Ordered mesoporous aluminosilicates with very low Si/Al ratio and stable tetrahedral aluminum sites for catalysis

New and ordered 2D-hexagonal (p6mm) mesoporous aluminosilicates (CMI-11) have been synthesized in strongly alkaline media using aluminosilicate ester ((Bu^sO)₂-Al-O-Si-(OEt)₃) as single-source molecular precursor and CTMABr as surfactant and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), N₂ adsorption–desorption and ²⁷Al and ²⁹Si MAS NMR spectroscopy. These mesoproous aluminosilicates exhibit a very low Si/Al ratio of 1.9 and highly thermal stable tetrahedral aluminum sites in the mesoporous walls. ²⁷Al and ²⁹Si MAS NMR spectroscopy indicates that the pore walls of CMI-11 are fully condensed with molecular homogeneity of Si–O–Al linkage. These materials are highly important in catalysis, in particular for the petroleum processing and the bulky molecules treatment.     

Solid state multinuclear NMR study of iron species in natural and modified clinoptilolite from Tasajera deposit (Cuba)

The present study has been conducted to elucidate the Fe-sites in natural clinoptilolite, and the possibility to produce a reversible replacement of these atoms in the zeolite framework. In order to achieve these results we have tried to introduce iron in clinoptilolite structure after the almost total extraction of the natural iron species. A sample of the purified natural clinoptilolite from Tasajeras deposit, Central region of Cuba, was modified by a hydrothermal treatment with orthophosphoric acid. Iron exchange forms of the orthophosphoric zeolite were obtained using FeSO₄ and Fe₂(SO₄)₃ solutions. The modified zeolites were studied by multinuclear magnetic resonance (²⁷Al, ²⁹Si, ³¹P MAS NMR and ¹²⁹Xe NMR). Other analytical techniques as Electron Paramagnetic Resonance, X-ray diffraction, Mössbauer and Infrared spectrometry, volumetric measurements and chemical analysis by Induced Plasma Coupled spectroscopy were used to support the results of NMR studies. The presence of iron species with tetrahedral and octahedral coordination in the structure of a natural clinoptilolite has been confirmed. The influence of iron in tetrahedral coordination in the thermal stability of the clinoptilolite structure was also confirmed.     

Synthesis and Characterization of a SiAION Glass

Homogeneous SiAION glasses containing up to 1 wt% nitrogen were synthesized via a pressureless method with a controlled quench rate and structurally investigated using ²⁷Al and ²⁹Si magic-angle spinning nuclear magnetic resonance (MAS NMR), Raman, and infrared (IR) spectroscopies. Minor changes occur with the incorporation of nitrogen into the aluminosilicate glass structure as evidenced by modifications to spectra of a nitrogen-free aluminosilicate glass. The ²⁷Al MAS NMR spectrum of the SiAION glass shows the existence of aluminum in 4-,5-, and 6-coordination to oxygen. The ²⁹Si MAS NMR spectra show a distribution of silicon sites in 4-coordination to oxygen. Raman and IR spectra of the SiAION glass show additional features due to incorporation of nitrogen in the structure compared with spectra of nitrogen-free aluminosilicate glasses.     

Effect of dealumination on the structure and acidity of H-Y Zeolites

The effect of dealumination using ammonium hexafluorosilicate and steaming has been studied on a series of HY zeolites. The structure of the zeolites after dealumination was studied using XRD, ²⁹Si NMR, ²⁷Al NMR, and IR of the hydroxyl region. The effect of dealumination on the pore structure was investigated using ¹²⁹Xe NMR experiments. Steam dealumination tends to result in the formation of a highly dispersed extralattice aluminum species within the zeolitic supercage. It is suggested that this extralattice species contributes to enhanced acidity.     

Influence of the SiO2/Al2O3 ratio on the synthesis and physicochemical characteristics of levyne-type zeolite

Levyne-type zeolites were synthesized from gels of initial compositions 4.5Na₂O-6MeQI-xAl₂O₃ 30SiO₂-500H₂O, with MeQ = methylquinuclidinium and 0.6 ≤ x ≥ 3 at 150 ≤ t ≥ 190 °C. The ²⁹Si NMR spectra show the presence of two crystallographically different sites in the structure. The ²⁷Al NMR spectra also suggest the presence of two different tetrahedral Al atoms incorporated in the structure. A rather high amount of defect groups SiOM and Si(OM)₂ with M = MeQ, Na and/or H are present in the precursor samples. The Si(OM)₂ groups are eliminated during calcination, and a certain amount of SiOM still persists after calcination. The combined ¹³C NMR and thermal analysis data allowed one to interpret the nature of the two different types of MeQ⁺ ions occluded in the levyne channels.     

