Comparative FT infrared study of structural changes occuring on dealumination of zeolite Na-Y with ethylenediaminetetraacetic or hydrochloric acid

IR lattice vibration spectra were used to monitor the changes in the structure of zeolite Na-Y upon its dealumination with ethylenediaminetetraacetic acid (EDTA) or with HCl. The terminal Si-O(H,Na) bonds thus formed (which are detectable by characteristic absorbance at v 900–950 cm^–1) are energetically less uniform when EDTA has been used as the dealuminating agent. This inhomogeneity is connected with the local deformations of zeolite structure which result in lowering the symmetry of silicon-oxygen tetrahedra. As a consequence, two novel bands appear at v 1090 cm^–1 and 1200 cm^–1 in addition to the fundamental absorption bands, v_as (TO₄) (T = Si, Al), at 1030 cm^–1 and 1145 cm^–1. A mechanism of dealumination is proposed, which takes into account the topochemical peculiarities involved in the chelation of the framework aluminum ions with EDTA.Translated fromIzyestiya Akademii Nauk. Seriya Khimicheskay, No. 2, pp. 284–287, February, 1993.     

高硅Y沸石的研制及性能——Ⅱ.沸石孔结构及吸附性能

LiNaY沸石经SiCl₄气相同晶脱铝补硅后制得系列高硅铝比、高结晶度的Y沸石,用低温氮吸附法,求得样品对N₂的吸附—脱附等温线,从而计算其比表面和孔体积,并采用BJH模型计算孔径分布。用真空重量法测定了四种C₆化合物(正己烷,2,3-二甲基丁烷、苯、环己烷)的吸附等温线,探讨吸附量与吸附物的性能(极性、几何构型)、吸附量与吸附剂脱铝深度的关系。从而得到,经SiCl₄同晶取代后Y沸石的孔结构和表面性质与脱铝深度的关系。     

Mechanism of silicon film deposition in the RF plasma reduction of silicon tetrachloride

Plasma-chemical reduction of SiCl₄ in mixtures with H₂ and Ar has been studied by optical emission spectroscopy (OES) and laser interferometry techniques. It has been found that the Ar:H₂ ratio strongly affects the plasma composition as well as the deposition (r _D) and etch (r _E) rates of Si: H, Cl films and that the electron impact dissociation is the most important channel for the production of SiCl_x species, which are the precursors of the film growth. Chemisorption of SiCl_x and the reactive surface reaction SiCl_x+H–SiCl_(x–1)0+HCl are important steps in the deposition process. The suggested deposition model givesr _D [SiCl_x][H], in agreement with the experimental data. Etching of Si: H, Cl films occurs at high Ar: H₂ ratio when Cl atoms in the gas phase become appreciable and increases with increasing Cl concentration. The etch rate is controlled by the Cl atom chemisorption step.     

IR study of the peculiarities of the stabilization of the NH4Na-Y zeolite structure during its hydrothermal dealumination

The variations in the structure of deep-level calcinated NH₄Na-Y zeolite (68 % NH₄ ⁺, Si/Al = 2.56) at 873 K (stage I of the hydrothermal dealumination) as a result of ammonation and subsequent calcination in water vapor at 973 and 1023 K (stageII) were studied using the IR spectra of zeolite framework vibrations. It was shown that ammonation of the product of stageI promotes the formation of linear disiloxane bonds and extra-framework =Al^VI-OH species identified by absorption at 482, 1196 cm^–1, and 524, 612, 829 cm^–1. The ammonation is also accompanied by an increase in the excessive negative framework charge (ENFC), which is manifested in the high-frequency (HF) shift of the bands that have maxima in thev _as (TO₄) region and equals 10 cm^–1, and also by a decrease in the unit cell parameter (a ₀) by 0.14 Å. The decrease in both the ENFC anda ₀ for the products of stageII, v _as (TO₄) = 10–20 cm^–1 and a ₀ = 0.07–0.14 Å, is due to the formation of nonlinear disiloxane bonds and non-framework aluminum hydroxide species identified by the absorption bands at 478, 1173 cm^–1 and 530, 615, 835 cm^–1.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 660–664, April, 1993.     

