An excellent universal catalyst support-mesoporous silica: Preparation,modification and applications in energy-related reactions

As a kind of versatile, excellent catalyst carriers, mesoporous silicas (mSiO₂) have been widely applied for preparing various supported catalysts with ideal catalytic properties due to their uniform and regular channels, adjustable medium pore size, big surface area, controllable wall composition, high hydrothermal stability, easy functional modification and good accessibility of larger reactant molecules. mSiO₂ not only enhances the dispersity of the active phase and generates more active sites for superior catalytic activity but also improves resulted selectivity and cyclic lifespan for enhanced interaction. And high adsorption capacity of mSiO₂ also increases the reactant molecule enrichment. In addition, mesoporous feature of the mSiO₂ pore wall can ensure diffusion of the substrate molecules and prevent leaching of active components. Thus, related investigation and application have been rapidly growing in the past decades. In this review, the development of mesoporous silica based catalysts on preparation, modification, pore size tune and energy-related applications, especially in hydrogenation reaction, esterification reaction, hydrogen production by alkane dry reforming and alcohol steam reforming and photocatalytic water splitting, is introduced in detail and the design ideas, preparation strategies and corresponding mechanism of different composite catalysts are discussed.     

Colored amorphous silica-based powder with TiN nanocrystals precipitated by ammonolysis of Ti–Si–O ternary glass

Coloration of amorphous silica powder containing titania was investigated by nitridation in an ammonia flow. The oxide precursors were obtained by the hydrolysis of a mixture of tetraethyl orthosilicate (TEOS) and tetrabutoxy titanium (TBT). The color changed with the amount of TBT in the mixture, the hydrolysis pH and the ammonolysis temperature. The original white color of the 8 mol% TBT powder hydrolyzed under basic pH conditions changed to pale goldenrod at 700°C, then to dark olive green at 800°C, and further darkened with increasing ammonolysis temperature. A steel-blue color appeared at 900°C for the powder obtained with 3 mol% TBT, and increased in darkness at 1000°C. A similar bluish color was observed for powders obtained by acidic hydrolysis after ammonolysis above 900°C, and this was independent of the amount of titania, although the chroma decreased with increasing firing temperature for the powder with 3 mol% TBT. The ammonolysis powder products were characterized using X-ray diffraction (XRD), electron probe micro analysis (EPMA), transmission electron microscopy-electron energy-loss spectroscopy (TEM-EELS), scanning transmission electron microscopy-high-angle annular dark-field imaging (STEM-HAADF) and Ti–K edge X-ray absorption fine structure (XAFS). The color change was related to both precipitated TiN nanocrystals and residual titanium in the amorphous silica matrix. The TiN exhibited a goldish reflection and also plasmonic absorption from light blue to gray depending on the TiN crystallite size. The plasmonic absorption and resonance of nanocrystalline TiN will be useful similarly to that of gold in nanotechnology for various kinds of energy application.     

Acoustic emission waveform characterization of crack origin and mode in fractured and ASR damaged concrete

Different constituents of concrete can have cracking behavior that varies in terms of the acoustic waveform that is generated. Understanding the waveform may provide insight into the source and behavior of a crack that occurs in a cementitious composite. In this study, passive acoustic emission (AE) was used to investigate the waveform properties of the individual components of concrete (i.e., aggregate, paste, and interfacial transition zone (ITZ)). First, acoustic events produced by cracks generated using mechanical loading in a wedge splitting test were detected. It was observed that cracks that occurred through the aggregate have an AE frequency range between 300 kHz and 400 kHz, while cracks that propagated through the matrix (paste and ITZ) have a frequency range between 100 kHz and 300 kHz. Second, tests were performed using samples that were susceptible to alkali silica reaction; and AE and X-ray computed tomography were used to detect cracking. AE events with a frequency range between 300 kHz and 400 kHz were detected at early ages, suggesting the initiation of cracks within reactive aggregate. At later ages, AE events were detected with frequency ranges of 100–300 kHz, indicating crack development and propagation in the matrix.     

Hierarchical mesoporous silica microspheres as unique hard-template for preparation of hierarchical mesoporous TiO2 microspheres with trimodal mesoporosities via nanocasting

This work for the first time reported that hierarchical meso-mesoporous SBA-15 silica microspheres (HMM-SiO₂-MSs) can serve as a unique and suitable hard-template for the nanocasting preparation of mesoporous TiO₂ with both hierarchical mesostructures and well-preserved microsphere particle morphology. A two-step impregnation (TSI) method was developed and customized and its effectiveness was studied in comparison with the single-step impregnation method. Trimodal mesoporosities and their origin are newly recognized and analyzed. The materials were examined by various techniques, including the FE-SEM, N₂ sorption, TEM and XRD. Under optimized conditions, the hierarchical mesostructures and spherical particle morphology of HMM-SiO₂-MSs can be replicated for HMM-TiO₂-MSs. The high surface area and pore volume of HMM-TiO₂-MSs reach 194 m² g^-1 and 0.68 cm³ g^-1, respectively, with the latter more than twice those templated by conventional SBA-15s. Besides HMM-TiO₂-MSs, such HMM-SiO₂-MSs as hard-template might be extended to the preparation of other materials with hierarchical mesostructures.     

MTMS基SiO_2气凝胶的制备及其影响因素

以甲基三甲氧基硅烷(MTMS)为前驱体,通过酸碱两步溶胶凝胶法,常压干燥制备了SiO2气凝胶,综合研究了反应条件对气凝胶导热系数,堆积密度,比表面积和孔径的影响,利用FT-IR分析了SiO2气凝胶的化学结构。     

Acidichromic Spiropyran-Functionalized Mesoporous Silica: Towards Stimuli-Responsive Metal Ion Separations Media

Abstract

An acidichromic silyl spiropyran was synthesized and covalently immobilized on the surface of mesoporous silica (SBA-15) through either post-modification or a co-condensation route. The integration of the spiropyran into the porous silica was probed by thermogravimetric analysis, nitrogen adsorption/desorption studies and UV-Vis optical spectroscopy. While the co-condensation route provides the higher spiropyran loading levels, it also leads to two different states of attachment. Both synthetic procedures favor the formation of the open, merocyanine form of the spiropyran within the framework, but this form can be readily switched from a protonated to a deprotonated state by treatment with buffered aqueous solutions. Preliminary evaluation of the metal ion sorption capabilities of the spiro-functionalized SBA-15 for selected monovalent, divalent, and trivalent metal ions indicates that the spiropyran-modified materials show modestly improved cation exchange characteristics versus the unfunctionalized mesoporous framework.     

Fabrication and characterization of large-core Yb/Al-codoped fused silica waveguides using dry etching

A deep inductively coupled plasma etching process was developed as a part of a continuous effort to develop an all-silica on-chip platform for high-power optical devices. Combined F and Cl based etching chemistry was found most suitable since silica matrix and Al doping are generally etched using different chemistries. First large-core (∼20 × 20 μm) Yb/Al-codoped fused silica waveguides on pure silica substrate were successfully fabricated, featuring ∼1 dB/cm optical propagation loss.