柠檬酸复合改性对多环芳烃选择性开环铂/Beta催化剂性能的影响

通过水热处理、柠檬酸处理及其复合处理对Beta分子筛进行后改性,并以改性后的载体制得铂/Beta催化剂。采用X射线衍射（XRD）、X射线荧光光谱仪（XRF）、程序升温脱附（NH₃-TPD）、红外吡啶吸附（Py-IR）、骨架铝核磁共振技术（²⁷Al MAS NMR）及骨架硅核磁共振技术（²⁹Si MAS NMR）等表征了改性前后Beta分子筛的物化性质,并考察了改性前后铂/Beta的多环芳烃选择性开环性能。结果表明,Beta分子筛在柠檬酸处理过程中可同时发生络合脱铝与骨架补铝,实现骨架铝的再分布;Beta分子筛在水热处理过程中优先脱除稳定性相对较低的Si（2 Al）处骨架铝,产生骨架缺陷的同时生成一定比例的二次介孔结构;水热-柠檬酸复合处理影响Beta分子筛骨架补铝及骨架铝再分布的效果,水热处理后Beta分子筛中存在更多的骨架缺陷,促进活性Al（OH）₂⁺物种的骨架补铝作用。当Beta分子筛采用水热-柠檬酸复合处理顺序时,骨架补铝及骨架铝再分布效果显著,样品以中强酸为主,且具有较高的B酸量与L酸量的比值,所制备催化剂的多环芳烃选择性开环活性及稳定性最优。     

Hydroxy-Al pillaring of concentrated suspensions of smectite clays

The addition of solid 5/6 basic aluminum chloride salt (ACH) to a concentrated (50% w/w) acetone suspension of various dioctahedral and trioctahedral smectites, followed by washing with distilled water and centrifugation, leads to the formation of well formed pillared derivatives (PILCs). The samples were characterized by chemical analysis, X-ray diffraction, N₂ adsorption, ²⁹Si and ²⁷Al MAS NMR spectroscopy, and turned out to be highly microporous with micropore volumes in the range 0.10–0.12 cm³/g, and with highly ordered clay sheets (d₀₀₁ = 1.8 nm). The number and strength of the acid sites were estimated by analysing the product distribution of the 1-butene isomerization reaction. A mechanism of the pillaring process is proposed on the basis of MAS NMR, XRD, and N₂ adsorption data.     

Study of Mn incorporation into SAPO framework: Synthesis, characterization and catalysis in chloromethane conversion to light olefins

MnAPSO-34 molecular sieve has been synthesized with triethylamine as the template, characterized with XRD, XRF, ³¹P, ²⁷Al and ²⁹Si NMR and FT-IR techniques and compared with SAPO-34. The template decomposition and removal have been investigated with TG–DTG–DSC coupled with mass spectrometer. Mn incorporation generates a negligible difference on the chemical shift in ³¹P and ²⁷Al MAS NMR, while an effect on the intensity of resonance peaks is revealed. ²⁹Si MAS NMR study has demonstrated that Mn incorporation favors the Si island formation, which may give rise to the stronger acidic sites. The thermal analysis (TG–DSC) on template removal in a diluted oxygen atmosphere, leading to the formation of CO₂, NO and H₂O, showed, besides a low temperature endothermic weight loss due to the desorption of water, two weight losses (200–400 and 400–600 °C) for SAPO-34 and MnAPSO-34, suggesting two different chemical location environments of template molecules in these two molecular sieves. The quantity of template removed at higher temperature range is much higher in MnAPSO-34, indicating stronger template–framework interaction and stronger acidity after calcination. The acid difference caused by Mn incorporation has also been evidenced by ammonia adsorption evaluated by FT-IR. Chloromethane transformation was carried out over MnAPSO-34 and SAPO-34 and the catalytic performance showed that both molecular sieves are very active and selective catalyst for light olefins production. MnAPSO-34 demonstrated higher activity and light olefins selectivity.     

