Amino-Modified Silicate Xerogels Complexed with Cu(II) as Catalyst Precursors. Coordination State and Thermal Decomposition

The sol-gel process is a useful method for preparing two series of organically and co-ordinately modified xerogels of the types [CuN _n ]·N _5–n ·5xSiO_4/2 (n < 4) and [Cu(N–N)_n]·(N–N)_2–n ·2x SiO_4/2(n 2), where N = NH₂(CH₂)₃ SiO_3/2, N–N = NH₂(CH₂)₂NH·(CH₂)₃SiO_3/2 and x = [SiO_4/2]/[N] or [SiO_4/2]/[N–N]. The amino groups in the materials are coordinately active and participate partly in the coordination sphere of Cu(II) ions. The composition of the coordination sphere can be varied with the SiO_4/2 content and also as a result of the thermal decomposition of the organic residues at higher temperatures.Because the xerogel materials are considered to be catalyst precursors, this study is focused on their coordination and thermal properties. The prepared xerogels, such as silica, aminated silicates with N and N–N, as well as those entities complexed with Cu(II), were characterised by FT-IR spectroscopy. During gelation and thermal decomposition the materials were analysed by electron paramagnetic resonance (EPR) spectroscopy. The xerogels were additionally studied by UV-Vis absorption spectroscopy. The gaseous products of the thermal decomposition of these materials in an Ar atmosphere were investigated by the use of FT-IR spectroscopy coupled with TG and DTG thermal analysis. These data were complemented by temperature-programmed decomposition (TPDec) in a 2% O₂ + 98% Ar stream coupled with quadrupole mass spectroscopy.     

Comparing the Atomic Structures of Binary MO2-SiO2 (M = Ti, Zr or Hf) Xerogels

The incorporation of transition-metal oxides into silica can give materials with useful optical, electronic or catalytic properties. For example, ZrO₂-SiO₂ and HfO₂-SiO₂ materials are of interest due to their high dielectric constants. Here we present a comparison of extended X-ray absorption fine structure and small-angle X-ray scattering results for acid-catalysed binary (MO₂) _x (SiO₂)_{1 – x} (M = Ti, Zr or Hf) xerogels, with x up to 0.4 and heat treatments up to 750°C. Detailed observations for TiO₂-SiO₂ and ZrO₂-SiO₂ xerogels provide a basis for interpretation of new results for HfO₂-SiO₂ xerogels. At low concentrations metal atoms are homogeneously incorporated into the silica network. Ti adopts coordinations of 4 or 6, and Zr and Hf both adopt higher coordination of 6 or 7 (the larger coordinations being due to ambient moisture). At higher concentrations, phase separation of metal oxide occurs. Such regions become clearly separated from the silica network for TiO₂, but remain very finely mixed with silica network for ZrO₂ and HfO₂.     

硼离子对铕掺杂SiO2干凝胶发光性能的影响

采用溶胶-凝胶法制备了Al单掺和B，Al共掺的Eu掺杂SiO2干凝胶。利用荧光光谱、IR，XRD，DSC，TG／DTG等技术研究了硼离子、退火温度对样品发光性质的影响。经500℃以上退火处理用248nm激发的样品，产生Eu^3＋离子^5D0→^7FJ的特征发射，^5D0→^7F1的跃迁分裂为两个峰。比较615nm处的发光强度，掺硼酸样品的发光强度是不加硼酸发光强度的3．3倍。这是因为B离子的加入，在材料中形成了Si—O—B键，破坏了网络的对称性，加强了Eu^3＋的红光发射。当退火温度上升到850℃用350nm激发时，样品有很强的Eu^2＋蓝光发射。Al单掺的发射中心在437nm处，发射半峰宽约为70nm，而B，Al共掺样品的发光中心蓝移到425nm处，单掺样品的蓝光强度几乎是共掺样品强度的2倍。这是由于硼酸的加入改变了基质的网络结构，从而导致单掺和共掺样品发射峰位和强度的改变。     

Effect of the Measurement Temperature on the Dispersive Component of the Surface Free Energy of a Heat Treated SiO2 Xerogel

The surface free energy of a monolithic silica xerogel treated at 1000°C has been measured by inverse gas chromatography in the temperature range 25–150°C using n-alkanes. Values of the dispersive component, _S ^D, vary from 49.07 mJ·m^–2 at 25°C to 17.20 mJ·m^–2 at 150°C. The _S ^D value obtained at 25°C is lower than that found for amorphous and crystalline silicas but higher than that found for glass fibres meaning that the heat treatment at 1000°C changes drastically the structure of the silica xerogel showing a surface similar to a glass. However, the higher value of _S ^D in comparison to glass fibres can be attributed to the mesoporous structure present in the silica xerogel. In the temperature range of 60–90°C there exists an abrupt change of the _S ^D values as well as in the dispersive component of the surface enthalpy, h _S ^D. Such abrupt change can be attributed to an entropic contribution of the surface free energy.     

