TEABr directed synthesis of ZSM-12 and its NMR characterization

Synthesis of ZSM-12 using tetraethylammonium bromide (TEABr) as the template was investigated. Among the various parameters that affect the crystallization of ZSM-12, aluminum content of the gel, OH⁻/SiO₂ and TEA/SiO₂ ratios were the important determinants. Systematic variations of these parameters revealed that the TEABr-assisted synthesis had many similarities to the synthesis using TEAOH template reported earlier, with the exception that the OH⁻/SiO₂ ratios had to be maintained at lower values. Furthermore, the OH⁻/SiO₂ ratios favorable for ZSM-12 formation lie in a very narrow range. The source of alkalinity also affected the rate of crystallization and the composition of the product. The crystallization was found to be faster and better incorporation of aluminum in the zeolite framework was obtained when NaOH was used to provide alkalinity rather than KOH. Successful synthesis of highly crystalline ZSM-12 samples with Si/Al ratio around 30 was achieved using a minimal amount of relatively inexpensive TEABr (TEA/SiO₂=0.125).

Aluminum-27 NMR spectroscopy unambiguously revealed that all aluminum atoms are incorporated in the zeolite framework in tetrahedral coordination. The NMR line-widths of aluminum signals of the calcined samples were significantly larger than those with template incorporated samples. Spin-lattice relaxation times, conventional and rotating frame, as well as magic angle spinning (MAS) cross-polarization data with variable contact time support that there is a significant proton reservoir in the aluminum framework. The NMR data indicate that many distorted tetrahedral sites are formed upon removal of the template and some of these sites contain Al–OH moieties.     

Aluminum-containing mesostructural materials

This article reviews syntheses of mesoporous aluminosilicates and aluminum oxides based on surfactant templating methods. The incorporation of aluminum in the silicate frameworks generates acid sites and ion-exchange sites. Both, tetrahedral framework aluminum and octahedral extraframework aluminum can be present, depending on the aluminum precursor used. The aluminum-containing structures tend to be less ordered than their purely siliccous analogs. Dealumination plays a significant role during template removal. Other methods for the synthesis of mesoporous aluminum-containing sieves are based on the structural transformation of kanemite, and on cluster precursors which may be connected by self-condensation or by condensation with silicate bridges. Purely aluminous mesostructures can be prepared with neutral templates or by condensing Keggin-like aluminum clusters in an ordered salt with an anionic surfactant.     

铵离子交换后脱胺对β沸石脱铝及酸性和结构的影响

采用 Py- TPD、XRD、IR等主要实验方法 ,研究了 Naβ沸石原粉经 NH+ 4 交换后脱胺对β沸石表面酸性和结构的影响以及焙烧温度对 NH+ 4 - β沸石骨架脱铝的影响。结果表明 ,高温脱胺 ,β沸石有明显的骨架脱铝过程发生 ,而迁移到 β沸石表面酸性位上 ,使表面较体相富铝 ,脱铝导致其表面酸性的减弱 ;β沸石随焙烧脱胺温度的升高 ,其表面酸量逐渐减少 ,酸强度也逐渐降低 ,L酸主要来源于骨架三配位铝 ,它比非骨架铝酸强度高 ;随脱胺温度的提高 ,β沸石晶相结构和骨架结构破坏程度均加深 ,NH+ 4 在脱胺过程中对 β沸石的结晶度影响不大 ,而交换后的 NH+ 4 较 Na+ 更不利于抑制骨架脱铝     

Selectivity effects of a new aluminum species in strongly dealuminated USY containing FCC catalysts

We have hydrothermally prepared and characterized a catalytically active tetrahedral aluminum species in faujasite distinct from the normal framework aluminum. The new tetrahedral species is formed after a severe steam dealummation at 830°C and is characterized by a²⁷A1 MASNMR shift of about 53 ppm compared to the 60 ppm shift observed for framework tetrahedral aluminum. DRIFTS experiments show that the 53 ppm species is associated with a Lewis rather than a protonic site. This species is associated with strong acidity and poor cracking selectivity compared to a conventional dealuminated faujasite at the same unit cell size. This site is very active and makes large amounts of gas and coke with poor gasoline selectivity compared to typical commercial FCC catalysts. After an appropriate sequence of hydrothermal dealumination and controlled pH washing steps, the 53 ppm species is the only species observed by NMR.     

