Hierarchical self-assembly in molecularly ordered phenylene-bridged mesoporous organosilica nanofilaments.

Herein we report on the mechanism of formation of a hybrid phenylene-bridged hexagonally ordered mesoporous organosilica with crystal-like walls (CW-Ph-HMM). Electron microscopy and X-Ray diffraction studies indicate that the formation of CW-Ph-HMM involves the surfactant-mediated hydrothermal transformation of an amorphous organosilica precursor and that the final product is hierarchically ordered. Significantly, the material is in the form of submicrometre-thick sheets that consist of co-aligned aggregates of needle-like particles (up to 500 nm in length and 50 nm in width). The results suggest that preferential growth along the channel direction of the hexagonally ordered mesostructure is coupled with the propagation of molecular periodicity in the pore walls. Together, these factors give rise to the growth of highly anisotropic primary nanofilaments that become co-aligned to produce micrometer-thick sheets consisting of a periodic array of mesoscopic channels oriented perpendicular to the surface of the flake-like particles.     

A NOVEL ALUMINOSILICATE WITH BIMODAL MESOPORE DISTRIBUTION ?a?a SYNTHESIS AND CHARACTERIZATION

A novel aluminosilicate material (denoted as NKF-2) with well defined bimodal mesopore distribution has been hydrothermally synthesized directly using cetyltrimethylammonium chloride and tetraethylammonium hydroxide as mixed templates, in which one mesopore is distributed at around 3.8 nm and the other at 2.6 nm. The synthesized samples were characterized by powder X-ray diffraction (XRD), scanning electron microscopy, N2 adsorption, infrared spectroscopy, thermo-gravimetic analysis and solid-state 27Al and 29Si magic-angle-spinning(MAS) NMR spectroscopies to understand both the pore structures and the Local atomic arrangements of these solid products.     

Tuning of Silver Catalyst Mesostructure Promotes Selective Carbon Dioxide Conversion into Fuels

An electrode's performance for catalytic CO₂ conversion to fuels is a complex convolution of surface structure and transport effects. Using well‐defined mesostructured silver inverse opal (Ag‐IO) electrodes, it is demonstrated that mesostructure‐induced transport limitations alone serve to increase the turnover frequency for CO₂ activation per unit area, while simultaneously improving reaction selectivity. The specific activity for catalyzed CO evolution systematically rises by three‐fold and the specific activity for catalyzed H₂ evolution systematically declines by ten‐fold with increasing mesostructural roughness of Ag‐IOs. By exploiting the compounding influence of both of these effects, we demonstrate that mesostructure, rather than surface structure, can be used to tune CO evolution selectivity from less than 5 % to more than 80 %. These results establish electrode mesostructuring as a powerful complementary tool for tuning both catalyst selectivity and efficiency for CO₂ conversion into fuels.     

表面高巯基功能化介孔材料的制备及对Hg~(2+)的吸附性能

在酸性条件下,以三嵌段非离子表面活性剂P123为模板剂,四氧基硅烷(TEOS)预水解后与3-巯基丙基三乙基硅(MPTES)共聚,合成了具有不同巯基官能团比例x[n(MPTES)/n(TEOS+MPTES)]的功能化介孔材料(SBA-SH-x),其结构和性能经FT-IR,元素分析,SEM,TEM,小角X-ray和N2吸附-脱附表征。结果表明:x10%,SBA-SH-x为六方p6mm介观结构;10%x15%,SBA-SH-x为立方Ia3d介孔结构;x20%,SBA-SH-x为无序结构。SBA-SH-x在水溶液中吸附Hg2+的研究结果表明:SBA-SH-10和SBA-SH-15对Hg~(2+)吸附性能较好。     

Heteropoly acid encapsulated SBA-15/TiO2 nanocomposites and their unusual performance in acid-catalysed organic transformations

The preparation of SBA-15/TiO(2) nanocomposites with different loadings of Keggin-type 12-tungstophosphoric acid (TPA) nanocrystals in their mesochannels through a simple and effective vacuum impregnation method is reported for the first time. The catalysts have been characterised by various sophisticated techniques, including XRD, HRSEM, and TEM. It has been found that the acidity and the textural parameters of the nanocomposites can be controlled by simply changing the loadings of TPA and TiO(2) or the calcination temperature. TPA and TiO(2) loadings of 15 and 22.4 wt %, respectively, and a calcination temperature of 1123 K have proved to be optimal for obtaining mesoporous nanocomposite materials with the highest acidity. Moreover, the activities of these catalysts in promoting hydroamination as well as Mannich and Claisen rearrangement reactions have been extensively investigated. The results show that the amount of TPA has a great influence on the activity of the nanocomposites in all of the reactions studied. The effects of other reaction parameters, such as temperature and reaction time, on the conversion and product selectivity have also been studied in detail. A kinetic analysis of the formation of the products under various reaction conditions is presented. It has been found that the activity of the nanocomposite composed of 15 wt % TPA deposited on 22.4 wt of TiO(2) on SBA-15 in promoting the studied reaction is remarkably higher than the catalytic activities shown by pure TPA, TiO(2)-loaded SBA-15, or TPA-loaded SBA-15. The results obtained have indicated that the acidity and the structural control of the nanocomposite materials are highly critical for obtaining excellent catalytic activity, and the presented highly acidic nanocomposites are considered to show great potential for use as catalysts in promoting many acid-catalysed organic transformations.     

Chemistry in confining reaction fields with special emphasis on nanoporous materials

The everyday routine of most chemists is dictated by large numbers. The chemical rules for ensembles of molar size (N approximately N(A)=6.022 x 10(23)) are well known and can be understood in most cases by using Boltzmann distribution. It is an interesting question how a small ensemble of a chemical system behaves and if it differs from the respective large-ensemble counterpart. The experimental approach presented in the current paper involves the division of a macroscopic volume into compartments that contain only a small number of reactants. The compartments represent the pores of tailor-made nanoporous materials.     

Three-Dimensional Graphene/Ag Aerogel for Durable and Stable Li Metal Anodes in Carbonate-Based Electrolytes

The use of Li metal as the anode for Li-based batteries has attracted considerable attention due to its ultrahigh energy density. However, the formation of Li dendrites, uneven deposition, and huge volume changes hinder its reliable implementation. These issues become much more severe in commercial carbonate-based electrolytes than in ether-based electrolytes. Herein, a rationally designed three-dimensional graphene/Ag aerogel (3D G-Ag aerogel) is proposed for Li metal anodes with long cycle life in carbonate-based electrolytes. The modified lithiophilic nature of G-Ag aerogel, realized through decoration with Ag NPs, effectively decreases the energy barrier for Li nucleation, regulating uniform Li deposition behavior. Moreover, the highly flexible, conductive 3D porous architecture with hierarchical mesopores and macropores can readily accommodate deposited Li and ensures the integrity of the conductive network during cycling. Consequently, high coulombic efficiency (over 93.5 %) and a significantly long cycle life (1589 h) over 200 cycles, with a relatively high cycling capacity of 2.0 mAh cm⁻², can easily be achieved, even in a carbonate-based electrolyte. Considering the intrinsic high voltage windows of carbonate-based electrolytes, matching the G-Ag aerogel Li metal anode with a high-voltage cathode can be envisaged for the fabrication of high-energy-density Li secondary batteries.