Ethanol Washing Effect on Textural Properties of the Sodium Silicate-Derived Silica Xerogel

This study deals with the use of ethanol as washing solvent in the preparation of the silica gels from sodium silicate in order to enhance the textural properties, especially surface area. We here examined the effect of ethanol-washing on surface area, micro- and mesopore volume, and average pore size. The silica xerogels prepared from sodium silicate solution exhibited an extremely high surface area of 1139 m2/g by washing their hydrogels with ethanol. Compared to water-washed xerogels, ethanol-washed xerogels showed higher surface areas, total pore volumes, and larger average pore sizes. Unlike the surface area of water-washed xerogel, that of the ethanol-washed xerogel was not affected by the silica concentration of initial solution. This study indicates that the textural properties of sodium silicate-derived xerogels are further enhanced by using ethanol as washing solvent.     

Thermal and Temporal Aging of Silica Gels in Monomer Solutions

In previous work we have introduced the idea of preparing ambient pressure dried silica aerogels by increasing the wet gels' stiffness by aging in a TEOS solution until shrinkage during drying is almost eliminated. The present work elucidates the possibilities for obtaining ambient pressure dried aerogels employing this idea, however, cheap water soluble sodium silicate (water glass) precursors have been used to increase the economic feasibility of the process.We have shown how the G modulus of water glass based gels can be increased by aging in TEOS solution and gels with a density down to 0.2 g/cm3 can be obtained. These wet gels show a higher reactivity towards TEOS compared to TEOS based gels. We have also introduced the idea of aging wet gels in a solution where the monomers are provided from water glass instead of TEOS and some initial results on G modulus and density are included.     

Surface influence on the rotational and translational dynamics of molecules confined inside a mesoporous carbon xerogel

Low-field nuclear magnetic resonance techniques are employed to extract information about the effects introduced by the interaction with the surface on the rotational and translational dynamics of molecules confined inside a mesoporous carbon xerogel. The molecules under study were water, cyclohexane, and hexane. They were chosen due to their different interaction strength with the carbonaceous matrix. Frequency dependent longitudinal relaxation measurements, using the fast field cycling technique, allowed extraction of the fractal dimension of the carbon xerogel surface. It was observed that the measured value is influenced by the molecule affinity to the surface. Diffusion measurements, using the pulse field gradient technique, have revealed that the stronger interaction with the surface of cyclohexane and hexane molecules leads to an increased diffusive tortuosity, as compared with water.     

Synthesis and characterization of side chain cholesteric liquid crystalline elastomers derived from chiral bisolefinic crosslinking units

In this work we prepared a nematic monomer (4′‐allyloxybiphenyl 4′‐ethoxybenzoate, M₁ ), a chiral crosslinking agent (isosorbide 4‐allyloxybenzoyl bisate, M₂ ) and a series of new side chain cholesteric liquid crystalline elastomers derived from M₁ and M₂ . The chemical structures of the monomers and polymers were confirmed by FTIR and ¹H NMR spectroscopy. The mesomorphic properties were investigated by differential scanning calorimetry, thermogravimetric analysis, polarizing optical microscopy and X‐ray diffraction. The effect of the content of the crosslinking unit on phase behaviour of the elastomers is discussed. Polymer P₁ showed a nematic phase, P₂ –P₇ showed a cholesteric phase; P₆ formed a blue Grandjean texture over a broad temperature range 145–209.6°C, with no changed on the cooling. Polymers P₄ –P₇ , with more than 6?mol?% of chiral crosslinking agent, gave rise to selective reflection. Elastomers containing less than 15?mol?% of the crosslinking units displayed elasticity, reversible phase transition with wide mesophase temperature ranges, and high thermal stability. Experimental results demonstrated that, with increasing content of crosslinking agent, the glass transition temperatures first fell and then increased; the isotropization temperatures and mesophase temperature ranges decreased.     

Selective water sorbents for multiple applications, 8. sorption properties of CaCl2?SiO2 sol-gel composites

This paper presents sorption properties of CaCl₂/SiO₂ composites synthesized by a sol-gel approach. Desorption isobars measured at T=30–140°C and vapor pressure 12.8–81.0 mbar clearly show a correlation between the sorbents pore structure and their sorption properties. The sample adsorptivities are found to exceed 1.2 kg H₂O/kg adsorbent (or 20–25 mol H₂O/mol of the salt). That is markedly higher than any reported before for silica-based materials. This results in a high energy storage capacity reaching 3,400 kJ/kg of dry sorbent, as confirmed by direct calorimetric measurements. The isosteric desorption heat is found to decrease from 67±5 kJ/mol to 46±5 kJ/mol with increase in the surface coverage.