysts supported on silica-alumina exhibited higher polymerization activity than those supported on silica and aluminophosphate. Besides, the activity of MAO/(nBuCp)₂ZrCl₂ catalytic system supported on silica-alumina and aluminophosphate decreased strongly with support calcination temperature, while remained almost constant when silica was employed as support. All these experimental features suggest a role of the support acid properties and hydroxyl group population in the generation of active polymerization species.     

VPI—5分子筛热相变转化成ALPO4—8的研究

VPI-5是具有十八元环超大孔道的磷酸铝分子筛,在加热过程中,随着孔道中的水分子的脱除,其骨架结构转化成具有十四元环孔道的AlPO_4-8分子筛。采用XRD及骨架结构模型计算等方法研究了这一相变过程,并对相变机理进行了探讨。     

基于遗传编程方法的微孔磷酸铝的定向合成研究

根据微孔磷酸铝合成数据的特点,针对合成数据库中合成参数过多和交叉描述等问题,利用改进的遗传编程算法对具有(6,8)元环的微孔磷酸铝合成参数进行特征提取,优化出新的复合特征来更好地描述磷酸铝合成中溶剂和模板剂的特征,并通过参数进化过程的研究,考察了模板剂和溶剂对产物生成的具体影响,从而指导具有特定结构磷酸铝的定向合成.     

不同钴含量CoAPO-5分子筛的合成、表征及其催化环己烷氧化性能

用水热法合成了一系列不同含量钴掺杂的磷酸铝分子筛CoAPO-5. 合成的样品用X射线衍射(XRD), 扫描电镜(SEM), 紫外可见漫反射光谱(UV-Vis DRS), 热重分析(TG)仪和电感耦合等离子体发射光谱(ICP-AES)等进行了表征. XRD表征显示, 合成的CoAPO-5分子筛具有较高的结晶度, 分子筛晶胞参数与Co含量之间存在较好的对应关系. UV-Vis漫反射光谱显示合成的CoAPO-5分子筛具有骨架钴的特征三重峰; 焙烧后峰的强度降低, 表明分子筛骨架中Co2+可被氧化成Co3+. SEM表明该分子筛具有典型的AlPO4-5分子筛形貌特征. TG结果也表明Co2+进入了分子筛骨架, 分子筛具有较好的稳定性. 在环己烷氧化反应中CoAPO-5具有较好的催化性能, 环己烷转化率与环己酮选择性均较高; 随着分子筛中钴含量的增加, 环己烷的转化率增加.     

以醚胺为模板剂合成含二价金属杂原子的开放骨架磷酸铝化合物M(Ⅱ)-CJ50

在水热体系中, 以2,2'-(乙烯二氧)双(乙胺)为模板剂, 合成了3种含二价金属杂原子的开放骨架磷酸铝化合物M(Ⅱ)-CJ50(|C₆H₁₇N₂O₂| [MAl₃P₄O₁₆], 其中M=Mg, Mn和Fe). 单晶及粉末X射线衍射分析表明, 这3种化合物与以咪唑为模板剂合成的含三价金属杂原子的M(Ⅲ)-CJ50具有相似的骨架拓扑结构. 二者的区别在于: 由于使用了还原性较强的醚胺作模板剂, M(Ⅱ)-CJ50结构中的金属杂原子具有比M(Ⅲ)-CJ50更低的氧化态; M(Ⅱ)-CJ50中的金属杂原子与1个醚胺模板剂分子中的2个醚氧原子形成双齿配位, 而M(Ⅲ)-CJ50中的金属杂原子则与2个咪唑模板剂分别形成单齿配位. 此外, 磁性测试结果表明, 由于金属杂原子的氧化态以及配体模板剂分子的差异, 导致M(Ⅱ)-CJ50中的过渡金属杂原子处于电子高自旋态, 而M(Ⅲ)-CJ50中的杂原子则处于低自旋态.     

