Detailed Structural Characterizations of SBA‐15 and MCM‐41 Mesoporous Silicas on a High‐Resolution Transmission Electron Microscope

Using high‐resolution transmission electronic micrograph (HR‐TEM) observation, one can clearly see the pore geometry of the MCM‐41 and SBA‐15 mesoporous silicas to determine that their pore shapes are hexagonal and round, respectively. With the perpendicular orientations of the nanochannels to the electron beam, parallel line images of the (100) and (110) repeating spacings were observed. In the SBA‐15 mesoporous silicas, there are byproducts of the granular silica and disordered mesostructures, attributed to the weak hydrogen interactions between Pluronic 123 blockcopolymer and the silica species. There are also many different and significant +π disclination defects in SBA‐15 and MCM‐41 surfactant‐silica composites. The SBA‐15 with a thicker silica wall is more stable under irradiation by high‐energy electron beams compared to MCM‐41, which has thinner wall thickness. Some carbon nanostructure impurities were found in some carbon films on the metal grids.     

Influence of Pore Structure on Catalytic Properties of Mesoporous Silica-supported Co-B Amorphous Alloys in Hydrogenation of Cinnamaldehyde to Cinnamyl Alcohol

Co‐B amorphous alloy catalysts supported on three kinds of mesoporous silica (common SiO₂, MCM‐41 and SBA‐15) have been systematically studied focusing on the effect of pore structure on the catalytic properties in liquid‐phase hydrogenation of cinnamaldehyde to cinnamyl alcohol (CMO). Structural characterization of a series of different catalysts was performed by means of N₂ adsorption, X‐ray diffraction, transmission electron microscopy, hydrogen chemisorption, and X‐ray photoelectron spectroscopy. Various characterizations revealed that the pore structure of supports profoundly influenced the particle size, location and dispersion degree of Co‐B amorphous alloys. Co‐B/SBA‐15 was found more active and selective to CMO than either Co‐B/SiO₂ or Co‐B/MCM‐41. The superior catalytic activity could be attributed to the higher active surface area, because most of Co‐B nanoparticles in Co‐B/SBA‐15 were located in the ordered pore channels of SBA‐15 rather than on the external surface as found in Co‐B/SiO₂ and Co‐B/MCM‐41. Meanwhile, the geometrical confinement effect of the ordered mesoporous structure of SBA‐15 was considered to be responsible for the enhanced selectivity to CMO on Co‐B/SBA‐15, inhibiting the further hydrogenation of CMO to hydrocinnamyl alcohol.     

Prearation of Highly Ordered Mesoporous Silica Materials and Application as Enzeme Supports

An enzyme, horseradish peroxidase (HRP), was adsorbed in the manner of single immersion method on the silica mesoporous materials, FSM-16, MCM-41 and SBA-15 with various pore diameters from 27 to 92 and their enzymatic activity in an organic solvent and the thermal stability were studied. FSM-16 and MCM-41 showed larger amount of adsorption of HRP than SBA-15 or silica gel,when the pore sizes were larger than the spherical molecular diameter of HRP (ca 64×37). The increased enzyme adsorption capacity may be due to the surface characteristics of FSM-16 and MCM-41, which would be consistent with the observed larger adsorption capacity of cationic pigment compared with anionic pigment for these materials. The immobilized HRP on FSM-16 and MCM-41 with pore diameter above 50 showed the highest enzymatic activity in an organic toluene and thermal stability in aqueous solution at the temperature of 70℃. The immobilized enzymes on the other mesoporous materials including large or small pore sized FSM-16 showed lower enzymatic activity in an organic solvent and the thermal stability. Both surface character and size matching between pore sizes and the molecular diameters of HRP were important in achieving high enzymatic activity in organic solvent and high thermal stability.     

Mesoporous Silica Layer: Preparation and Opportunity

Periodic mesoporous silicas, which were prepared from silica‐surfactant mesostructured materials, have been investigated for a wide range of application due to their very large surface area, high porosity, pore size uniformity and variation, periodic pore arrangement and possible pore surface modification, after the pioneering papers on the formation of mesoporous silicas (MCM‐41 and FSM‐16). Morphosyntheses from such macroscopic morphologies as bulk monolith and film to nanoscopic ones, nanoparticles and their stable suspension, make mesoporous materials more attractive for applications and detailed characterization. Mesoporous silicas have been studied initially for such applications as adsorbent and catalyst, and more recently, optical, electronic, and bio‐related applications have been investigated. This review summarizes the studies on mesoporous silica film to highlight the present status and future of the preparation, characterization and application of the mesoporous silica film.     