State of Co2+ ions in the structures of A and P1 type zeolites

Zeolite types A and P₁ containing Co²⁺ dopant ions were synthesized. Using the methods of optical electron spectroscopy and structural-sorption analysis it is shown that the Co²⁺ ions are localized in the exchange positions of the type-A zeolite and are occluded in its cavities in the form of insoluble compounds of the cobalt silicate type. In the structure of P₁-type zeolite the Co²⁺ ions not only occupy exchange positions, but enter the Si(Al)-O anion lattice. Co²⁺ Si⁴⁺(Al³⁺) isomorphism leads to significant changes in the vibrational spectra of the zeolite in the region of the Si(Al)-O stretching vibrations.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 24, No. 6, pp. 753–756, November–December, 1988.     

Darstellung und Eigenschaften einiger Hochchlorierter Oligosilane

Preparation and Properties of Some Highly Chlorinated Oligosilanes Tetrakis(trichlorosilyl)silane (neo-Si₅Cl₁₂) is cleaved by HCl in SiCl₄ solution to tris(trichlorosilyl)silane, HSi(SiCl₃)₃, and SiCl₄. HSi(SiCl₃)₃ and bis(trichlorosilyl)silane, H₂Si(SiCl₃)₂, can also be prepared in good yield by reaction of the methoxy compounds HSi[Si(OCH₃)₃]₃ and H₂Si[Si(OCH₃)₃]₂ with BCl₃. The mass, ¹H-n.m.r., and vibrational spectra of HSi(SiCl₃)₃ and H₂Si(SiCl₃) as well as some ¹H-n.m.r. data of HClSi(SiCl₃)₂, HCl₂SiSiCl₃ and H₂ClSiSiCl₃ are reported and discussed. An improved synthesis for neo-Si₅Cl₁₂ is given.     

Magic-Angle-Spinning NMR (MAS-NMR) Spectroscopy and the Structure of Zeolites

After outlining the chemical features and properties which make zeolites such an important group of catalysts and sorbents, the article explains how high-resolution solid-state NMR with magic-angle spinning reveals numerous new insights into their structure. ²⁹Si-MAS-NMR readily and quantitatively identifies five distinct Si(OAl)_n(OSi)_4-n structural groups in zeolitic frameworks (n = 0, 1,….4), corresponding to the first tetrahedral coordination shell of a silicon atom. Many catalytic and other chemical properties of zeolites are governed by the short-range Si, Al order, the nature of which is greatly clarified by ²⁹Si-MAS-NMR. It is shown that, as expected from Pauling's electroneutrality principle and Loewenstein's rule, both in zeolite X and in zeolite A (with Si/Al = 1.00) there are no ? Al? O? Al? linkages. In zeolite A and zeolite X with Si/Al = 1.00 there is strict alternation of Si and Al on the tetrahedral sites. Ordering models for Si/Al ratios up to 5.00 (in zeolite Y) may also be evaluated by a combination of MAS-NMR experiments and computational procedures. ²⁹Si-MAS-NMR spectra reveal the presence of numerous crystallographically distinct Si(OSi)₄ sites in silicalite/ZSM-5, suggesting that the correct space group for these related porosilicates is not Pnma. ²⁷Al-MAS-NMR clearly distinguishes tetrahedrally and octahedrally coordinated aluminum, proving that, contrary to earlier claims, Al in silicalite is tetrahedrally substituted within the framework. In combination, ²⁹Si- and ²⁷Al-MAS-NMR is a powerful tool for monitoring the course of solid-state processes (such as ultrastabilization of synthetic faujasites) and of gas-solid reactions (dealumination of zeolites with silicon tetrachloride vapor at elevated temperatures). They also permit the quantitative determination of framework Si/Al ratios in the region 1.00 < Si/Al < 10 000. Since most elements in the periodic table may be accommodated within zeolite structures, either as part of the exchangeable cations or as building units of the anionic framework, there is immense scope for investigation by MAS-NMR and its variants (cross-polarization, multiple pulse and variable-angle spinning) of bulk, surface and chemical properties. Some of the directions in which future research in zeolite science may proceed are adumbrated.     

Extra-framework aluminium in thermally treated zeolite CaA

Nuclear magnetic resonance spectra of aluminium including magic-angle spinning (²⁷Al MAS NMR) have been measured in order to study the dealumination which is caused by a heat treatment of zeolite CaA. The extra-lattice aluminium exists partly in the form of Al(OH)₄⁻ anions, corresponding to at most about 17% of lattice dealumination.     