spin-lattice relaxation in cobalt-containing aluminophosphate molecular sieves

Phosphorus spin-lattice relaxation was studied in aluminophosphate molecular sieves containing various concentrations of either framework or non-framework cobalt. The behaviour of nuclear magnetisation in the presence of these paramagnetic centres was described successfully in the limit of no spin-diffusion. The diffusionless regime was strongly indicated with non-exponential magnetisation recovery and was therefore easy to recognise. According to the model, spin-lattice relaxation rates depend on the square of cobalt concentration. Measured relaxation rates agreed well with calculations if effective cobalt concentration was considered rather than the average one. The latter was obtained by bulk elemental analysis, while the former was extracted from cobalt concentration depth-profiles measured with Auger electron spectroscopy. These measurements indicated that in impregnated samples containing non-framework cobalt there could be much more cobalt near the crystal surface than within the crystal. Because high cobalt concentration can lead to an invisible phosphorus, only nuclei deep within the crystal contribute to the NMR signal. In such a case, the effective concentration is simply the concentration of cobalt far from the crystal surface. In our case, two impregnated samples with different bulk cobalt concentrations exhibited equal relaxation rates. Previously, such a case was misinterpreted as a case, in which nuclear spin-lattice relaxation was independent of cobalt concentration. AES measurements, however, revealed, that although average concentrations of the two samples were different by a factor of two, their effective concentrations were equal and thus in complete agreement with observed relaxation rates.     

Parallelizing acquisitions of solid-state NMR spectra with multi-channel probe and multi-receivers: Applications to nanoporous solids

A five-channel (¹H, ¹⁹F, ³¹P, ²⁷Al, ¹³C) 2.5 mm magic-angle-spinning (MAS) nuclear magnetic resonance (NMR) probe is used in combination with three separate receivers for the parallel acquisitions of one (1D) and two-dimensional (2D) NMR spectra in model fluorinated aluminophosphate and porous Al-based metal-organic framework (MOF). Possible combinations to record simultaneously spectra using this set-up are presented, including (i) parallel acquisitions of quantitative 1D NMR spectra of solids containing nuclei with contrasted T₁ relaxation rates and (ii) parallel acquisitions of 2D heteronuclear NMR spectra. In solids containing numerous different NMR-accessible nuclei, the number of NMR experiments that have to be acquired to get accurate structural information is high. The strategy we present here, i.e. the multiplication of both the number of irradiation channels in the probe and the number of parallel receivers, offers one possibility to optimize this measurement time.     

spin-lattice relaxation in cobalt-containing aluminophosphate molecular sieves

Phosphorus spin-lattice relaxation was studied in aluminophosphate molecular sieves containing various concentrations of either framework or non-framework cobalt. The behaviour of nuclear magnetisation in the presence of these paramagnetic centres was described successfully in the limit of no spin-diffusion. The diffusionless regime was strongly indicated with non-exponential magnetisation recovery and was therefore easy to recognise. According to the model, spin-lattice relaxation rates depend on the square of cobalt concentration. Measured relaxation rates agreed well with calculations if effective cobalt concentration was considered rather than the average one. The latter was obtained by bulk elemental analysis, while the former was extracted from cobalt concentration depth-profiles measured with Auger electron spectroscopy. These measurements indicated that in impregnated samples containing non-framework cobalt there could be much more cobalt near the crystal surface than within the crystal. Because high cobalt concentration can lead to an invisible phosphorus, only nuclei deep within the crystal contribute to the NMR signal. In such a case, the effective concentration is simply the concentration of cobalt far from the crystal surface. In our case, two impregnated samples with different bulk cobalt concentrations exhibited equal relaxation rates. Previously, such a case was misinterpreted as a case, in which nuclear spin-lattice relaxation was independent of cobalt concentration. AES measurements, however, revealed, that although average concentrations of the two samples were different by a factor of two, their effective concentrations were equal and thus in complete agreement with observed relaxation rates.