Photosynthetic oxygen evolution in mesoporous silica material: adsorption of photosystem II reaction center complex into 23 nm nanopores in SBA

An oxygen-evolving photosynthetic reaction center complex (PSII) was adsorbed into nanopores in SBA, a mesoporous silica compound. We purified the dimer of PSII complex from a thermophilic cyanobacterium, Thermosynechococcus vulcanus, which grows optimally at 57 °C. The thermally stable PSII dimeric complex has a diameter of 20 nm and a molecular mass of 756 kDa and binds more than 60 chlorophylls. The SBA particles, with average internal pore diameters of 15 nm (SBA(15)) and 23 nm (SBA(23)), adsorbed 4.7 and 15 mg of PSII/g SBA, respectively. Measurement with a confocal laser-scanning microscope indicated the adsorption of PSII to the surface and the inner space of the SBA(23) particles, indicating the adsorption of PSII into the 23 nm silica nanopores. PSII did not bind to the inner pores of SBA(15). PSII bound to SBA(23) showed the high and stable activity of a photosynthetic oxygen-evolving reaction, indicating the light-driven electron transport from water to the quinone molecules added in the outer medium. The PSII-SBA conjugate can be a new material for photosensors and artificial photosynthetic systems.     

Three‐Dimensional Ultralarge‐Pore Ia3d Mesoporous Silica with Various Pore Diameters and Their Application in Biomolecule Immobilization

Highly ordered mesoporous three‐dimensional Ia3d silica (KIT‐6) with different pore diameters has been synthesized by using pluronic P123 as surfactant template and n‐butanol as cosolvent at different synthesis temperatures in a highly acidic medium. The materials were characterized by XRD and N₂ adsorption. The synthesis temperature plays a significant role in controlling the pore diameter, surface area, and pore volume of the materials. The material prepared at 150 °C, KIT‐6‐150, has a large pore diameter (11.3 nm) and a high specific pore volume (1.53 cm³ g^?1). We also demonstrate immobilization of lysozyme, which is a stable and hard protein, on KIT‐6 materials with different pore diameters. The amount of lysozyme adsorbed on large‐pore KIT‐6 is extremely large (57.2 μmol g^?1) and is much higher than that observed for mesoporous silicas MCM‐41, SBA‐15, and KIT‐5, mesoporous carbons, and carbon nanocages. The effect of various parameters such as buffer concentration, adsorption temperature, concentration of the lysozyme, and the textural parameter of the adsorbent on the lysozyme adsorption capacity of KIT‐6 was studied. The amount adsorbed mainly depends on solution pH, ionic strength, adsorption temperature, and pore volume and pore diameter of the adsorbent. The mechanism of adsorption on KIT‐6 under different adsorption conditions is discussed. In addition, the structural stability of lysozyme molecules and the KIT‐6 adsorbent before and after adsorption were investigated by XRD, nitrogen adsorption, and FTIR spectroscopy.     

Function of membrane protein in silica nanopores: incorporation of photosynthetic light-harvesting protein LH2 into FSM

A high amount of functional membrane protein complex was introduced into a folded-sheet silica mesoporous material (FSM) that has nanometer-size pores of honeycomb-like hexagonal cylindrical structure inside. The photosynthetic light-harvesting complex LH2, which is a typical membrane protein, has a cylindrical structure of 7.3 nm diameter and contains 27 bacteriochlorophyll a and nine carotenoid molecules. The complex captures light energy in the anoxygenic thermophilic purple photosynthetic bacterium Thermochromatium tepidum. The amount of LH2 adsorbed to FSM was determined optically and by the adsorption isotherms of N2. The FSM compounds with internal pore diameters of 7.9 and 2.7 nm adsorbed LH2 at 1.11 and 0.24 mg/mg FSM, respectively, suggesting the high specific affinity of LH2 to the interior of the hydrophobic nanopores with a diameter of 7.9 nm. The LH2 adsorbed to FSM showed almost intact absorption bands of bacteriochlorophylls, and was fully active in the capture and transfer of excitation energy. The LH2 complex inside the FSM showed increased heat stability of the exciton-type absorption band of bacteriochlorophylls (B850), suggesting higher circular symmetry. The environment inside the hydrophobic silica nanopores can be a new matrix for the membrane proteins to reveal their functions. The silica-membrane protein adduct will be useful for the construction of new probes and reaction systems.     

