Silver nanoparticles synthesized from mesoporous Ag/SBA-15 composites

Silver nanoparticles were prepared by removing silica from mesoporous Ag/SBA-15 composites. The results of nitrogen adsorption–desorption isotherms, X-ray diffraction, transmission electron microscopy and UV–vis spectroscopy indicated that Ag nanoparticles existed in the pore channels of SBA-15. Ag nanoparticles with diameters in the range of 2.5–5.5 nm and a narrow size distribution were confirmed by atomic force microscope images and energy-dispersive X-ray spectroscopy. UV–vis spectroscopy showed a broad emission peak of Ag nanoparticles centered at ca. 438 nm.     

Tuning of nanostructured SBA-15 silica using phosphoric acid

A simple method is described to synthesize mesoporous SBA-15 with controlled distinct morphologies. Using the same initial synthesis mixture composition consisting of non-ionic P123 block co-polymer, tetra-ethyl orthosilicate as silica source and phosphoric acid, well-ordered mesoporous films, cakes, fibers and bundle-like structures were produced simply by changing the stirring rate. Free-standing films at the air–water interface and cake-like structures were obtained simultaneously under static conditions. On the other hand, fibers and bundles of threads resulted under vigorous and slow stirring conditions, respectively. Transmission electron microscopy (TEM) images of these bundles revealed straight parallel nanochannels oriented along the long axis of the bundles. X-ray fluorescence (XRF) measurements of the calcined samples indicated the presence of phosphorus, which might provide additional Brønsted acid sites for potential applications in catalysis.     

A comparative investigation on the properties of Cr-SBA-15 and CrOx/SBA-15

High-surface area and well-ordered mesoporous Cr-incorporated SBA-15 (Cr-SBA-15) and SBA-15-supported chromia (CrO_x/SBA-15) with Cr surface density = 0.05–1.11 Cr-atom/nm² have been prepared, respectively, using the one-step synthesis and incipient wetness impregnation method, and characterized by AAS, XRD, BET, ESEM, TEM, XPS, laser Raman, UV-Vis, FT-IR, and H₂-TPR. It is observed that the Cr-SBA-15 and CrO_x/SBA-15 samples showed an evolution of surface morphology from long chain-shaped to short rod-like and further to an irregularly spherical architecture at elevated Cr content, which might arise from the interaction of Cr ions or CrO_x domains with SBA-15. There were co-presence of tetrahedrally coordinated mono- and poly-chromate (Cr⁶⁺) as well as octahedrally coordinated Cr³⁺ species in Cr-SBA-15 and CrO_x/SBA-15, with the Cr⁶⁺ species being dominant at Cr surface density ≤0.22 Cr-atom/nm² in Cr-SBA-15 and Cr ≤0.54 Cr-atom/nm² in CrO_x/SBA-15, whereas the amount of the Cr³⁺ species increased markedly at Cr surface density ≥0.53 Cr-atom/nm² due to the formation of crystal Cr₂O₃ phase. Maximal Cr incorporation into Cr-SBA-15 and one monolayer surface CrO_x coverage on CrO_x/SBA-15 occurred at Cr surface density ≤0.53 Cr-atom/nm² and <1.11 Cr-atom/nm², respectively. The CrO_x/SBA-15 samples exhibited better reducibility than the Cr-SBA-15 samples, with the best reducibility exhibited at Cr surface densities of 0.54 and 0.12 Cr-atom/nm², respectively.     

