A Novel Highly Sensitive Humidity Sensor Based on ZnO/SBA‐15 Hybrid Nanocomposite

This work deals with the study of hydrothermally synthesized zinc oxide (ZnO) loaded mesoporous SBA‐15 hybrid nanocomposite for relative humidity sensing (RH) at room temperature. The sensor exhibits an excellent ~5 orders impedance change along with excellent linearity, quick response time (17 s), rapid recovery time (18 s), negligible hysteresis (1.2%), good repeatability, and stability (1.8%) in 11%–98% RH range. In addition, complex impedance spectra of the sensor at different RHs were analyzed to understand the humidity sensing mechanism. Our study can open a new way for realizing ZnO/SBA‐15 hybrid nanocomposite for fabrication of high‐performance RH sensors.     

Highly Stable Amine-modified Mesoporous Silica Materials for Efficient CO2 Capture

A highly efficient and stable solid adsorbent invoking a direct incorporation of tetraethylenepentamine (TEPA) onto the as-synthesized mesocelullar silica foam (MSF) has been developed for CO₂ capture. Unlike most amine-functionalized silicas, which typically exhibit CO₂ adsorption capacities less than 2.0 mmol/g, such organic template occluded mesoporous silica-amine composites exhibited remarkably high CO₂ uptake as high as 4.5 mmol/g at 348 K and 1 atm. Moreover, notable increases in CO₂ adsorption capacities of the composite materials were observed when in the presence of humidity. Durability test performed by cyclic adsorption–desorption revealed that such adsorbents also possess excellent stability, even though a slight decrease in adsorption capacity over time was observed.     

Improving Physical Adsorption of CO2 by Ionic Liquids‐Loaded Mesoporous Silica

CO₂ sorption capacities of the neat and silica‐supported 1‐butyl‐3‐methylimidazolium‐based ionic liquids (ILs) were measured under atmospheric pressure. The silica‐supported ILs were synthesized by the impregnation‐vaporization method and charactrized by N₂ adsorption/desorption and thermogravimeteric analysis (TGA). Evaluation of the effects of influential factors on sorption capacity demonstrated that by increase of the temperature, flow rate, and the weight percentage of ILs in sorbents, the sorption capacity decreases. Among the sorbents, [Bmim][TfO] and SiO₂‐[Bmim][BF₄](50) had the highest capacity. By increasing the IL portion in SiO₂‐[Bmim][BF₄], the selectivity for CO₂ to CH₄ could be improved. The CO₂‐rich sorbents could be easily recycled.     

Filter‐Through Method of Making Highly Efficient Polymer‐Clay Nanocomposite Membranes

Electrospun filter with hierarchical pore structure and variable pore diameter is used for the first time in making a flexible, strong, and high gas‐barrier membrane. A versatile, technical, benign processing method for the fabrication of highly filled (>25 wt%) efficient gas‐barrier polymer membrane with perfectly aligned synthetic high‐aspect ratio layered silicate (clay) of variable and considerable thickness (up to 5 µm) is presented. This process combines advantageous features of an electrospun substrate like high porosity, variable pore size (typically <5 µm), thermoplasticity and of an aqueous suspension of a synthetic clay consisting of single 1 nm thick layers with a huge median lateral extension (>10 µm) in a layered structure. By simple and fast filtration, a gas‐barrier self‐assembled layer of variable and appropriate thickness is obtained on a mechanically stable thermoplastic electrospun filter support that subsequently can be laminated adhesively or via hot pressing, even in a multilayer structure, if required. The resulting composite membranes are flexible, strong, transparent, and show enhanced gas‐barrier properties.     