Synthesis and Characterization of Gold Nanoparticle‐Functionalized Ordered Mesoporous Materials

We report the synthesis and characterization of three different ordered mesoporous materials, labeled MCM‐48, SBA‐155, and SBA‐16 type materials, which were functionalized with gold nanoparticles using three different strategies. The functionalization strategies can be categorized as (i) in situ growth of gold nanoparticles, (ii) template loading, and (iii) diffusion loading of prefabricated gold nanoparticles. Two different particle sizes were employed in the latter two strategies, 5 nm and 10 nm. For all mesoporous structures, functionalization strategies, and particle sizes attempted, the materials retained their long‐range order upon incorporation of nanoparticles. From the adsorption isotherms, incorporation of gold nanoparticles altered the pore structure of the mesoporous support of some of the SBA‐15 and SBA‐16 type materials, with the effect on incorporation on the pore structure being particle size dependent in most cases. The majority of gold nanoparticles were found to reside on the external surface of the materials regardless of substrate and functionalization strategy; however, for the in situ synthesis and the template loading strategies, a significant fraction of the particles was determined to reside within the pore system of the material. In situ growth resulted in the highest content of gold nanoparticles in the solid phase. The relative effectiveness in retaining gold nanoparticles in the solid phase for each functionalization strategy was determined to be, in descending order, in situ synthesis, template loading, and diffusion loading.     

Encapsulation of Homogeneous Catalysts in Mesoporous Materials Using Diffusion‐Limited Atomic Layer Deposition

The heterogenization of homogeneous metal complex catalysts has attracted great attention. The encapsulation of metal complexes into nanochannels of mesoporous materials is achieved by coating metal oxides at/near the pore entrance by diffusion‐limited atomic layer deposition (ALD) to produce a hollow plug. The pore size of the hollow plug is precisely controlled on the sub‐nanometer scale by the number of ALD cycles to fit various metal complexes with different molecular sizes. Typically, Co or Ti complexes are successfully encapsulated into the nanochannels of SBA‐15, SBA‐16, and MCM‐41. The encapsulated Co and Ti catalysts show excellent catalytic activity and reusability in the hydrolytic kinetic resolution of epoxides and asymmetric cyanosilylation of carbonyl compounds, respectively. This ALD‐assisted encapsulation method can be extended to the encapsulation of other homogeneous catalysts into different mesoporous materials for various heterogeneous reactions.     

Polyurethane‐mesoporous silica gas separation membranes

The concept of mixed matrix membrane comprising dispersed inorganic fillers into a polymer media has revealed appealing to tune the gas separation performance. In this work, the membranes were prepared by incorporation of mesoporous silica into polyurethane (PU). Mesoporous silica particles with different pore size and structures, MCM‐41, cubic MCM‐48 and SBA‐16, were synthesized by templating method and functionalized with 3‐aminopropyltriethoxysilane (APTES). High porosity and aminated surface of the mesoporous silica enhance the adhesion of the particles to the PU matrix. The SEM and FTIR results showed strong interactions between the particles and the PU chains. Moreover, the thermal stability of the hybrid PUs improved compared to the pure polymer. Gas transport properties of the membranes were measured for pure CO₂, CH₄, O₂, and N₂ gases at 10 bar and 25°C. The results showed that the gas permeabilities enhanced with increasing in the loading of modified mesoporous silica particles. High porosity and amine‐functionalized particles render opportunities to enhance the gas diffusivity and solubility through the membranes. The enhanced gas transport properties of the mixed matrix membranes reveal the advantages of mesoporous silica to improve the gas permeability (CO₂ permeability up to ~70) without scarifying the gas selectivity (α(CO₂/N₂)~ 30 for 5 wt% SBA‐16 content).     

铑-三苯基膦配合物功能化的聚合物@介孔氧化硅复合材料在1-辛烯氢甲酰化反应中的应用(英文)

通过在介孔氧化硅材料中原位聚合的方法制备了三苯基膦功能化的有机聚合物@介孔氧化硅复合材料PPh3polymer@FDU-12.采用X射线衍射、氮气吸附脱附、透射电镜和热重等手段对其结构和组成进行了表征.该复合材料与金属前驱体Rh(acac)(CO)2配位后得到的固体催化剂,在长链烯烃1-辛烯的氢甲酰化反应中,醛选择性可达92%–96%,并表现出高于聚合物的活性(99%转化率).这主要归因于介孔氧化硅材料的高比表面积和有序的孔结构更有利于反应物和催化活性中心的接触.研究发现,调变复合材料中聚合物的含量或使用不同孔道结构的氧化硅载体(SBA-15,MCM-41和FDU-12)都会影响固体催化剂的反应活性和选择性.该方法得到的多相催化剂具有较好的循环使用性能,在循环使用15次后仍能保持较好的反应活性,但醛选择性有所降低.     

