A study of silver species on silver-exchanged ETS-10 and mordenite by XRD, SEM and solid-state 109Ag, 29Si and 27AI NMR spectroscopy

Silver zeolites, especially Ag-ETS-10 and Ag-mordenite, actively bind xenon and iodine, two prime contaminants common to nuclear accidents. The evolution of silver species on silver exchanged ETS-10 (Ag/ETS-10) and mordenite (Ag/Mor) has been investigated by exposing the materials to a series of activation conditions in Ar, air and H2. The samples were characterized by XRD, SEM and solid-state 109Ag, 29Si and 27AI MAS NMR. The silver reduction and structural evolution have been illustrated by those techniques. The effectiveness of one sample of each type of sieve was tested for its ability to trap mercury from a gas stream. However, the results from this study demonstrate that the adsorption characteristics of silver-loaded sieves cannot necessarily be predicted using a full complement of structural characterization techniques, which highlights the importance of understanding the formation and nature of silver species on molecular sieves.     

沸石降解法合成孔壁含有沸石结构单元的介孔结构材料

提出了一种合成孔壁含有沸石结构单元的介孔结构材料的新方法一降解法,即利用不同硅铝比的β沸石和ZSM-5沸石为原料在碱溶液中处理得到降解液,然后以此降解液为硅铝源在表面活性剂P123的模板作用下组装了孔结构类型为SBA-15的介孔结构材料,分别简称为MSB(β沸石降解合成)和MSZ(ZSM-5沸石降解合成).产物的IR光谱、N₂吸附、29Si MAS NMR图谱和对重芳烃的加氢脱烷基反应催化活性均说明降解法合成的介孔结构材料MSB和MSZ的孔壁中含有了沸石的结构单元.     

Slow motion of confined molecules: NMR and broadband dielectric spectroscopy investigations

Nuclear magnetic resonance (NMR) and broadband dielectric spectroscopy are used to investigate the dynamics of small glass-forming molecules confined to restricted geometries. Ethylene glycol molecules are embedded in the supercages of NaX zeolites. The combined application of NMR and broadband dielectric spectroscopy advances the understanding of the slowing down of the motion near the glass transition temperature of these confined molecules. In combination with nuclear spin relaxation and nuclear magnetic resonance spectroscopy, dielectric relaxation studies on glass forming molecules allow conclusions on the character of the motion. High resolution 1H magic angle spinning (MAS) NMR measurements not only enable a characterisation of the state of the adsorbed molecules via a chemical shift analysis. By means of an analysis of MAS spinning sidebands we may also estimate a correlation time the meaning of which will be discussed in comparison to the results of longitudinal proton spin relaxation measurements. In addition to broadband dielectric spectroscopy slow molecular motions of partially deuterated ethylene glycol adsorbed in NaX are studied by means of 2H NMR line-shape analysis.     

(Na4BH4) guests inside aluminosilicate, gallosilicate and aluminogermanate sodalite host frameworks studied by H, B, and Na MAS NMR spectroscopy

We report tetrahydroborate aluminosilicate, gallosilicate and aluminogermanate sodalites studied by ¹¹B, ¹H and ²³Na MAS NMR spectroscopy. The spectral parameters are consistent with the local environments of each investigated nucleus obtained from the crystal structures. The ¹¹B MAS NMR spectra exhibit a sharp narrow line at about −49.0 ppm, which is assigned to BH₄⁻ enclathrated into the sodalite framework matrix. The lineshape of the signal shows no quadrupolar interactions due to discreteness and high symmetry of the BH₄⁻ unit as well as possible fast dynamic site exchange of hydrogen atoms. The ²³Na MAS NMR signals also show a narrow Gaussian lineshape, which clearly indicates a single type of sodium coordination, and a centrosymmetrical charge distribution around the sodium atom. The ¹H MAS NMR spectra can clearly distinguish between hydrogen in BH₄⁻ anions (−0.6 ppm), H₃O₂⁻ anions (1.2 ppm) and H₂O molecules (5.0 ppm). The structural properties of BH₄⁻ intercalation into sodalite framework matrix help connect the microporous materials to hydride-containing A, X and Y type zeolites.     