IR study of heterogeneity of OH groups in zeolite HY-splitting of OH and OD bands

We have been studying the problem of heterogeneity of OH groups in zeolites HY for a long time. The heterogeneity was suggested by the shift of the IR band of OH groups restoring upon ammonia desorption and also by the fact that the band of OH groups forming hydrogen bonds was relatively broad (broader than for homogeneous acidic OH). In the present study we present another important argument for heterogeneity: the splitting of the IR band of free OH and OD groups in a zeolite of Si/Al=8.3 dealuminated by (NH₄)₂SiF₆ treatment. Such a splitting is the best seen in low temperature spectra of OD groups. We found less acidic 3640 cm⁻¹ (AlO)(SiO)₂SiO₁HAl(OSi)₃ and more acidic 3625 cm⁻¹ (SiO)₃SiO₁HAl(OSi)₃ groups. The presence of these two kinds of hydroxyls corresponds to the presence of Si(2Al) and Si(1Al), respectively, detected in ²⁹Si MAS NMR spectra. We also found a small amount of strongly acidic 3599 cm⁻¹ hydroxyls interacting with extraframework Al species.     

29Si-NMR-Untersuchungen zur Verteilung der Silicium-und Aluminiumatome im Alumosilicatgitter von Zeolithen mit Faujasit-Struktur

²⁹SiNMR Investigation of Silicon-Aluminum Ordering in the Aluminosilicate Framework of Faujasite-Type Zeolites The high resolution magic angle spinning ²⁹Si NMR spectra of a series of NaX and NaY zeolites with Si/Al ratios of 1.18 to 67 exhibit up to five sharp signals which could be assigned to the central silicon atoms of Si(OSi)_4–n(OAl)_n building units (n = 0–4) of the aluminosilicate framework. From the signal intensities the quantitative distribution of the building units and the Si/Al ratio of the aluminosilicate lattice have been estimated. By comparison of the building units obtained from the ²⁹Si NMR spectra with those from theoretical model structures detailed information on silicon-aluminum ordering of the zeolite framework has been derived. Except for NaX of Si/Al = 1.4 a centrosymmetrical distribution of Si and Al atoms within a double-cubooctahedra unit has been found which agrees well with the Si/Al ordering scheme proposed by Dempsey.     

Raman Spectroscopic Study of Aluminum Silicate Complexes at 20°C in Basic Solutions

Raman spectroscopic measurements were performed at ambient temperature onaqueous silica-bearing solutions (0.005 < m _Si < 0.02; 0 < pH < 14). The spectraare consistent with the formation of monomeric Si(OH)^o ₄, SiO(OH)^– ₃ andSiO₂(OH)^2– ₂ species at acid to neutral, basic, and strongly basic pH, respectively.Raman spectra of aqueous Al-bearing solutions at basic pH confirm thepredominance of the Al(OH)^– ₄ species in a wide concentration range (0.01 < m _Al < 0.1).Raman spectra of basic solutions (12.4 < pH < 14.3), containing both Al andSi, exhibit a strong decrease in intensities of SiO(OH)^– ₃, SiO₂(OH)^2– ₂, andAl(OH)^– ₄ bands in comparison with Al-free Si-bearing and Si-free Al-bearingsolutions of the same metal concentration and pH, suggesting the formation ofsoluble Al—Si complexes. The amounts of complexed Al and Si derived fromthe measurements of the Al and Si band intensities in strongly basic solutions(pH 14) are consistent with the formation, between Al(OH)^– ₄ andSiO₂(OH)^2– ₂, of the single Al—Si dimer SiAlO₃(OH)^3– ₄ according to the reactionSiO₂(OH)^2– ₂ + Al(OH)^– ₄ SiAlO₃(OH)^3– ₄ + H₂OAt lower pH ( 12.5) the changes in band intensities are consistent with theformation of several, likely more polymerized, Al—Si complexes.     