Ruthenium Carbenes Supported on Mesoporous Silicas as Highly Active and Selective Hybrid Catalysts for Olefin Metathesis Reactions under Continuous Flow

In the search for a highly active and selective heterogenized metathesis catalyst, we systematically varied the pore geometry and size of various silica‐based mesoporous (i.e., MCM‐41, MCM‐48, and SBA‐15) and microporous (ZSM‐5 and MWW) versus macroporous materials (D11‐10 and Aerosil 200), besides other process parameters (temperature, dilution, and mean residence time). The activity and, especially, selectivity of such “linker‐free” supports for ruthenium metathesis catalysts were evaluated in the cyclodimerization of cis‐cyclooctene to form 1,9‐cyclohexadecadiene, a valuable intermediate in the flavor and fragrance industry. The optimized material showed not only exceptionally high selectivity to the valuable product, but also turned out to be a truly heterogeneous catalyst with superior activity relative to the unsupported homogeneous complex.     

Mesoporous silica SBA-15 sheet with perpendicular nanochannels

Free-standing thin sheet form of mesoporous silica materials with perpendicular orientation is a much desired materials for its possible applications in catalysis, mask, and separation. A three component amphiphile system of sodium dodecyl sulfate/hexadecyltrimethylammonium bromide/pluronic-123(C(16)TMAB/SDS/P123) was employed to template the condensation of sodium silicates for the formation of SBA(⊥), a thin sheet of SBA-15 with perpendicular nanochannels. SBA(⊥) can be synthesized at SDS/C(16)TMAB=1.5 and T≥40°C and shows pH-dependent morphology. It has uniform pore size ～9 nm, homogeneous sheet thickness in the range of 60-300 nm and dimension of several microns. We studied in details the structure and morphology of the SBA(⊥) with variation of three experimental parameters: the SDS/C(16)TMAB ratio, the temperature, and the pH condition in the synthetic gel. It is proposed that the mixed surfactants of SDS and C(16)TMAB form catanionic vesicle in which the P123 and silicates are condensed. The balanced interaction of P123/silicate with the narrow confinement under surfactant bi-layers of C(16)TMAB/SDS promoted the formation of perpendicular nanochannels. Low temperature and pH conditions favor stronger segregation of the PPO and PEO-oligosilicate segments in the SBA(⊥) structure which gives the basis of thickness control of the sheet. The control of structure and morphology are discussed with modern theory of microphase separation in block copolymers under confinement.     

MSU-SMFI和MCM-41的催化裂化及烷基化活性比较

以MFI沸石前驱体作为基本结构单元组装介孔硅铝分子筛MSU-S_MFI. XRD和氮气吸附数据表明MSU-SMFI具有类似MCM-41的六方排列介孔孔道结构,而且其织构参数和以传统方法合成的含铝MCM-41也大体相当.NH₃-TPD显示由沸石前驱体组装的MSU-S_MFI较硅铝比相同的含铝MCM-41介孔分子筛的固体酸量显著提高.MSU-S_MFI上的异丙苯催化裂化转化率比含铝MCM-41提高31％, 1,3,5-三异丙苯在MSU-S_MFI上也发生了更深的裂解. MSU-S_MFI上萘的叔丁基化的转化率比含铝MCM-41提高了15％.以沸石前驱体作为基本结构单元是提高介孔分子筛固体酸性的有效方法.     

Remarkable effect of pore size on the catalytic activity of mesoporous silica for the acetalization of cyclohexanone with methanol

The catalytic activity of mesoporous silica (MCM-41) for the acetalization of cyclohexanone shows a volcano-shaped dependence on the pore diameter. The diameter of the cyclohexanone molecule is ca. 0.75 nm, while its acetalization with methanol was well accelerated on MCM-41 with a pore diameter of approximately 1.9 nm, and smaller or larger pores were not suitable for the catalysis. The catalytic activity was independent of the Al concentration.     