Location of Aluminum in Substituted Calcium Silicate Hydrate (C-S-H) Gels as Determined by 29Si and 27Al NMR and EELS

Solid-state ²⁷Al and ²⁹Si magic angle spinning NMR spectroscopy has been combined with electron energy loss spectroscopy carried out in the transmission electron microscope to determine the location of Al substituting in a semicrystalline C-S-H gel present in a hydrated synthetic slag glass. The gel is found to contain mainly pentameric silicate chains in which the central silicon is substituted by aluminum.     

Early-Stage Thermal Oxidation of Carbothermal β-Sialon Powder

Early-stage thermal oxidation (below 1100°C) of carbothermally synthesized β-sialon powder was monitored by X-ray powder diffraction, solid-state ²⁹Si and ²⁷Al MAS NMR spectroscopy, and thermogravimetry. No crystalline oxidation products were detected by XRD but ²⁹Si and ²⁷Al MAS NMR indicated the early formation of amorphous silica, followed by the formation of an amorphous aluminosilicate with an atomic environment similar to that of mullite. The initial oxidation was described by a linear kinetic law with an activation energy of 170 kJmol⁻¹, suggesting the rate-limiting step to be due to dissolution of O₂ in an amorphous silica surface layer on the β-sialon particles.     

Benzylation of benzene and other aromatics by benzyl chloride over mesoporous AlSBA-15 catalysts

Aluminum-containing mesoporous molecular sieves AlSBA-15 with different n_Si/n_Al ratios and AlMCM-41 have been synthesized hydrothermally and characterized in detail by physicochemical methods, viz. XRD, N₂ adsorption and ²⁷Al NMR spectroscopy. The low angle XRD and N₂ adsorption measurements reveal that the structural order of SBA-15 was retained after the incorporation of Al. The increase of the unit cell parameter with increasing aluminum content and ²⁷Al MAS NMR spectroscopy confirm the incorporation of aluminum in the framework. Benzylation of benzene and substituted benzenes reaction employing benzyl chloride as the alkylating agent over AlSBA-15 and AlMCM-41 have been investigated. The influence of various reaction parameters such as reaction temperature, reactant feed ratio and catalyst amount affecting the activity and selectivity of AlSBA-15, have been studied. Among the mesoporous catalysts studied, AlSBA-15(45), where the number in parentheses indicates the molar n_Si/n_Al ratio, shows both high conversion and high selectivity for the benzylation of benzene. The activity of this catalyst for the benzylation of different aromatic compounds is in the following order: benzene > toluene > p-xylene > mesitylene > anisole. Kinetics of the benzene benzylation over different catalysts have also been investigated.     

Synthesis and characterization of the layered sodium silicate ilerite

A sodium ilerite, molar ratios 1Na₂O:8.2SiO₂:10.2H₂O, was obtained with a good crystalline structure and characterized by several NMR techniques in addition to X-ray diffraction (XRD). The X-ray pattern of the as-synthesized ilerite is in very good agreement with the structure proposed by Gies and coworkers. The narrow ²⁹Si MAS NMR signals (FWHM=0.3 ppm) indicate a good short-range order of the framework. The proton dynamics influences several ²⁹Si NMR parameters. The 16 ppm signal in the ¹H MAS NMR spectra is explained by a proton in a bridging position in the short (2.3 Å) O4–O4 bonding. The quadrupole coupling constant C_qcc=100 kHz with η=0.2 for the 16 ppm signal, which was obtained from the ²H MAS NMR spectra, confirms this explanation. ¹⁷O NMR shows also a separate signal for SiOH groups but cannot resolve the three expected lines for SiOSi. PFG NMR detects a small mobile portion of water in the ilerite, which is located probably on the external surface of the crystallites. An intracrystalline diffusion coefficient of the intercalated water molecules of the order of magnitude 10⁻¹⁵ m² s⁻¹ was obtained by NMR tracer exchange experiments.     

Effect of leaching agent in the dealumination of stabilized Y zeolites

X-ray diffraction and ²⁷Al multiquantum MAS NMR combined with global elemental analysis have been used to identify and quantify extra-framework aluminum (EFAL) in Y zeolites stabilized by steaming followed by EFAL extraction using nitric acid, ammonium hexafluorosilicate (AHFS) or ethylenediaminetetraacetic acid (EDTA). Both the ease of extraction and the type of EFAL extracted are found to vary with the strength and nature of the leaching agent. Polymeric amorphous alumina, removed easily at low concentrations of nitric acid, is extracted progressively with increasing concentrations of other agents. This type of EFAL accounts for less than half of the extra-framework aluminum. Aluminum atoms linked to the zeolite framework in a distorted tetrahedral environment are also removed by acid leaching but are resistant to high concentrations of AHFS and EDTA, whereas isolated cationic EFAL shows the reverse behavior.     

