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.     

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.     

Si and Al MAS NMR characterization of non-hydrated zeolites Y upon adsorption of ammonia

Solid-state NMR characterization of zeolite catalysts in the hydrated state is often accompanied by an uncontrolled hydrolysis of the framework. In the present work it is demonstrated that the limitations occurring for ²⁹Si and ²⁷Al MAS NMR spectroscopy of non-hydrated zeolites Y, such as strong decrease of resolution and significant line broadening, can be overcome by loading these materials with ammonia. In the ²⁹Si MAS NMR spectra of non-hydrated and ammonia-loaded zeolites Y, no dehydration-induced high-field shift of Si(nAl) signals (n = 3, 2, 1) occurs, which is generally responsible for the loss of resolution in the spectra of non-hydrated materials. The ²⁷Al MAS NMR spectra of the non-hydrated and ammonia-loaded zeolites Y consist exclusively of signals of the tetrahedrally coordinated framework aluminum atoms with spectroscopic parameters similar to those of framework aluminum atoms in hydrated samples. The framework n_Si/n_Al ratios of the non-hydrated zeolites Y obtained by both ²⁹Si and ²⁷Al MAS NMR spectroscopy upon ammonia-loading agree well with each other.     

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.     

利用13C NMR技术探究叔胺溶液中HCO3-的生成

利用¹³C NMR技术对CO₂捕获叔胺溶剂进行了碳元素的定量研究,主要考察了对胺溶剂解吸热影响较大的HCO₃^-的生成规律。重点对叔胺分子结构中羟基官能团(-OH)、羟烷基数目、烷基支链及氮原子(N)所连接烷基链大小对胺溶剂生成HCO₃^-的影响。在20℃条件下分别对1 mol·L^-1具有不同CO₂负载的1-二甲基氨基-2-丙醇(1DMA2P)、N-甲基二乙醇胺(MDEA)、3-二甲氨基-1-丙醇(3DMA1P)、二乙氨基-2-丙醇(1DEA2P)、N,N-二乙基乙醇胺(DEEA)、N,N-二甲基乙醇胺(DMMEA)及三乙醇胺(TEA)溶液进行了¹³C NMR测试研究。实验结果显示:在相同浓度的叔胺水溶液中,同一CO₂负载下的叔胺-CO₂-水体系中HCO₃^-的含量顺序为:DMMEA > MDEA>3DMA1P > 1DMA2P > TEA > DEEA > 1DEA2P。通过对各叔胺分子结构中N原子的电子云密度大小及空间位阻效应分析,得出如下结论:3DMA1P分子中-OH官能团离N原子的距离大于其在DMMEA分子中的距离,导致其生成了较少的HCO₃^-;DMMEA分子中N原子上连接的烷基链小于DEEA分子中N原子上的烷基链,导致DMMEA溶液中生成了更多的HCO₃^-;MDEA分子中羟烷基数目少于TEA分子中的羟烷基数目,且MDEA比TEA多了一个甲基,导致MDEA溶液中含有更多的HCO₃^-;3DMA1P相比1DMA2P、DEEA相比1DEA2P分子中都少了一个甲基支链,导致3DMA1P溶液相比1DMA2P溶液、DEEA溶液相比1DEA2P溶液生成了更多的HCO₃^-。     

Two-dimensional H- and C-NMR spectra of some azo dyes containing amino or acetamido groups

The ¹H- and ¹³C-NMR spectra of 12 azo dyes containing amino or acetamido groups have been measured. Two-dimensional H,H-COSY, NOESY, H,C-COSY and COLOC spectra and one-dimensional selective INEPT spectra have been used in the assignment of ¹H and ¹³C chemical shifts. Hydrogen bonding has also been studied in these compounds.     