Control of Wall Thickness and Extraordinarily High Hydrothermal Stability of Nanoporous MCM‐41 Silica

Wall thickness of siliceous MCM‐41 could be controlled systematically up to 36.1 Å. A reasonable model explaining formation of thicker MCM‐41 walls, not enlarging pore channel is proposed on the basis of TGA and ¹³C MAS NMR data of samples. Thermal restructuring process under mild basic condition favors the silica redeposition on silica wall and building up thicker wall. Most mesostructure of calcined MCM‐41 with thicker wall was retained even after hydrothermal treatment in boiling water for 14 days. To our best knowledge, the excellent hydrothermal stability of the MCM‐41 silica reported herein has not been described before and facilitates practical applications of mesoporous molecular sieves in future.     

Hydrogen bonding of water confined in mesoporous silica MCM-41 and SBA-15 studied by 1H solid-state NMR

The adsorption of water in two mesoporous silica materials with cylindrical pores of uniform diameter, MCM-41 and SBA-15, was studied by 1H MAS (MAS=magic angle spinning) and static solid-state NMR spectroscopy. All observed hydrogen atoms are either surface -SiOH groups or hydrogen-bonded water molecules. Unlike MCM-41, some strongly bound water molecules exist at the inner surfaces of SBA-15 that are assigned to surface defects. At higher filling levels, a further difference between MCM-41 and SBA-15 is observed. Water molecules in MCM-41 exhibit a bimodal line distribution of chemical shifts, with one peak at the position of inner-bulk water, and the second peak at the position of water molecules in fast exchange with surface -SiOH groups. In SBA-15, a single line is observed that shifts continuously as the pore filling is increased. This result is attributed to a different pore-filling mechanism for the two silica materials. In MCM-41, due to its small pore diameter (3.3 nm), pore filling by pore condensation (axial-pore-filling mode) occurs at a low relative pressure, corresponding roughly to a single adsorbed monolayer. For SBA-15, owing to its larger pore diameter (8 nm), a gradual increase in the thickness of the adsorbed layer (radial-pore-filling mode) prevails until pore condensation takes place at a higher level of pore filling.     

中孔硅酸盐材料MCM-41的合成与表征研究(英文)

以十六烷基三甲基溴化铵为模板剂,硅酸钠为硅源,铝酸钠为铝源,在水热条件下成功地合成出了ＭＣＭ－４１中孔硅酸盐材料。采用ＸＲＤ、低温Ｎ２吸附脱附等测试手段对合成的ＭＣＭ－４１样品进行了表征。通过优化合成条件,合成出孔径３.２ ｎｍ、比表面９０４ｍ２／ｇ和孔壁厚约１.４６ ｎｍ的ＭＣＭ－４１分子筛。催化活性测定采用微反应活性实验来评价其活性和选择性。     

Cobalt Functionalization of Mesoporous Silica by Organosilane Grafting

MCM‐41, MCM‐48, and SBA‐15 have been functionalized with cobalt by grafting of different organosilane molecules and then calcined to remove the organic moieties. The materials have been characterized by N₂‐sorption, UV‐vis spectroscopy, TPR, ICP‐AES, XRD, and TGA. The nature of the formed cobalt species is dependent upon the number of amine groups in the organosilane molecules, due to the strength of the complexation. Only one amine group in the silane molecule leads to precipitation of Co₃O₄ particles during calcination, while two or more amine groups lead to the formation of cobalt silica at the surface. The obtained amount of precipitated cobalt in the samples is also dependent upon the number of amine groups and on the chain length of the silane molecules and the pore structure on the mesoporous material.     

Modified Mesoporous Silicate MCM-41 for Zinc Ion Adsorption: Synthesis, Characterization and Its Adsorption Behavior

Modified MCM‐41 has been prepared by bi‐functionalization of thiol and amino functional groups onto mesoporous silicate MCM‐41. Elemental analysis (EA), thermogravimetry analysis (TGA) and FTIR techniques were used to quantify the attachment of the thiol and amino functional groups to the mesoporous silicate pore wall. Powder X‐ray diffraction (PXRD) and nitrogen adsorption techniques were used to establish the pore diameter, packing of the pores and specific surface area of the modified mesoporous silicate MCM‐41. Adsorption behavior for 18 metal ions on this sorbent has been studied and discussed. This sorbent has high affinity for zinc ions against amino‐ or thiol‐functionalized MCM‐41 sorbents.