Comparison of catalytic performance of synthesized EU-1 zeolite with dealuminated EU-1 zeolite for <Emphasis Type="Italic">m</Emphasis>-xylene isomerization reaction

EU-1 zeolite was synthesized with high purity by a hydrothermal method and under optimum conditions: synthesis time 72 h, temperature 200°C, and aging time 12 h. Then, the synthesized EU-1 zeolite was modified by dealumination with nitric acid and the changes of the properties such as surface area, pore volume, and Si/Al ratio were investigated. The catalytic performance of these two catalysts was studied and compared with a commercial mordenite catalyst for meta-xylene isomerization reaction in a fixed bed reactor. The results showed that the modification of catalyst with acid increases Si/Al ratio from 25 to 50 due to the removal of a number of aluminium atoms from the framework of zeolite. Also the catalyst surface area increased from 300.237 m² g^?1 for EU-1 to 333.639 m² g^?1 for modified EU-1. According to results, the modified Eu-1 had higher para/ortho ratio, meta-xylene conversion, and para-xylene yield than EU-1 and commercial mordenite in the meta-xylene isomerization reaction.     

Catalytic activity of palladium supported on mesoporous modified Y-zeolite in methane combustion

Palladium-based catalysts were prepared by the ion-exchange method with dealuminated HY zeolite as support. The support dealumination was realised using acid solution of HNO₃, HCl or H₂SiF₆. The high activity of prepared catalysts for methane combustion was observed. This activity was dependent on the Al concentration, structural and textural properties of the support changed after the dealumination. Especially, Pd loaded on supports developing a second pore system, and having the highest Si/Al ratio, was more active than that on unmodified supports. It was also expected that the active sites in the methane combustion, which are suspected to be PdO, were influenced by the acidic properties of the support.     

Effect of alkaline modification of products of thermal vacuum and hydrothermal treatment of NH4Na-Y zeolite according to the IR spectral data

The effect of alkaline modification on the structure of the products of heat treatment of NH₄Na-Y zeolite (53% NH ₄ ⁺ , Si/Al - 2.37) in a vacuum at 573 K and in water vapors at 873 K was investigated with the IR spectrum of vibrations of the zeolite framework in the 400–1200 cm^–1 region. It was shown that the high-frequency shift of the bands in the spectra of the products obtained, the stretching vibration of v_as(TO₄) tetrahedrons in particular (T=Si, Al) at 1023 cm^–1 by 6 and 19 cm^–1, is determined by a decrease in the excess negative charge of the framework due to weakening and hydrolytic splitting of Al-O bonds of the deammoniated units with the formation of bridging Si-O(H)...Al and terminal Si-OHHO-Al hydroxyl groups. Treatment of these samples with an aqueous solution of KOH (pH 13.4) at 293 and 353 K restores the normal framework Si-O-Al bonds at the sites of formation of bridging and terminal hydroxyl groups. In the second case, restoration is hindered by substitution of H⁺ by K⁺ with some silanol groups.Institute of Physical Chemistry, Russian Academy of Sciences, 117915 Moscow. I. V. Grebenshchikov Institute of Silicate Chemistry, Russian Academy of Sciences, 199164 St. Petersburg. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1733–1739, August, 1992.     

1,3,2-Diazasilols based on 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene

Reduction of 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (1, dpp-bian) in the presence of SiCl₄ with two equivalents of potassium graphite (KC₈) in tetrahydrofuran leads to the formation of compound (dpp-bian)SiCl₂ (2), which was also synthesized by the exchange reaction of SiCl₄ with the magnesium complex (dpp-bian)Mg(THF)₃. An analog of compound 2, the bromo derivative (dpp-bian)SiBr₂ (3), was obtained by the reaction of SiBr4 with one equivalent of Na2(dpp-bian) (in situ from Na and dpp-bian) in toluene. The silylene (dpp-bian)Si (4) was synthesized by the reduction of a mixture of dpp-bian and SiCl₄ (1: 1) with four equivalents of potassium graphite in tetrahydrofuran. Treatment of compound 4 with diimine 1 gives the derivative (dpp-bian)₂Si (5). Compounds 2–5 were characterized by ¹H, ¹³C, and ²⁹Si NMR spectroscopy, as well as by elemental analysis, their molecular structure was established by X-ray diffraction studies.     

Kinetic exchange studies of metal ion substitution in EDTA chelates Fe(III)- UO2 EDTA exchange

A kinetic study of the exchange reaction between UO₂EDTA complex and Fe(III), at a constant ionic strength of 0.1, over the concentration range of 5×10^–3–1×10^–2 M of each reactant and pH 4.5–5.5 has been carried out radiometrically. The rate of the exchange process can be expressed by the equation: R=k₁[UO₂EDTA][Fe]+k₂[EDTA][H⁺]^–1. The activation parameters calculated were H^*=25.95 kJ mol^–1 and S^*=0.67 kJ mol^–1 K^–1.     