Immobilization of uranium in cristobalite ceramic through adsorption on mesoporous SBA-15 and further sintering process

The development of an adsorbent which can be easily transformed into stable ceramic waste forms through a simple route is necessary for the treatment of the radioactive wastewater. Herein, we report on the immobilization of uranium in cristobalite ceramic through adsorption on mesoporous SBA-15 and further sintering process. The mesoporous SBA-15 with short pore length was synthesized and employed to remove uranium from aqueous solution. Subsequently, the SBA-15 with adsorbed U (U/SBA-15) was solidified by sintering. The effects of sintering temperature and U content on the structure, densification and aqueous durability of the obtained cristobalite ceramic waste forms were investigated. The results indicate that the U/SBA-15 can be transformed into stable cristobalite ceramic after sintering at 1100–1400 °C for 6 h. Furthermore, all the obtained cristobalite ceramic waste forms exhibit good aqueous durability (∼10⁻⁴ g m^-2 d^-1). This work demonstrates a potential route and adsorbent to dispose the radioactive wastewater.     

Use of mesoporous SBA-15 for nanostructuring titania for photocatalytic applications

SBA15–TiO₂ samples prepared by introducing titanium with a grafting method and having TiO₂ loadings below 15 wt.% have been characterized by XRF, XRD, IR, porosimetry, SEM, HRTEM, and UV–Visible diffuse reflectance. Differently from the samples reported in the literature characterized by a high TiO₂ loading, no evidences have been found for the presence of titania particles inside or outside the mesopores of SBA-15. Three different titanium species were instead evidenced to be present. The first two derive from the reaction of titanium with silanol groups in the corona area of inner SBA-15 walls leading to the formation of either TiO₄ tetrahedral sites (by reaction by hydroxyl nests of surface defect sites) and/or pseudo-octahedral surface sites anchored by two (or more) Si or Ti ions through bridging oxygens. The third species derives from the reaction of titanium in the regions with high sylanol density, e.g. in the micropores located in the corona of SBA-15 channels, leading to the formation of TiO₂-like nanoareas (probably Si-doped) with dimensions of around 1–2 nm maximum. The potential interest of these materials as photocatalysts, for the presence of a TiO₂-like nanoareas highly accessible by reactants, is discussed.     

MgO-modified VOx/SBA-15 as catalysts for the oxidative dehydrogenation of n-butane

VO_x catalysts supported on SBA-15 with and without MgO modification were prepared and characterized by N₂ adsorption–desorption, XRD, HRTEM, H₂-TPR, NH₃-TPD and XPS. Compared to the VO_x/SBA-15 catalyst, the VO_x/MgO/SBA-15 ones exhibit much higher C₄-olefins selectivity and yield in the oxidative dehydrogenation of n-butane. The enhanced performance can be attributed to the rise in VO_x reducibility as well as to the relatively lower acidity of the MgO-modified SBA-15 materials.     

Application of mesoporous MCM-48 and SBA-15 materials for the separation of biochemicals dissolved in aqueous solution

The application of molecular sieves for the separation and purification of biological molecules has been limited because of their available pore size (>1.3 nm). With the development of synthetic mesoporous materials, the available pore size range (1.5-10 nm) has been extended. They have pores large enough to allow access for a number of biological molecules. This work investigated the use of two mesoporous materials (MCM-48 and SBA-15) with different pore sizes and structures for adsorption of cephalosporin C as a model compound of biological molecules in terms of ethanol concentration, solution pH, and temperature. It was found that these materials have the potential for the separation and purification processes of biochemicals including antibiotics, amino acids, and proteins.     

Direct synthesis and superior catalytic performance of V-containing SBA-15 mesoporous materials for oxidative dehydrogenation of propane

V-containing SBA-15 mesoporous materials have been directly synthesized in an acidic and peroxidic medium. Compared to V/SBA-15 and V/SiO₂ samples prepared by impregnation method, the materials thus synthesized show larger surface areas, higher dispersion and reducibility of VO _x species, and superior catalytic performance for oxidative dehydrogenation of propane.     