Humidity Sensing Property of NaCl‐Added Mesoporous Silica Synthesized by a Facile Way with Low Energy Cost

NaCl‐added mesoporous silica SBA‐15 was prepared by a simple grind method which needs low energy cost. Humidity sensing property was studied. Study results indicated that NaCl‐added material possesses higher humidity sensitivity. Its impedance changed more than four orders of magnitude when the relative humidity changed from 11% RH to 95% RH. From the viewpoint of economy, NaCl‐added SBA‐15 material which possesses high sensitivity and needs low energy cost is more suitable to be a promising humidity sensing material. Complex impedance spectra, the corresponding equivalent circuit, and bode diagrams were carefully analyzed to explore sensing mechanism.     

Sinterability Enhancement by Collapse of Mesoporous Structure of SBA‐15 in Fabrication of Highly Transparent Silica Glass

Highly transparent silica glass was prepared from mesoporous silica SBA‐15 powders at low temperature using Spark Plasma Sintering. It was found that the combined effect of pressure and temperature resulted in collapse of porous structure of SBA‐15 and transformation to transparent glass. A sinterability enhancement mechanism involving generation of incremental surface area from pore collapse during sintering process was proposed to interpret the fully densification at low temperature.     

Highly Ordered N-Containing Mesoporous Silica from Carbothermal Reduction–Nitridation with the Nanocasting Procedure

Highly ordered N-containing mesoporous silica materials with high specific surface area were prepared by heat treatment of the as-synthesized mesoporous silica nanocasted with carbon in its channels in flowing N₂ at high temperatures. This is the first time N₂-assisted carbothermal reduction–nitridation with nanocasting procedure has been used to prepare ordered mesoporous materials.     

High Temperature Nanocomposite Through Engineered Synthesis of Hafnia Nano-Dispersoids in Hexagonal Mesoporous Silica

In this communication, we show a solution-based synthetic route that yields a dual-phase SiO₂-based ceramic–ceramic composite capable of retaining nano-structural features up to very high temperatures. The nanocomposite was produced by self-assembly of mesoporous silica using a non-ionic surfactant, and subsequent infiltration of the mesoporosity with a solution containing a high-temperature metal-oxide-based composition (HfO₂). The nanocomposite was consolidated and processed up to 1500°C.     

Synthesis and Characterization of Highly Dispersed Molybdenum Carbides in Mesoporous Silica

Highly dispersed molybdenum carbides in MCM-41 mesoporous silica are synthesized by temperature-programmed carburization and are characterized. Two methods of preparation are examined: (i) insertion of molybdenum during the synthesis of the MCM-41 silica and (ii) postsynthesis incorporation into a MCM-41 silica matrix by the incipient wetness method. Propene transformation (hydrogenation and metathesis) was used as a probe reaction; the observed catalytic behavior can be explained as a result of the preparation method, i.e., of the relative strength of interaction between the molybdenum oxide precursor and the support.     

Mesoporous Silica: A Suitable Adsorbent for Amines

Mesoporous silica with KIT-6 structure was investigated as a preconcentrating material in chromatographic systems for ammonia and trimethylamine. Its adsorption capacity was compared to that of existing commercial materials, showing its increased adsorption power. In addition, KIT-6 mesoporous silica efficiently adsorbs both gases, while none of the employed commercial adsorbents did. This means that KIT-6 Mesoporous silica may be a good choice for integrated chromatography/gas sensing micro-devices.     

Grafting of Molecularly Ordered Mesoporous Phenylene‐Silica with Molybdenum Carbonyl Complexes: Efficient Heterogeneous Catalysts for the Epoxidation of Olefins