Growth of calcium phosphate on phosphorylated chitin fibres

Calcium phosphate growth on chitin phosphorylated fibres was studied using scanning electron microscopy and energy dispersive X-ray analysis (SEM, EDX), micro-Fourier transform infrared spectroscopy (FTIR), and solid state magic angle spinning nuclear magnetic resonance (MAS NMR) techniques. The C6 chemical shift positions of 13C MAS NMR in the chitin fibres phosphorylated using urea and H3PO4 are obvious indicating that phosphorylation takes place not in the C1 but in the C6 region. Micro-FTIR and 31P MAS NMR suggested that ammonium hydrogen phosphate formed during the phosphorylation procedure. Chitin fibres phosphorylated using urea and H3PO4 and then soaked in saturated Ca(OH)2 solution at ambient temperature, which lead to the formation of thin coatings formed by partial hydrolysis of the PO4 functionalities, were found to stimulate the growth of a calcium phosphate coating on their surfaces after soaking in 1.5×SBF solution for as little as one day. The thin layer after Ca(OH)2 treatment functioned as a nucleation layer for further calcium phosphate deposition after soaking in 1.5×SBF solution. EDX-measured Ca : P ratios of the coatings of Ca(OH)2-treated phosphorylated chitin in 1.5×SBF solution suggested that calcium-deficient apatite was formed.     

Local structures of mesoporous bioactive glasses and their surface alterations in vitro: inferences from solid-state nuclear magnetic resonance

We review the benefits of using (29)Si and (1)H magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy for probing the local structures of both bulk and surface portions of mesoporous bioactive glasses (MBGs) of the CaO-SiO(2)-(P(2)O(5)) system. These mesoporous materials exhibit an ordered pore arrangement, and are promising candidates for improved bone and tooth implants. We discuss experimental MAS NMR results from three MBGs displaying different Ca, Si and P contents: the (29)Si NMR spectra were recorded either directly by employing radio-frequency pulses to (29)Si, or by magnetization transfers from neighbouring protons using cross polarization, thereby providing quantitative information about the silicate speciation present in the pore wall and at the MBG surface, respectively. The surface modifications were monitored for the three MBGs during their immersion in a simulated body fluid (SBF) for intervals between 30 min and one week. The results were formulated as a reaction sequence describing the interconversions between the distinct silicate species. We generally observed a depletion of Ca(2+) ions at the MBG surface, and a minor condensation of the silicate-surface network over one week of SBF soaking.     

Local structures and photocatalytic reactivities of the titanium oxide and chromium oxide species incorporated within micro- and mesoporous zeolite materials: XAFS and photoluminescence studies

Transition metal oxides (titanium, chromium oxides) photocatalysts can be designed within the cavities and frameworks of various zeolites and mesoporous molecular sieves by ion-exchange and hydrothermal synthesis. A combination of in situ XAFS and photoluminescence spectroscopic techniques has revealed that these transition metal oxide species incorporated within zeolites exist in a highly dispersed state with a tetrahedral coordination and such a high dispersion state allows them to act as efficient photocatalysts for various photocatalytic reactions. These results clearly suggest that the utilization of zeolites and mesoporous materials is one of the most promising approaches to design and development of highly efficient and effective photocatalysts with well-defined local structures at the molecular level.     

Synthesis of 3-dimensional mesoporous silica using a di-block copolymer template

Exploring polymeric surfactants as templates for synthesizing ordered mesoporous silicas has become increasingly important for both academic interests and industrial applications. In this work, we employed C₁₆EO₄₀, a di-block copolymer polyethylene-poly(ethylene oxide), as template in an attempt to synthesize a modified 3-dimensional wormhole mesoporous silicas (WMS-39). In addition, various synthesizing conditions were investigated, including pre-hydrolysis time of TEOS, reaction temperatures and the ratios of TEOS to template. The products were characterized using powder XRD, TEM, ²⁹Si MAS NMR and nitrogen adsorption measurements. The characteristics of as-synthesized mesoporous silica were compared with SBA-15, a highly ordered mesoporous silica, prepared using non-ionic tri-block copolymers of poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) as templates. The WMS-39 materials have a BET surface area of 600–970 m²/g and narrowly distributed pore diameter around 3.9 nm. The morphology of WMS-39 was found to be wormhole framework as indicated in TEM diagrams. Thermal transformation of the as-synthesized mesoporous materials were carefully analyzed with TGA/DTA. Findings obtained from this work enable us to propose a modified assembly mechanism of mesoporous silicas.     