Co-Mo／SBA-15柴油加氢脱硫研究

以介孔分子筛SBA-15为载体,担载Co—Mo双金属活性组分制备了深度加氢脱硫催化剂。通过XRD和BET表征表明,负载金属后SBA-15分子筛仍然保持二维晶相结构,表面积略有下降。以直馏柴油为原料,在固定床反应器上评价了催化剂的脱硫反应活性的结果表明,SBA-15介孔分子筛Co—Mo的负载量为W（CoO）=5％,w（MoO3）=25％;脱硫适宜的反应条件为：反应温度360℃,压力4．0MPa,氢油体积比400．0,空速2．0h^-1。在此条件下,柴油硫含量可由1350μg／g降至39μg／g。     

V/ SBA-15分子筛的制备及其对乙苯制苯乙酮反应的催化性能

以聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物(简称P123)为模板剂,正硅酸乙酯为硅源,前驱体为柠檬酸氧钒配合物,采用水热法在酸性条件下制备了V-SBA-15有序介孔材料。考察了不同晶化时间、模板剂用量等因素对介孔分子筛V-SBA-15制备的影响。结果表明,最优晶化时间为96 h、模板剂用量n=1.0〔以n(P123)/n(V+Si)计〕,在该条件下所制备的材料具有类似于分子筛SBA-15高度有序的六方介孔结构,且活性组分钒在介孔氧化硅基体中均匀分散。用XRD、FTIR、BET、SEM及TEM等方法对制备的分子筛V-SBA-15进行结构表征,同时在乙苯制苯乙酮反应中以苯乙酮选择性及收率来验证催化剂的催化性能。结果表明,在催化氧化乙苯制苯乙酮反应较优工艺条件下,苯乙酮选择性及收率分别为82.0%和38.60%。     

Effect of the preparation method on the structural stability and hydrodesulfurization activity of NiMo/SBA-15 catalysts

Defined hexagonal cylindrical pore structure SBA-15 material was synthesized as support for hydrotreating catalysts. The stability of the mesoporous material under acid and basic environments commonly used to prepare hydrotreating catalysts was investigated. The effects of the acid and basic treatments on the stability of SBA-15 and NiMo/SBA-15 catalysts were evidenced by different characterization techniques such as N₂ adsorption–desorption, X-ray diffraction (XRD), Raman Spectroscopy and high resolution transmission electron microscopy (HRTEM). Supported NiMo/SBA-15 catalysts prepared by pore volume co-impregnation in acidic, neutral and basic solutions of the Ni and Mo precursor salts were characterized to evaluate the textural and structural changes caused by the method of preparation. Characterization of the support after accelerated stability tests indicates large deterioration of the SBA-15 structural order at basic pH. The characterization results of oxide and sulfided catalysts indicate, for the catalysts prepared at high pH, an increasing presence of β–NiMoO₄ phase in the oxide catalysts, and a relatively lower population of MoS₂ in the sulfided catalysts. The activity of the different catalysts evaluated in the thiophene hydrodesulfurization reaction was higher for the catalysts prepared at low pH.     

超声对Cu(I)/SBA-15脱硫吸附剂制备和性能的影响

分别采用超声浸渍法和普通浸渍法制备了Cu(I)/SBA-15吸附剂,利用静态吸附实验比较了这两种方法制备的吸附剂在模型汽油中的噻吩吸附脱硫性能,并利用BET,TEM,XPS等手段对所制备的吸附剂进行了表征.结果表明,超声浸渍法制备的Cu(I)/SBA-15吸附剂的脱硫性能明显优于普通浸渍法制备的吸附剂.BET结果显示,超声促进了活性组分铜在吸附剂表面的分散.TEM分析表明,在超声场下制备的Cu(I)/SBA-15吸附剂表面的铜粒子颗粒较小,且分布均匀.XPS分析显示,超声有效地提高了铜离子在吸附剂表面的负载量,并且促进Cu(I)在其表面含量的增加,从而有利于吸附脱硫性能的提高.     