MAS NMR Studies of Partially Carbonated Portland Cement and Tricalcium Silicate Pastes

²⁹Si, ²⁷Al, and ¹H MAS NMR studies of partially carbonated mature ordinary Portland cement (OPC) and tricalcium silicate (C₃S) pastes have been carried out. The water-to-solid ratios ( W/S ) have been varied between 0 and 1 at hydration temperatures of 23^o and 90^oC. Various Q ⁿi units with n =0, 1,2,3, and 4, and a Q³ (1Al) group have been identified using ²⁹Si NMR. Cross-polarization experiments, in addition, have made it possible to assign the OH groups. Two types of fourfold- and one type sixfold-coordinated aluminum have been distinguished using ²⁷Al NMR. In C₃S pastes for w/s >0.7, progressive carbonation leads to a nearly perfect three-dimensional network consisting of Q³ and Q⁴only. In contrast, in OPC pasted only about 40% of the highly polymerized silicate units are formed, partially copolymerized with AlO₄ tetrahedra.     

Reactivity of titanosilicates-supported catalysts for the selective catalytic reduction of NO with NH3

The zeolites with MEL structure were synthesized via the hydrothermal method and the zeolites-supported catalysts, such as Cu²⁺, Ga³⁺, Co³⁺, Ce²⁺ and VO²⁺/zeolites, were prepared by the incipient wetness impregnation. The structures of the synthesized zeolites were characterized by techniques of XRD, FT-IR, SIMS, ²⁹Si and ²⁷Al MAS NMR. The selective catalytic reduction (SCR) of NO by ammonia was carried out with a glass reactor under a downstream flow. The synthesized TS-2 showed no significant DeNO_x activity, instead of catalyzing the ammonia oxidation at a high temperature. Furthermore, the catalytic activity of TS2 zeolite can be effectively modified and tuned up through incorporating second metal ion such as Fe³⁺, Co³⁺, and Al³⁺ into the framework (i.e., [Fe,Ti]Z11, [Co,Ti]Z11, and [Al,Ti]Z11). Among the synthesized bimetallosilicates, the [Fe,Ti]Z11 zeolite is the most active catalyst for the SCR DeNO_x with ammonia; the NO conversion and the N₂ yield reach around 80%. In addition, impregnating the metal ions on TS2 or bimetallosilicates is also a very effective way to improve the SCR DeNO_x activity. Ga³⁺/[Fe40,Ti40]Z11 and Co³⁺/[Fe40,Ti40]Z11 are the most active catalysts and show a potential for the practical applications.     

Multinuclear MAS NMR studies of zeolites MCM-22 and MCM-49

MCM-22 and MCM-49 comprise a new class of molecular sieves that crystallizes as thin sheets or platelets and has many unusual structural features. MCM-22 is first synthesized hydrothermally as a precursor, MCM-22(P), that condenses upon calcination to a three-dimensional framework (MCM-22). Its framework topology is comprised of two independent pore systems, both accessible through 10-membered rings. One of these pore systems is defined by two-dimensional sinusoidal channels, which maintain an effective 10-ring diameter throughout the structure. The other consists of large supercages whose inner free diameter, 7.1 Å, is defined by 12 rings with inner height of 18.2 Å. MCM-49 has the same framework topology as MCM-22, but is synthesized directly in the reaction gel and therefore still contains the organic template. Multinuclear MAS NMR studies of MCM-22 (P), MCM-22, and MCM-49 are presented and discussed in light of the proposed structure and provide new insights into this novel class of materials. The structural information obtained from this NMR investigation is complementary to and consistent with the structure proposed from X-ray diffraction measurements. ¹³C NMR data support the existence of different dual pore systems within both MCM-22(P) and MCM-49. ²⁷Al MAS NMR spectra exhibit three distinct T_d resonances that can be interpreted in terms of the proposed framework topology. ²⁹Si MAS studies of a highly siliceous MCM-22 prepared by hydrothermal dealumination confirm the presence of at least one buried T-site in its framework structure that is not accessible to a channel wall, favor the orthorhombic form of the proposed structure, and support the presence of the modified dodecasil-1H cage.     