Study of the effect of isomorphic substitutions in the framework of zeolites with a Beta structure on their porosity and sorption characteristics

Zeolites of a Beta structure with different degrees of substitution of aluminum atoms by those of boron in the aluminum–silicon–oxygen framework have been investigated. The characteristics of the porosity-texture of the fabricated zeolites and the surface properties and sorption capacities of samples to a model drug substance (thiamine hydrochloride) have been examined. It has been demonstrated that isomorphic substitutions could affect the properties of the zeolite under study, whereas the largest effect is associated with the simultaneous presence of aluminum and boron atoms in the zeolite framework. Such samples are characterized with a larger specific area and pore diameters, a high concentration of Lewis acidic sites on the surface, and high adsorption capacity.     

Synthesis of mesoporous aluminosilicates with low Si/Al ratios using a single-source molecular precursor under acidic conditions

A single molecular precursor, bis(sec-butoxy)-aluminoxy-triethoxysilane, was used as aluminum source for the synthesis of mesoporous aluminosilicates with Si/Al ratios ranging from 1 to 10 under acidic conditions. Aluminum can be stoichiometrically incorporated into the mesoporous materials at pH = 1.5. The mesoporous aluminosilicates synthesized with the single molecular precursor display larger unit cell parameter and pore diameter than that of the materials prepared with aluminum sulfate, aluminum nitrate, aluminum hydroxide, and aluminum isopropoxide as the aluminum sources. IR spectra of adsorbed pyridine and NH₃-TPD showed that both Br?nsted acidic sites and Lewis acid sites with medium strength are present in the materials. However, no direct relationship between the acidic properties and the content of aluminum was observed when the Si/Al ratios of the mesoporous aluminosilicates are lower than 10.     

Synthesis of mesoporous aluminosilicates with low Si/Al ratios using a single-source molecular precursor under acidic conditions

A single molecular precursor, bis(sec-butoxy)-aluminoxy-triethoxysilane, was used as aluminum source for the synthesis of mesoporous aluminosilicates with Si/Al ratios ranging from 1 to 10 under acidic conditions. Aluminum can be stoichiometrically incorporated into the mesoporous materials at pH = 1.5. The mesoporous aluminosilicates synthesized with the single molecular precursor display larger unit cell parameter and pore diameter than that of the materials prepared with aluminum sulfate, aluminum nitrate, aluminum hydroxide, and aluminum isopropoxide as the aluminum sources. IR spectra of adsorbed pyridine and NH₃-TPD showed that both Brönsted acidic sites and Lewis acid sites with medium strength are present in the materials. However, no direct relationship between the acidic properties and the content of aluminum was observed when the Si/Al ratios of the mesoporous aluminosilicates are lower than 10.     

Solid acidity of 2 : 1 type clay minerals activated by selective leaching

Various 2 : 1 type clay minerals were activated by H₂SO₄ treatment and their solid acidities were evaluated by NH₃-temperature programmed desorption (TPD). Clay minerals with various degrees of Al substitution in the tetrahedral sheets were used as the starting materials. These included montmorillonite (ideally no tetrahedral Al), saponite (low content of tetrahedral Al), vermiculite (intermediate content of tetrahedral Al) and phlogopite (high tetrahedral Al content). All these samples showed increased solid acidity after selective leaching, the solid acidities varying in the order phlogopite < montmorillonite < vermiculite < saponite. The NH₃-TPD spectra were deconvoluted into two peaks; the L-peak at < 200 °C corresponds to a weak acid site and the H-peak at > 250 °C corresponds to a strong acid site. The temperature of the H-peak was lowest in phlogopite (252 °C) and highest in saponite (305 °C). The generation of solid acidity in these samples is found to be related to the evolution of new tetrahedral Al sites showing a slightly different ²⁷Al MAS NMR chemical shift from the original tetrahedral Al NMR resonance.     

The influence of surface acidity and basicity on adhesion of poly (ethylene-co-acrylic acid) to aluminum

This work demonstrates the usefulness of flow microcalorimetry for surface characterization of metal foils (aluminum) and polymer [poly (ethylene-co-acrylic acid)] fibers. It shows that the polymer to aluminum adhesion is dominated by Lewis acid/Lewis base type interactions. These interactions are predictable from the measured heats of surface adsorption and desorption of probe molecules from dilute solution. The heats of interaction are a measure of the strengths of these sites. Adhesion between basic aluminum foil and acidic polymer resin increases with increasing numbers of either acidic sites on the polymer or basic sites on the foil. The calorimetry and adhesion results are in good agreement. This study supports recent observations vide infra that wettability of the aluminum is much less important for polymer/aluminum adhesion than chemical bonding.     