均三嗪衍生物比色识别Cu2+及荧光识别Zn2+

以对氨基苯腈、邻叔丁基苯酚和3,5-二叔丁基水杨醛为原料合成了两种含有均三嗪对称结构的离子探针1和2,通过核磁共振氢谱、核磁共振碳谱、红外、质谱对合成产物进行表征,确认其结构。利用紫外吸收光谱和荧光光谱两种手段分别考察了探针1和探针2在N,N-二甲基甲酰胺（DMF）溶液中对金属离子（Cr³⁺、Mn²⁺、Fe³⁺、Co²⁺、Ni²⁺、Cu²⁺、Zn²⁺、Cd²⁺、Hg²⁺）的识别性能,通过核磁共振氢谱对探针1与Zn²⁺的识别机理进行研究。结果表明,两种探针热稳定性强,探针1溶液中加入Zn²⁺会引起荧光强度的显著增强,抗干扰性强,是一种高选择性识别Zn²⁺的荧光增强型探针;探针2中加入Cu²⁺后溶液由无色变成黄色,紫外光谱长波长处出现新吸收峰,是一种可裸眼识别的、高效的紫外Cu²⁺探针。     

Co2+掺杂ZnO-MgO-Al2O3-SiO2系微晶玻璃的制备及光学性能

本文采用熔融法和热处理制备了Co²⁺掺杂的ZnO-MgO-Al₂O₃-SiO₂(ZMAS)系透明微晶玻璃,基于X射线衍射的结果确定了微晶玻璃的主要晶相为ZnAl₂O₄/MgAl₂O₄,并且随着晶化处理时间的增加,微晶玻璃的物相构成没有发生明显变化,尖晶石相的结晶度和平均晶粒尺寸呈现先增大后减小的趋势。吸收光谱和发射光谱的结果表明Co²⁺进入了尖晶石相ZnAl₂O₄/MgAl₂O₄中,并取代了四面体位置(T_d)的Zn²⁺或Mg²⁺。随着晶化处理时间的增加,样品的吸收光谱强度和发射光谱强度均呈现先升高后降低的趋势,这与X射线衍射结果的变化趋势一致,说明可以通过控制微晶玻璃的结晶度来调控光学性能,这对制备性能优良的微晶玻璃材料具有一定的指导意义。对比了采用不同价态Co的氧化物原料制备的微晶玻璃,结果表明无论是掺杂CoO还是Co₂O₃,微晶玻璃尖晶石相中的Co元素均以Co²⁺形式存在。此外,将所制备的微晶玻璃材料在1 540 nm处的基态吸收截面(σ_gas)同Co掺杂的其他基体材料进行了对比,发现它有望作为可饱和吸收体应用于调Q激光器中。     

EPR and optical spectra of Cu2 in dioptase

EPR and optical absorption studies of Dioptase have been carried out at room and low temperatures. The observed, absorption bands have been attributed to Cu²⁺ ion in C_4V symmetry. From the g-values, the ground state of Cu²⁺ is found to be ²B₁. The octahedral and tetragonal field parameters and the spin-orbit reduction parameters have been evaluated. The NIR and IR spectra have also been reported.     

Zeolite synthesis in the presence of flexible diquaternary alkylammonium ions (C2H5)3N(CH2)nN(C2H5)3 with n=3–10 as structure-directing agents

The use of flexible diquaternary alkylammonium ions (C₂H₅)₃N⁺(CH₂)_nN⁺(C₂H₅)₃ (Et₆-diquat-n with n=3–10) as structure-directing agents for zeolite synthesis in the presence of alkali metal cation is described. Among the organic structure-directing agents studied here, a considerable diversity in the phase selectivity was observed only for the Et₆-diquat-5 ion: this cation can produce five different zeolite structures (i.e., P1, SSZ-16, SUZ-4, ZSM-57, and mordenite), depending on the oxide composition of synthesis mixtures. Analysis of the variable-temperature ¹H CRAMPS NMR spectra obtained from the Et₆-diquat-5 molecules in these five zeolites reveals that the host–guest interactions occurring within the respective materials maintain in a manner different from one another even at 160 °C at which the zeolite hosts crystallize.     

Solid-state V NMR for characterization of vanadium-containing systems

This overview paper includes both published and original data of the current state of the field of ⁵¹V NMR in solid-state chemistry. Advantages and shortcomings of different NMR techniques in their applications to vanadium are discussed on the examples of their application to various vanadia based systems (including individual highly crystalline compounds, solid solutions, glasses, catalysts). New correlations between local structure of vanadium atoms and NMR parameters allowing to discriminate at least seven different types of vanadium sites (tetrahedral sites of Q⁰, Q¹ and Q² types; trigonal pyramids of 3=1 and 3=2 (V₂O₅ like) types; tetragonal pyramids of 4=1, 4=2 types) are proposed. It is demonstrated that competent combination of different NMR approaches permits now not only to describe different vanadium sites in highly crystalline and amorphous materials, but also to insight into the structural aspects of disorder in crystallinity as well as to reveal the behavior of different functional groups at elevated temperatures. The influence of low valence vanadium atoms on ⁵¹V NMR spectra is also discussed.     