Nature and centers of localization of extraframework particles in Y zeolite dealuminated by silicon tetrachloride

X-ray diffraction, XPS, and NMR have been used to investigate the nature and centers of localization of nonframework particles in Y zeolite dealuminated by silicon tetrachloride. It has been established that the reaction products formed upon dealumination consist mainly of aluminum compounds that migrate from the volume of the zeolite to the surface and are also partially localized in internal supercages and small cages (sodalite cells). Water washing removes the particles localized in the supercages but does not affect the particles localized in sodalite cells. It has been shown that, by plotting maps of electron density on the basis of x-ray powder diffraction patterns, the sites of localization of extraframework particles can be determined. The results are consistent with those obtained by other methods, and the maps of electron density give a graphic picture of changes in internal structure of the Y zeolite.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1729–1734, August, 1989.The authors wish to express their appreciation to V. M. Mastikhin for assistance in taking the²⁷Al and²⁹Si NMR spectra.     

Modeling the similarities and differences between the sodalite cages (β-cages) in the generic materials

Initially in this review the sodalite framework [T₁₂O₂₄]^6– (T=Al, Si] is modeled with regular tetrahedra and disordered T atoms. Equations are given for calculating atomic coordinates from the unit cell parameter a and the T—O distancet; the expansion or contraction of the sodalite-cage is related quantitatively to changes ina through the cooperative twists of TO₄ tetrahedra about 4 axes and changes in < TOT bridge angles. The fully expanded cage has=0° and the maximum value ofa. The equations are general for any framework formed by isomorphous substitution of T by atoms other than Al, Si and for any SiAl ratio. The model and equations are extended to the zeolite A framework, which can be built from fully expanded sodalite cages. With the cooperative tilt of the TO₄ tetrahedra of zeolite A, described by Depmeier, the major variable features of the zeolite A framework are explained quantitatively. The faujasite framework has twisted-cages (>0), as in sodalite examples, and is quantitatively modeled most conveniently from sodalite examples with similar-cage contents. The review is extended to structures with T-ordering and distorted tetrahedra. Methods are given for estimating a for sodalites from a knowledge of the cavity contents, especially the sizes of cations and anions, and so on, present. Ways of predicting cavity sites in zeolite A as a function of cation size are presented, and the principal cavity sites in the faujasite-cage region are discussed. Finally the review considers isomorphous replacement of T atoms (Si or Al) by B, Be, Fe, Ga, Ge, and P; many of these substituted frameworks are stabilized by templates, or guest molecules, which reside in the cavities. Templates also stabilize Si, Al frameworks with high SiAl ratios. The modeling approach reviewed here is tested on a range of isomorphously substituted frameworks isotypic with sodalite; observed and calculated values of twist and 12O₂₄]^12– with distorted tetrahedra; these are structures with Al-O-Al bridges, which violate Loewenstein's Rule.     

ab initio calculations of complexes of group IVA tetrachlorides: I. Dynamics of complex formation of SiCl4 with pyridine

Quantum-chemical calculations of a trans-octahedral complex of SiCl₄ with pyridine involving complete optimization of its geometry and variation of the coordinate of the complex-formation reaction were fulfilled by the RHF/6-31G(d) method. The calculated electron distributions of chlorine atoms in the complex were confirmed by experimental ³⁵Cl NQR data. As the components of the system SiCl₄←2NC₅H₅ come closer together, the electron density on N atoms increases and on the Si atom decreases as a result of polarization of these components. On further mutual approach of the components, the electron density is transferred from the ligand to chlorine atoms (mainly on their p orbitals).     

Decomposition of SiCl4 and deposition of Si in inductively coupled plasmas of H2+SiCl4

The mechanism of homogeneous reactions in plasmas of H₂+5%SiCl₄ was studied by mass spectrometry and was compared to the mechanism observed in plasmas of Ar+H₂+SiCl₄. Contrary to the behavior with Ar, the results indicate that without argon the SiCl₄ molecule undergoes only fragmentation and the deposition proceeds through SiCl₂. No polymerization was observed. The deposition rates of c-Si were lower and the amounts of chlorine incorporated in the films were higher in the plasma of SiCl₄+H₂ than in the argon-containing plasma.