Catalytic properties of dealuminated and cation-exchanged Y-type zeolites

Cumene dealkylation activity was determined for a series of dealuminated zeolites which were prepared by treatments with EDTA, SiCI₄, and steam al elevated temperatures. Upon dealumination the catalytic activity increased progressively up to 50% of framework aluminum removal. This is related to the increase of acid strength after aluminum removal and the extraction of weak acid site. However, beyond Si/Ai ratio close to 6, the acid strength of zeolite do not vary and the TOF based on framework aluminum is constant. Nonframework aluminum played a positive role in the enhanced catalytic activity. The variation of catalytic activity with cation was also examined. Catalytic activity is greatest for the small polyvalent cations. Comparison of the hydroxyl group with catalytic activity shows that the active sites are the acidic hydroxyl groups.     

A new charge alternating model of localization of bivalent cations in high silica zeolites with distantly placed aluminum atoms in the framework

The present communication reports an unexpected result on quantitative substitution in HZSM-5 of all acidic protons by bivalent zinc cations via chemical reaction with zinc vapor at 800 K. Based on this result we suggest a new model for localization of bivalent cations in high silica zeolites with distantly placed aluminum atoms in the framework. According to this model some of the bivalent cations can be localized at the isolated singly negatively charged aluminum occupied oxygen tetrahedra. In parallel the equivalent number of the isolated framework aluminum atoms remains without compensating protons or zinc cations. Their negative charges are compensated indirectly by coulomb interaction with the surrounding excessively charged cationic sites. The resulting Lewis sites with only partially compensated positive electric charges possess unusually high chemical activity. They very strongly perturb molecular hydrogen at 77 K and dissociatively adsorb it at temperatures only slightly above room temperature. Application of low temperature H₂ adsorption as a molecular probe enables us to distinguish such unusual sites from Zn²⁺ cations at the conventional ion exchange positions. The similar unusual Lewis sites distantly separated from basic oxygen have also been previously detected by low temperature hydrogen adsorption in the samples prepared by conventional incipient wetness impregnation of HZSM-5 with aqueous solution of zinc nitrate though in smaller amount.     

Structure and catalytic activity correlation of CoAlPO4 in the synthesis of N,N-biphenyl urea via alkylation of aniline using dimethyl carbonate

Two sets of cobalt aluminophosphate materials, one at different pH (4.5, 7, 10, and 11.5) and the other containing different percentage of cobalt (0.5–20) were prepared by co-precipitation method. All the materials were characterized by XRD, SEM, ²⁷Al MASS NMR, TGA and DSC, FTIR, for their textural and structural properties. The surface area of the samples was determined by BET method and total surface acidity by n-butylamine titration method. The CoAlPO₄ obtained under acidic pH were found to be crystalline AlPO₄ with nonmicroporous tridymit structure associated with cobalt phosphate, whereas the one obtained under alkaline pH were amorphous aluminophosphate and also associated with cobalt phosphate. Tridymit-AlPO₄ crystals exhibited Al atom in a tetrahedral environment of phosphate groups. In the amorphous material the Al atoms were in a mixed tetrahedral and octahedral environment. The concentration of acid sites were found to be higher in the sample obtained under alkaline pH. This has been attributed due to the partial coordination of hydroxyl groups in the octahedral aluminum sites. The amorphous materials obtained under alkaline pH were found to be thermally stable up to 900 °C.The catalytic activity of all the materials was investigated in aniline alkylation using dimethyl/ethyl carbonates (DMC/DEC) under refluxing conditions. N-methyl/ethyl aniline (NMA/NEA) and biphenyl urea (BPU) were formed as the major products with the catalysts prepared at acidic and alkaline pH, respectively. A good correlation has been observed between the catalytic activity of CoAlPO₄ materials towards their selectivity for NMA/NEA and/or BPU and their textural and structural properties. Reaction conditions such as the amount of the catalyst, duration of the reaction, reusability and efficiency of the catalyst have also been evaluated. CoAlPO₄ prepared under alkaline pH with 5% of cobalt has been found to be the best catalyst for BPU synthesis from aniline and DMC/DEC under refluxing conditions.     