Effect of post-synthesis hydrothermal treatments on the adsorptive volume of surfactant-templated mesostructures

Ordered aluminosilicate mesostructures of the MCM-41 family having a SiO₂/Al₂O₃ ratio5 were prepared using cetyltrimethylammonium chloride. These mesophases were subsequently exposed to a hydrothermal treatment (110°C for one week at autogeneous pressure). The effects of the hydrothermal treatment were documented by analyzing the samples before and after the treatments by scanning electron microscopy, N₂ sorption for pore volume and pore sizes, powder X-ray diffraction and solid-state, magic-angle-spinning (MAS)-NMR spectroscopy for the ²⁷Al and ²⁹Si nuclei. The post-synthesis hydrothermal treatment increased the mesostructure adsorptive volume by as much as 55% in mesostructures prepared from Na-aluminate (from 0.29 to 0.45 ml/g) and 27% in mesostructures prepared from Al-hydroxide (from 0.44 to 0.56 ml/g) while the average pore diameter remained essentially unchanged.

The post-synthesis hydrothermal treatment caused only small changes in the SiO₂/Al₂O₃ ratio when the source of the aluminum ion was Al-hydroxide (6.4–6.6) and Na-aluminate (5.6–5.8). The crystal symmetry did not change after successive treatments, the unit cell size of the samples prepared from Al-hydroxide increased slightly (5.5–5.7 nm) and the peak width at mid-height changed very little. The mesophases prepared from either source of aluminum showed tetrahedral (T_d) symmetry, as confirmed by ²⁷Al-MAS NMR before the hydrothermal treatment. After two successive hydrothermal treatments, almost all the Al ions show T_d symmetry together with a small population of Al ions in the octahedral (O_h) symmetry. The calcined mesostructures all showed Al ions in T_d and O_h environments.     

Mesoporous AlPO4 Glass from a Simple Aqueous Sol–Gel Route

Transparent and colorless AlPO₄ gel and glass are prepared via a simple aqueous sol–gel route using aluminum lactate and phosphoric acid as precursors. The stoichiometric AlPO₄ glass derived from this sol–gel route has a mesoporous structure with a surface area of 504 m²/g after calcination to 600°C. With increasing gel-to-glass processing temperature, the average degree of P/Al connectivity increases. After sample calcination at 600°C for 4 h, ²⁷Al MAS NMR spectra indicate that aluminum is almost completely converted into AlO₄ units. ²⁷Al{³¹P} rotational echo double resonance and ³¹P{²⁷Al} rotational echo adiabatic passage double resonance NMR experiments as well as ²⁷Al and ³¹P MAS NMR results further confirm that the prepared AlPO₄ glass has a three-dimensional network based on alternating Al(OP)₄ and P(OAl)₄ tetrahedral units in analogy to the local structure of crystalline AlPO₄.     

Silicon Substitution for Aluminum in Calcium Silicate Hydrates

²⁷Al MAS and multiquantum (MQ) MASNMR (magic-angle spinning nuclear magnetic resonance) spectroscopy were used to study the substitution of silicon by aluminum in calcium silicate hydrates (C-S-H), which are the main component of hydrated portland cement. Synthetic C-S-H samples were prepared, and their chemical stability was studied. Two-dimensional 3Q-MASNMR spectra revealed the chemical shift and quadrupolar parameters (delta_iso, nu_Q) that labeled aluminum sites in the C-S-H. Tetrahedral aluminum was observed in the bridging and nonbridging sites of the silicate chains.     

Characterization of Synthetic and Naturally Occurring Clays by 27Al and 29Si Magic-Angle Spinning NMR Spectroscopy

Magic-angle spinning nuclear magnetic resonance (MASNMR) spectroscopy (²⁷Al) detected the coordination of Al in clays containing as little as 0.26% Al₂O₃. The ²⁹Si MASNMR of fluorphlogopite showed three distinct Si chemical environments which suggested short-range ordering. Synthetic laponite and mica-montmorillonite showed broad ²⁹Si resonances indicative of short-range disorder. A saponite showed four ²⁹Si resonances. Considerable insight into the short-range ordering of clays can be gained by ²⁷Al and ²⁹Si MASNMR.