Arenetricarbonyl complexes, or the general formula  C₆H₄Mo(CO)₃ , were incorporated into crystal‐like mesoporous phenylene‐silica by liquid‐phase deposition of molybdenum hexacarbonyl [Mo(CO)₆]. By adjusting the reaction conditions, different molybdenum loadings of 1.5 and 5.9 wt% were obtained, which correspond to 3% and 14% of the phenylene contents. The texture properties of the materials as well as the nature of the surface‐fixed complexes were characterized by powder X‐ray diffraction, transmission electron microscopy (TEM), N₂ adsorption, FT‐IR, UV‐vis and MAS (¹³C, ²⁹Si) NMR spectroscopy. The derivatized organosilicas were examined as catalyst precursors for the liquid‐phase epoxidation of cis‐cyclooctene, 1‐octene, trans‐2‐octene and (R)‐(+)‐limonene at 55 °C, using tert‐butyl hydroperoxide as the oxidant. For each olefin the corresponding epoxide was the only product detected. In the case of cyclooctene, the intrinsic reaction rates per surface molybdenum atom were similar for both Mo loadings (TOF∼1150 mol mol_Mo⁻¹ h⁻¹), suggesting that the resultant materials act as single site epoxidation catalysts. Leaching tests and metal analyses of reaction solutions showed that the catalytic activity stemmed from the immobilized species and not from the leaching of active species into solution. The oxidation of limonene gave limonene oxide as the only product in 95% yield at 3 h, which reveals an outstanding regioselectivity to the epoxidation of the endocyclic double bond.     

Pt-supported Spherical Mesoporous Silica as a Nanosized Catalyst for Efficient Liquid-Phase Hydrogenation

Mesoporous silica nanospheres with an average diameter of approximately 240 and 600 nm have been used as catalyst supports of active Pt nanoparticles, which were found to be highly efficient for liquid-phase hydrogenation under atmospheric H₂ compared to the micron-sized conventional mesoporous silica because of the suppression of mass-transport limitation toward active sites.     

Kinetics of CO2 Adsorption/Desorption of Polyethyleneimine‐Mesoporous Silica

The kinetics of adsorption of CO₂ on solid sorbents based on polyethyleneimine/mesoporous silica (PEI/MPS) was studied by following the mass gain during CO₂ flow. Linear (PEI‐423) and branched (PEI‐10k) polymers were studied. The solid sorbents were synthesized by impregnating the PEI into MPS foam. The kinetics of adsorption was fitted with a double‐exponential model. In contrast, the desorption process obeyed first‐order kinetics. The activation energy of desorption of PEI‐423 was lower than that of PEI‐10k, presumably because the branched polymer required more energy to expose its nitrogen to CO₂. To increase the CO₂ sorption capacity, the MPS was treated with nonionic surfactant materials prior to impregnation with PEI. This also lowered the maximum sorption temperature and desorption activation energies.     

Effect of Milling Time on the Rheology of Highly Loaded Aqueous-Fused Silica Slurry

The effects of milling time on the rheological behavior of 70-vol% loaded fused silica slurries were studied. A transition from shear thickening to shear thinning behavior was observed with milling time. Slurry viscosity and thixotropy attained a minimum after 18 h of milling and remained almost unchanged with additional milling. Infrared spectroscopy and particle surface charge measurements confirmed the development of increasing amount of surface hydroxide and surface charge respectively with progress in milling time, leading to shear thinning behavior. An initial static aging treatment of 24 h aided the development of silanol groups, indicating that the milling time can be reduced to save energy and time.     

Enhanced Oxidative Desulfurization of Dibenzothiophene by Functional Mo‐Containing Mesoporous Silica

Functional mesoporous Mo–SiO₂ materials were synthesized by a one‐pot and facile room‐temperature procedure, and characterized by X‐ray diffraction, TEM, Raman spectroscopy, FT‐IR, diffuse reflectance spectra, and BET analysis. The experimental results demonstrated that the mesoporous materials presented a high dispersion of molybdenum species and excellent catalytic activity for the removal of dibenzothiophene (DBT) without organic solvents as extractants. The catalytic performance on different sulfur‐containing compounds was also investigated in detail. After recycling for eight times, the removal of the oxidation desulfurization system could still reach high values. GC‐MS analysis detected the oxidation product of DBT. A mechanism was proposed for the absorptive oxidation process of sulfur compounds.     