苯并噻唑基修饰的开链Cu2+比色探针的合成及性能

以N-苯基二乙醇胺和2-巯基苯并噻唑为原料通过亲核取代反应合成了一种新型的苯并噻唑基修饰的开链冠醚类化合物1,并用核磁共振氢谱, 核磁共振碳谱及元素分析方法对合成产物进行了表征。利用紫外光谱仪考察了化合物1与多种金属离子（Mn²⁺、Co²⁺、Cu²⁺、Zn²⁺、Ni²⁺ 、Fe³⁺、 Hg²⁺、Cr³⁺、Al³⁺）在乙腈溶液中的光谱变化,并探究了化合物1处理过的滤纸条在水溶液中对金属离子的识别效果,通过核磁共振氢谱讨论了化合物1与金属离子形成配合物的作用机理。实验发现,化合物1的乙腈溶液中添加Cu²⁺后溶液颜色变为棕色,明显区别于添加其他离子;在水溶液中,特制的滤纸条遇到Cu²⁺会呈现黄色,而遇其他离子均无颜色变化。结果表明,化合物1仅对Cu²⁺具有选择性,且能通过裸眼进行识别,是一种高效、简便的Cu²⁺探针。     

Synthesis and crystal structure of carbonate cancrinite Na8[AlSiO4]6CO3(H2O)3.4, grown under low-temperature hydrothermal conditions

The synthesis of cancrinite in the system Na₂O–SiO₂–Al₂O₃–Na₂CO₃–H₂O was studied under low-temperature hydrothermal conditions in the 353 K<T<473 K interval. The aim was to reveal the suitable range for the crystallization of pure-phase carbonate cancrinite with the ideal composition Na₈[AlSiO₄]₆CO₃(H₂O)₂ without cocrystallization of sodalite or intermediate disordered phases between cancrinite and sodalite. It was found that cancrinite formation reacts very sensitive on the temperature within the autoclaves whereas the concentration of reactants and the alkalinity of the hydrothermal solution have a much lower influence on the phase formation. Thus the temperature of crystallization of carbonate cancrinite without any by-products should not remain below 473 K. At the lower reaction temperature of 353 K the formation of a disordered intermediate phase between the cancrinite and the sodalite structure has been obtained in every case, independent of the template concentrations and the base. Some problems to detect this in a typical powder product mixture are discussed. Besides the ²⁹Si and ²⁷Al MAS NMR characterization of the products, the crystal structure refinement of pure carbonate cancrinite of ideal composition Na₈[AlSiO₄]₆CO₃(H₂O)_3.4, has been carried out from X-ray powder data using the Rietveld method: P6₃, a=1271.3(1) pm, c=518.6(1) pm, R_WP=0.073, R_F=0.016 for 347 structure factors and 45 variable positional parameters.     

铝合金表面钒酸铈改性环氧涂层的制备与性能研究

通过水热合成法制备钒酸铈(CeVO4)纳米填料,将CeVO4分散到环氧树脂中获得改性涂层.分别涂覆在打磨后碱洗处理铝合金和直接喷砂处理铝合金上.采用XRD、FT-IR和SEM对CeVO4粉体进行表征,并通过附着力测试、电化学阻抗和长期浸泡实验对改性前后的涂层进行研究.结果表明:利用水热合成法可成功制备CeVO4纳米填料...     

Spectroscopic and corrosion resistance characterization of GLYMO–TEOS Ormosil coatings for aluminum alloy corrosion inhibition

Corrosion resistance properties of spray- and dip-coated 3-glycidoxypropyltrimethoxysilane (GLYMO)–tetraethoxysilane (TEOS) Ormosil films have been investigated using salt spray analysis. ¹H–¹³C and ¹H–²⁹Si CP/MAS NMR analyses indicate that organic content and hydrolysis water ratio affect the Ormosil structure, and in turn, the corrosion resistance properties of the Ormosil film. For spray-coated samples, films derived from the 11 mol% GLYMO Ormosil prepared using hydrolysis water content (W=2 and 4) provided good corrosion protection, as this combination of organic content, water ratio, and deposition method produced films of the appropriate thickness, hydrophobicity, and density for good corrosion protection. Films prepared from high organic contents (25 and 67 mol% GLYMO) and low hydrolysis water content values (W=1 and 2) exhibited the best corrosion resistance for films prepared by dip coating. Presumably, these films comprise a dense network structure with organic groups dispersed throughout the film, providing a hydrophobic barrier coating capable of repelling water and corrosion initiators.     