Template-directed synthesis of mesoporous silicas containing phosphonic acid derivatives in the surface layer

A template-directed process, using 1-dodecylamine as a template, is developed for the synthesis of mesoporous silicas containing the phosphonic acid derivatives ≡Si(CH₂)₂P(O)(OC₂H₅)₂ and ≡Si(CH₂)₃P(O)(CH₃)(ONa) in the surface layer. The porous materials obtained by removing the template with boiling methanol have specific surfaces of 854 and 505 m²/g, accessible pore volumes of 0.42 and 0.37 cm³/g, and pore diameters of 2.2 and 2.5 nm, respectively. As shown by scanning electron microscopy and x-ray diffraction, the mesoporous silicas are nonuniform in particle shape and size, and their structure is less ordered than that of classic mesoporous silicas, such as MCM-41. IR and ¹³C, ³¹P, and ²⁹Si CP/MAS NMR spectroscopy data indicate that, in the surface layer of the mesoporous silica prepared with the use of ≡Si(CH₂)₂P(O)(OC₂H₅)₂, the functional groups are present in the form of T ² and T ³ structural units. In addition, the surface layer contains alkoxy groups and water, which participates in hydrogen bonding.     

Detection of Brønsted acid sites in zeolite HY with high-field 17O-MAS-NMR techniques

The acidity and unique porous structures of zeolites play an important role in controlling the activity and selectivity of many zeolite-based catalysts. Although (27)Al, (29)Si and (1)H NMR spectroscopy represent standard analytical tools with which to study these materials, (17)O-NMR investigations are much less routine, owing to the very low natural abundance of (17)O (0.037%), its relatively low resonant frequency and its large quadrupole moment. (17)O-NMR resonances from framework oxygen sites in a variety of zeolites have been detected, but the (17)O-NMR resonance from oxygen directly bound to the Br?nsted acid site (Si-O(H)-Al) has remained elusive. Here we report the direct observation of this resonance in dehydrated zeolite HY, by using high magnetic-field strengths. (17)O-(1)H double-resonance NMR experiments are used to prove unambiguously that the (17)O signal arises from O nearby H atoms. A large quadrupolar coupling constant, the measure of the local distortion of this site, of 6.6 MHz is determined, which is similar to that obtained in ab initio calculations of zeolite HY-like clusters; this value drops to 5 MHz on acetone binding. The results presented in this paper open up methods for characterizing zeolite acidity and investigating H(+)-sorbent interactions.     

Curing of carbon-fibre reinforced epoxy resin; non-invasive viscosity measurement by NMR imaging

Nuclear magnetic resonance (NMR) images have been obtained from small-scale samples (multi-laminate and rolled) made from a continuous carbon-fibre reinforced epoxy resin. Empirical relationships may be established between the image intensity observed and the internal viscosity of the polymer phase. Using slice-selective techniques, it is possible to obtain internal images, and hence measure local internal viscosity, non-invasively during the curing process. The results show that NMR imaging may be useful in optimizing both the processing conditions and performance of such materials by enabling the measurement of curing characteristics during manufacture.     

Structural and spatially resolved studies on the hardening of a commercial resin-modified glass-ionomer cement

A commercial photopolymerizable resin-modified glass-ionomer (Fuji II LC) was studied using a variety of nuclear magnetic resonance (NMR) techniques. ¹H and ¹⁹F stray-field imaging (STRAFI) enabled to follow the acid–base reaction kinetics in self-cured (SC) samples. Gelation and maturation processes with 25 min and 40 h average time constants, respectively, were distinguished. In self- & photo-cured (SPC) samples, two processes were also observed, which occurred with 2 s and 47 s average time constants. ¹H, ²⁷Al and ²⁹Si magic angle spinning (MAS) NMR, ¹³C cross-polarization (CP)/MAS NMR and ²⁷Al multiple quanta (MQ)MAS NMR spectroscopy were used to obtain structural information on the glass and cements that were either SC or SPC. The presence of methacrylate groups was identified in the solid component. Unreacted hydroxyl ethylmethacrylate (HEMA) was detected in self-cured cement. ²⁷Al data showed that approximately 28% and 20% of Al is leached out from glass particles in SC and SPC samples, respectively. The upfield shift detected in ²⁹Si MAS NMR spectra of the cements is consistent with a decrease in the number of Al species in the second coordination sphere of the silicon structures. Scanning electron microscopy (SEM) showed existence of 3D shrinkage of the cement matrix in photo-cured cements.     