Synthesis and characterization of acidic properties of Al-SBA-15 materials with varying Si/Al ratios

Al-SBA-15 of varying Si/Al ratios in the range 11.4–78.4 was synthesized using tri-block copolymer P123. The calcined materials were examined by XRD, pore size distribution, surface area, ²⁷Al NMR spectroscopy. The acidity and acid strength distribution were studied using microcalorimetric adsorption of NH₃. The acidic properties were also examined by cumene cracking reaction as a function of Si/Al ratios. Systematic variation of acidity and activity was observed as a function of Si/Al ratio. The initial heats of NH₃ adsorption correlated well with activity indicate that acid sites with ΔH > 100 kJ/mole is responsible for cumene cracking activity. Linear correlations were obtained with total acidity and cumene cracking activities. The tetrahedral aluminum was found to be responsible for the observed acidities and catalytic activities.     

Sn-Beta沸石合成研究进展

含强L酸中心的Sn-Beta沸石在生物质平台化合物转化中表现出独特的活性和选择性,具有广阔的应用前景。Sn-Beta沸石主要合成方法有干胶法、水热法和同晶取代法。不同方法制备的Sn-Beta沸石Sn活性位的微环境及酸性质存在差异,在反应中表现出不同的反应性能。主要介绍Sn-Beta沸石合成方法及控制合成的影响因素。     

Characterization of Aluminum in Cation-Exchanged NH4NaY and USY Zeolites by 27Al MAS NMR Spectroscopy

The effects of cations on the local electromagnetic environments of catalytic sites in Y-zeolites are studied as a function of cation type and concentration. Quadrupolar coupling parameters measurable using ²⁷Al MAS NMR at multiple field strengths, provide a window to study aluminum’s local electronic structure. Quadrupolar parameters calculated for framework tetrahedral aluminum are related to cation concentration and Brønsted acidity for potassium-, zinc-, and lanthanum-exchanged NH₄NaY and USY zeolites.     

Effects of the nature of the aluminum source on the acidic properties of some mesostructured materials

Mesostructured aluminosilicates have been synthesized using gels prepared by reacting colloidal silica (Ludox AS) with Al(OH)₃, aluminum isopropoxide (Al(iPrO)₃) or NaAlO₂ in the presence of a surfactant. The hydrothermal transformation at 110°C of these gels produced solids with the hexagonal structure typical of MCM-41-type materials. These crystals have been characterized by X-ray diffraction, thermal analysis (TG/DTA), N₂ sorption and ²⁷Al magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy. The type, strength and density of acid sites have been studied using microcalorimetry and infrared (IR) spectroscopy.As a general trend, pore volume and average pore size decreased as the gel SiO₂/Al₂O₃ ratio decreased from 32–8, while the pore wall thickness remained in the 1.0–1.5 nm range. Except for one sample, Al was incorporated in tetrahedral coordination inside the pristine crystals. However, as expected, dealumination occurred upon calcination at 600°C/12 h, yielding materials having both tetrahedral and octahedral Al-species. Fourier transform infrared (FTIR) experiments with pyridine have indicated that these mesostructured aluminosilicates contain both Brönsted and Lewis acid sites and that acidity is strongest in samples prepared with NaAlO₂.Microcalorimetry experiments with ammonia as the probe molecule have shown that Al insertion into the mesoporous silicate framework affects acid site strength and distribution in a manner controlled by synthesis condition. Samples prepared with Al(OH)₃ contain a wide distribution of acid site strengths, indicating the absence of preferred locations of Si-O-Al groups within the pore walls. In contrast, distinct populations of acid sites with strengths in the 130–140 kJ mol⁻¹ range or near 150 kJ mol⁻¹, appear in materials prepared with Al(iPrO)₃ or with NaAlO₂, respectively. Al sites may be located at the surface of the pore wall, where they interact directly with the basic probe molecule. They may also be sandwiched between silica layers within the pore wall (3–4 Si layers thick), giving acid sites with a strength comparable with that of smectites. Finally, they may also be present in the pore (or within the pore walls) as extraframework Al(VI)-species. The nature, size, concentration, ease of hydrolysis and condensation of the aluminum precursors during synthesis control aluminum incorporation, distribution and location within the structure and with it the acidity of the resulting mesoporous aluminosilicate.     