Highly Efficient Near-IR Photoluminescence of Er Immobilized in Mesoporous SBA-15

SiO₂ mesoporous molecular sieve SBA-15 with the incorporation of erbium ions is studied as a novel type of nanoscopic composite photoluminescent material in this paper. To enhance the photoluminescence efficiency, two schemes have been used for the incorporation of Er³⁺ where (1) Er³⁺ is ligated with bis-(perfluoromethylsulfonyl)-aminate (PMS) forming Er(PMS)_x-SBA-15 and (2) Yb³⁺ is codoped with Er³⁺ forming Yb-Er-SBA-15. As high as 11.17 × 10⁻²¹cm² of fluorescent cross section at 1534 nm and 88 nm of “effective bandwidth” have been gained. It is a 29.3% boost in fluorescent cross section compared to what has been obtained in conventional silica. The upconversion coefficient in Yb-Er-SBA-15 is relatively small compared to that in other ordinary glass hosts. The increased fluorescent cross section and lowered upconversion coefficient could benefit for the high-gain optical amplifier. Finally, the Judd–Ofelt theory has also been used for the analyses of the optical spectra of Er(PMS)_x-SBA-15.     

以十二烷基三甲基溴化铵为模板制备高度有序的介孔二氧化硅材料

以长碳链阳离子表面活性剂如十六烷基三甲基溴化铵为模板,可制得高度有序的介孔二氧化硅材料,而碳链较短的表面活性剂如十二烷基三甲基溴化铵,由于其表面活性较差,以其为模板难以制得有序介孔二氧化硅材料.以十二烷基三甲基溴化铵为模板剂,考察了不同硅源、碱源以及pH值对介孔材料结构的影响,采用XRD、FTIR、SEM、HRTEM和N2物理吸附等手段分别对产物的晶体结构、织构性质、形貌和孔道结构进行表征.结果 表明,以正硅酸乙酯为硅源,在有机碱四甲基氢氧化铵存在下,以十二烷基三甲基溴化铵为模板,制得了具有规整六方结构的高度有序介孔二氧化硅材料,其孔径和晶胞常数分别为2.25 nm和3.72 nm.     

Highly Active Silica Gel‐Supported Metathesis (Pre)Catalysts

Highly active Hoveyda–Grubbs and Hoveyda–Blechert type (pre)catalysts, immobilized on silica gel, are presented. These (pre)catalysts are synthesized in a few steps from readily available precursors and demonstrate high activity in a number of test metathesis reactions. The catalyst is easily separated by simple filtration of the non‐swelling material.     

Highly Effective Oxidative Dehydrogenation of Propane Over Vanadia Supported on Mesoporous SBA-15 Silica

Vanadia-containing mesoporous SBA-15 catalysts were prepared and characterized for the oxidative dehydrogenation (ODH) of propane. It is demonstrated that the vanadia-supported SBA-15 catalysts exhibit a much higher catalytic activity than those reported in the literature obtained over vanadium-supported mesoporous MCM-41 catalysts in the ODH of propane. The high catalytic performance of the mesoporous SBA-15 catalysts is attributed to the particularly large pore diameters and low surface acidity.     

Calixarene‐Derived Mono‐Iminophosphoranes: Highly Efficient Ligands for Palladium‐ and Nickel‐Catalysed Cross‐Coupling

The first mono‐iminophosphoranes based on a calix[4]arene skeleton have been synthesised and tested in the arylation of aryl bromides and aryl chlorides. Combining these ligands with [Pd(OAc)₂] or [Ni(cod)₂] resulted in highly active Suzuki–Miyaura and Kumada–Tamao–Corriu cross‐coupling catalysts, respectively. TOFs up to ca. 4×10⁵ mol(ArBr)⋅mol(M)⁻¹⋅h⁻¹ were obtained in each case. The remarkable activities observed probably arise from the ligands’ ability to form complexes with cavity‐entrapped “MArX” moieties (endo‐complexes), their highly crowded metal environment favouring formation of mono‐ligated intermediates over that of less reactive bis‐ligated ones. Possible supramolecular interactions within the cavity involving the receptor wall and the aromatic substrate may also significantly influence the reaction rates, notably by increasing the proportion of endo‐complexes.