Synthesis, structure and thermal properties of a novel 3D aluminophosphate UiO-26

The synthesis of a novel 3D aluminophosphate is described. The thermal properties of the material were investigated, and the existence of three high-temperature variants was revealed. The crystal structures of the as-synthesized material (UiO-26-as) and the material existing around 250°C (UiO-26-250) were solved from powder X-ray diffraction data. UiO-26-as with the composition [Al₄O(PO₄)₄(H₂O)]²⁻[NH₃(CH₂)₃NH₃]²⁺ crystallizes in the monoclinic space group P2₁/c (no. 14) with a=19.1912(5), b=9.3470(2), c=9.6375(2) Å and β=92.709(2)°. It exhibits a 3D open framework consisting of connections by PO₄ tetrahedra with AlO₄ tetrahedra, AlO₅ trigonal bipyramids and AlO₅(H₂O) octahedra forming two types of layers stacked along [1 0 0] and connected by Al–O–P bondings. The structure possesses a 1D 10-ring channel system running along [0 0 1], in which doubly protonated 1,3-diaminopropane molecules are located. UiO-26-250 with the composition [Al₄O(PO₄)₄]²⁻[NH₃(CH₂)₃NH₃]²⁺ crystallizes in the monoclinic space group P2₁/c with a=19.2491(4), b=9.27497(20), c=9.70189(20) Å and β=93.7929(17)°. The transformation to UiO-26-250 involves removal of the water molecule which originally is coordinated to aluminum. The rest of the structure remains virtually unchanged. The crystal structures of the two other variants existing around 400 (UiO-26-400) and 600°C (UiO-26-600) remain unknown.     

In situ solid-state NMR studies of ethanol photocatalysis: characterization of surface sites and their reactivities

In situ solid-state NMR methodologies have been employed to investigate the photocatalytic oxidation of ethanol (C₂H₅OH) over two TiO₂-based catalysts, Degussa P-25 powder and a monolayer TiO₂ catalyst dispersed on porous Vycor glass. Two adsorption sites were observed for ethanol, a chemisorbed species identified as an ethoxide species, and a hydrogen-bonded species. The Ti-bound ethoxide was found to be the more photocatalytically reactive species. ¹³C magic-angle spinning (MAS) experiments revealed that long-lived intermediates, including acetaldehyde (CH₃CHO), acetic acid, formic acid, and acetate were observed under dry conditions and in the presence of molecular oxygen. Similar reaction intermediates form on the surfaces of both catalysts. ¹³C cross-polarization MAS experiments allowed us to identify and follow the evolution of surface-bound species during UV irradiation. Acetate, which forms from mobile acetic acid, appears to be bound to the non-irradiated surfaces of the powdered TiO₂ catalyst, and was also observed on the surface of TiO₂/PVG catalyst, and further degradation was not possible. The presence of molecular oxygen was found to be essential for photooxidation to proceed.     

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.     

Spectroscopic analysis of carbon dioxide and nitrogen mixed gas hydrates in silica gel for CO2 separation

In this study solid-state NMR spectroscopy was used to identify structure and guest distribution of the mixed N₂ + CO₂ hydrates. These results show that it is possible to recover CO₂ from flue gas by forming a mixed hydrate that removes CO₂ preferentially from CO₂/N₂ gas mixture. Hydrate phase equilibria for the ternary CO₂–N₂–water system in silica gel pores were measured, which show that the three-phase H–L_w–V equilibrium curves were shifted to higher pressures at a specific temperature when the concentration of CO₂ in the vapor phase decreased. ¹³C cross-polarization (CP) NMR spectra of the mixed hydrates at gas compositions of more than 10 mol% CO₂ with the balance N₂ identified that the crystal structure of mixed hydrates as structure I, and that the CO₂ molecules occupy mainly the abundant 5¹²6² cages. This makes it possible to achieve concentrations of more than 96 mol% CO₂ gas in the product after three cycles of hydrate formation and dissociation.