Chain order and mobility of high-density c(18) phases by solid-state NMR spectroscopy and liquid chromatography

C(18) phases prepared by different synthetic pathways are examined by solid-state NMR spectroscopy. Silane functionality is clearly indicated by (29)Si CP/MAS NMR spectroscopy. Order and mobility of the alkyl chains are investigated with high-speed (1)H MAS and (13)C CP/MAS NMR spectroscopy. Differences in coverage are monitored by (1)H line widths,( 13)C chemical shifts, (13)C cross-polarization constants, and (1)H relaxation times in the rotating frame. It is shown that C(18) phases prepared by the surface polymerization technique exhibit a more regular surface coverage than sorbents prepared by conventional polymeric synthesis. The findings from solid-state NMR investigations are discussed in the context of liquid chromatography (LC) separations of linear and bulky polycyclic aromatic hydrocarbon (PAH) solutes.     

Poly(ethylene-co-acrylic acid) stationary phases for the separation of shape-constrained isomers

A new approach for the synthesis of long alkyl chain length stationary phases for use in reversed-phase liquid chromatography is described. Poly(ethylene-co-acrylic acid) copolymers (i.e., (-CH2CH2-)x[CH2CH(CO2H)-]y) with different levels of acrylic acid were covalently bonded to silica via glycidoxypropyl or aminopropyl linkages. 13C cross polarization magic angle spinning (CP/MAS) nuclear magnetic resonance (NMR) spectroscopy was used to characterize the new reversed-phase materials. Aspects of shape selectivity were evaluated for six different columns with Standard Reference Material (SRM) 869a, Column Selectivity Test Mixture for Liquid Chromatography. Selectivity for isomer separations was enhanced for stationary phases prepared with poly(ethylene-co-acrylic acid) containing a mass fraction of 5% acrylic acid. The relationship between alkyl conformation and chromatographic properties was studied by 13C magic angle spinning (MAS) NMR measurements, and correlations were made with the composition of the polymer. Finally, the effectiveness of this phase is demonstrated by the separation of several beta-carotene isomers.     

Zeolite (In)Stability under Aqueous or Steaming Conditions

Zeolites are among the most environmentally friendly materials produced industrially at the Megaton scale. They find numerous commercial applications, particularly in catalysis, adsorption, and separation. Under ambient conditions aluminosilicate zeolites are stable when exposed to water or water vapor. However, at extreme conditions as high temperature, high water vapor pressure or increased acidity/basicity, their crystalline framework can be destroyed. The stability of the zeolite framework under aqueous conditions also depends on the concentration and character of heteroatoms (other than Al) and the topology of the zeolite. The factors critical for zeolite (in)stability in the presence of water under various conditions are reviewed from the experimental as well as computational sides. Nonreactive and reactive interactions of water with zeolites are addressed. The goal of this review is to provide a comparative overview of all-silica zeolites, aluminosilicates and zeolites with other heteroatoms (Ti, Sn, and Ge) when contacted with water. Due attention is also devoted to the situation when partial zeolite hydrolysis is used beneficially, such as the formation of hierarchical zeolites, synthesis of new zeolites or fine-tuning catalytic or adsorption characteristics of zeolites.     

Controlled silica synthesis inspired by diatom silicon biomineralization

Silica becomes increasingly used in chemical, pharmaceutical, and (nano)technological processes, resulting in an increased demand for well-defined silicas and silica-based materials. The production of highly structured silica from cheap starting materials and under ambient conditions, which is a target for many researchers, is already realized in the formation of diatom biosilica, producing highly hierarchical ordered meso- and macropores silica structures. This notion formed the starting point in our integrative biomolecular and biomimetic study on diatom silicon biomineralization in which we have analyzed silica transformations and structure-direction in polymer-mediated silica syntheses using a combination of (ultra)small-angle X-ray scattering and (cryo)electron microscopy. Using bio-analogous reaction conditions and reagents, such as waterglass and (combinations of) polyethylene oxide (PEO) based polymers, we demonstrate in this review the synthesis of tailor-made mesoporous silicas in which we can, as in biosilica synthesis, control the morphological features of the resulting materials on the nanometer level as well as on the micrometer level.     