Realumination of zeolite Y under acidic conditions

Dealuminated zeolites Y were treated with aqueous solutions of various acids and ammonium salts to investigate the realumination behavior under acidic conditions. From the results of ²⁷Al MAS NMR, ²⁹Si MAS NMR and FT-IR measurements, it was found that a part of non-framework aluminum species in the dealuminated zeolite Y is effectively reinserted into the zeolite framework in CH₃COONH₄ and C₆H₅COONH₄ aqueous solutions. Pyridine adsorption experiments also revealed that most of incorporated aluminum species generate tetrahedrally coordinated framework aluminum species, namely Brönsted acid sites. Although the realumination also proceeded in H₂SO₄ and CH₃COOH aqueous solutions, large amounts of incorporated aluminum species were not necessarily responsible for generation of Brönsted acid sites. Framework connected aluminum species, presumably as 3-fold-coordinated Lewis acidic framework aluminum species, were mainly generated. In the TEM image of the realuminated zeolite Y, needle-like crystals with ca. 25–80 nm in length were observed, which are probably due to AlOOH generated from non-framework aluminum species.     

Electrodeposition of aluminum from molten AlCl3–NaCl–KCl mixture

Electrochemical deposition of aluminum from basic and acidic molten NaCl-KCl-AlCl₃ mixture on a graphite electrode at 140 °C was studied by voltammetry, chronopotentiometry and constant current deposition. The deposition of aluminum was found to proceed via a nucleation/growth mechanism in basic melt, while it was found to be diffusion controlled in acidic melt. The diffusion coefficient calculated for Al₂Cl⁻ ₇ ions in acidic melt by voltammetry was in agreement with the deductions of voltammetry. The morphology of the aluminum deposits was examined using a metallographic microscope and by SEM. It was shown that, depending on the current density (c.d.) and AlCl₃ concentration (acidic or basic melt) different aluminum morphologies were evident but a silver-bright, compact, and very stable metallic form of aluminum deposit was obtained in acidic melt with KI addition as surfactant.     

纳米片Ga-MFI分子筛合成及其对航空燃油催化裂解反应中低碳烯烃选择性的影响

在纳米片Al-MFI分子筛合成的基础上,以镓源[Ga(NO₃)₃·xH₂O]替换铝源[Al₂(SO₄)₃·18H₂O],合成出类质同象纳米片Ga-MFI分子筛,采用X射线衍射、扫描电镜、BET比表面积分析和NH₃程序升温脱附法等技术对其进行了表征,并考察了普通ZSM-5分子筛、纳米片Al-MFI分子筛和纳米片Ga-MFI分子筛对航空燃油裂解反应的催化性能。结果表明,合成的分子筛是具有MFI骨架拓扑结构的纳米片状分子筛,具有较大的比表面积（482m²/g）和中孔孔容;与铝原子相比,镓原子与硅、氧原子形成的酸性位点的酸性减弱。在高温下（600℃）,它抑制了氢转移反应的进行,减少了低碳烯烃的二次反应和结焦前体（芳香烃）在酸性位点上的吸附,使其具有更高催化活性和低碳烯烃选择性,从而获得了比纳米片Al-MFI分子筛高14.47%的热沉。该研究为高超音速飞行器的主动热防护提供了技术支撑。     

Characteristics of the Photocatalytic Oxidation of Methane into Methanol on V-Containing MCM-41 Catalysts

V-containing MCM-41 catalysts were prepared by a direct synthesis method under acidic and basic conditions and impregnation. Their photocatalytic reactivity was evaluated for the selective photocatalytic oxidation of methane with NO under UV irradiation at 295 K. Selective methanol formation was observed on V-MCM-41 prepared in acidic solution and imp-V/MCM-41, while only coupling reaction products were obtained on V-MCM-41 prepared in basic solution. The photocatalytic reactivity of the catalysts for the partial oxidation of methane was found to strongly depend on the local structure of the V-oxide species including the coordination and loading sites, i.e., the charge transfer excited states of the isolated tetrahedral V⁵⁺-oxide species supported on the catalyst surface act as the active sites for the selective photocatalytic oxidation of methane into methanol.