Solid-state NMR and TGA studies of silver reduction in chabazite

Silver-exchanged molecular sieves have shown great promise in applications ranging from antimicrobial materials to the adsorption of xenon and iodide, two key contaminants emitted from nuclear reactors. In this work, solid-state 27Al and 29Si MAS NMR and TGA were used to study silver reduction in silver-exchanged chabazite under various thermal conditions. The solid-state NMR results for both 27Al and 29Si show that there are no major changes in the chabazite during silver reduction in an argon stream; however a progressive structural change does take place in the hydrogen stream. The structural change likely involves breaking the silicon oxygen bond of the Si-O-AI fragment of chabazite, leading to the formation of extra-framework aluminum oxide. The TGA results at temperatures up to 600 degrees C indicate that silver reduction is less complete in an argon stream than in a hydrogen stream. In this paper we propose that silver reduction occurs via the following reactions: 2(Ag + ZO-)+H2O --> 1/2O2+2Ag0 + 2ZOH and nAg + mAg = Ag(m+n)n+ (in an argon stream); and Ag(+) + ZO(-) + 1/2H2 = Ag0 + ZOH and 2ZOH = ZO(-) + Z(+) + H2O (in a hydrogen stream).     

Nanopore-Supported Metal Nanocatalysts for Efficient Hydrogen Generation from Liquid-Phase Chemical Hydrogen Storage Materials

Hydrogen has emerged as an environmentally attractive fuel and a promising energy carrier for future applications to meet the ever-increasing energy challenges. The safe and efficient storage and release of hydrogen remain a bottleneck for realizing the upcoming hydrogen economy. Hydrogen storage based on liquid-phase chemical hydrogen storage materials is one of the most promising hydrogen storage techniques, which offers considerable potential for large-scale practical applications for its excellent safety, great convenience, and high efficiency. Recently, nanopore-supported metal nanocatalysts have stood out remarkably in boosting the field of liquid-phase chemical hydrogen storage. Herein, the latest research progress in catalytic hydrogen production is summarized, from liquid-phase chemical hydrogen storage materials, such as formic acid, ammonia borane, hydrous hydrazine, and sodium borohydride, by using metal nanocatalysts confined within diverse nanoporous materials, such as metal–organic frameworks, porous carbons, zeolites, mesoporous silica, and porous organic polymers. The state-of-the-art synthetic strategies and advanced characterizations for these nanocatalysts, as well as their catalytic performances in hydrogen generation, are presented. The limitation of each hydrogen storage system and future challenges and opportunities on this subject are also discussed. References in related fields are provided, and more developments and applications to achieve hydrogen energy will be inspired.     

Synthesis of Engineered Zeolitic Materials: From Classical Zeolites to Hierarchical Core–Shell Materials

The term “engineered zeolitic materials” refers to a class of materials with a rationally designed pore system and active‐sites distribution. They are primarily made of crystalline microporous zeolites as the main building blocks, which can be accompanied by other secondary components to form composite materials. These materials are of potential importance in many industrial fields like catalysis or selective adsorption. Herein, critical aspects related to the synthesis and modification of such materials are discussed. The first section provides a short introduction on classical zeolite structures and properties, and their conventional synthesis methods. Then, the motivating rationale behind the growing demand for structural alteration of these zeolitic materials is discussed, with an emphasis on the ongoing struggles regarding mass‐transfer issues. The state‐of‐the‐art techniques that are currently available for overcoming these hurdles are reviewed. Following this, the focus is set on core–shell composites as one of the promising pathways toward the creation of a new generation of highly versatile and efficient engineered zeolitic substances. The synthesis approaches developed thus far to make zeolitic core–shell materials and their analogues, yolk–shell, and hollow materials, are also examined and summarized. Finally, the last section concisely reviews the performance of novel core–shell, yolk–shell, and hollow zeolitic materials for some important industrial applications.     

Modulus-density scaling behaviour and framework architecture of nanoporous self-assembled silicas

Natural porous materials such as bone, wood and pith evolved to maximize modulus for a given density. For these three-dimensional cellular solids, modulus scales quadratically with relative density. But can nanostructuring improve on Nature's designs? Here, we report modulus-density scaling relationships for cubic (C), hexagonal (H) and worm-like disordered (D) nanoporous silicas prepared by surfactant-directed self-assembly. Over the relative density range, 0.5 to 0.65, Young's modulus scales as (density)n where n(C)相似文献