SBA-15 grafted with 3-aminopropyl triethoxysilane in supercritical propane for CO2 capture

Supercritical propane (SC-propane) was found to be a promising solvent for grafting (3-aminopropyl)triethoxysilane (APS) onto synthesized SBA-15 for CO₂ capture. The influence of operating conditions in SC-propane for CO₂ adsorption at different pressures (8.3–13.8 MPa), temperatures (85–120 °C), and periods of time (4–16 h) were evaluated. The CO₂ adsorption conditions under different partial pressures, temperatures and moisture were evaluated. The results showed a reduction in pore characteristics and an increased amount of grafted APS with increasing pressure and temperature after grafting. After grafting in SC-propane at 11.0 MPa and various temperatures for 16 h, a 3–20% increase in the amount of grafted APS and a 6–49% increase in the CO₂ adsorption capacity over the toluene refluxing was observed. The time required for grafting in SC-propane could be reduced while maintaining higher nitrogen content and CO₂ adsorption capacity compared with grafting in toluene refluxing.     

Al/SBA-15催化剂在萘异丙基化反应中的抗硫中毒性能

在磷酸介质中合成了SBA-15分子筛,并采用嫁接法合成了Al/SBA-15介孔分子筛催化剂,以噻吩为硫源,考察了该催化剂_存萘异丙基化反应过程中的抗硫中毒性能.通过XRD、TEM、FT-IR等多种表征手段对催化剂进行了表征,同时探讨了催化剂硫中毒机理.结果表明,在反应体系中,当噻吩浓度低于300×10~(-6)(摩尔分数)时,该催化剂在萘异丙基化反应中萘的转化率可达到47%以上,能够保持较高的催化活性,但是当噻吩浓度高于300×10-6时,催化活性明显下降,萘的转化率降至30%以下.     

Synthesis and characterization of Co-containing SBA-15 catalysts

Two Co-SBA-15 catalysts were synthesized and characterized by thermogravimetry, X-ray diffraction, scanning electron microscopy, transmission electron microscopy, porosity, UV–visible diffuse reflectance and temperature programmed reduction with H₂. The first catalyst was prepared synthesizing SBA-15 and then adding Co ions by impregnation (Co_imprSBA-15). The second catalyst was prepared using a more complex procedure of immobilization of cobalt ions in the presence of pyridine and H₂O₂ on –COOH groups anchored to the SBA-15 structure [Co-SBA-15(COOH)]. These COOH groups were created starting from cyano groups introduced during the synthesis of the periodic mesoporous materials as 4-triethoxysilylbutyronitrile. Characterization of the samples indicates that in both cases the typical 2D periodical hexagonal structure of SBA-15 was obtained, but with less ordered packing in the second case. The cobalt is highly dispersed in the SBA-15 (up to 9% w/w) and is present mainly as Co²⁺ ions in highly distorted tetrahedral or square pyramidal coordination. Some coordinatively unsaturated Co(II) Lewis acid centers are present in Co_imprSBA-15, while in Co-SBA-15(COOH) coordination of pyridine to cobalt tentatively may induce the formation of Co³⁺ ions, although in both catalysts the dominant species are Co²⁺ ions in a very close environment.     

氮化SBA-15负载高分散过渡金属用于丙烷高效直接脱氢

以氮化法修饰的介孔二氧化硅（SBA-15）为载体,采用浸渍法制备了不同过渡金属（钴、镍、铁、铜）脱氢催化剂。通过X射线衍射光谱和N2吸附-脱附分析表明氮化后的载体仍能保持良好的介孔结构;通过扫描电子显微镜分析表明金属处于高度分散的良好状态;通过程序升温还原和X射线光电子能谱分析表明氮化SBA-15改变了金属的电子结构,增强了载体与金属之间的相互作用力。采用定量浸渍法制备了金属负载量为1%（质量分数）的脱氢催化剂,并进行了性能评价。结果表明,丙烷脱氢催化剂活性顺序由高到低依次为Co-SBA-15N900-1%、Fe-SBA-15N900-1%、Cu-SBA-15N900-1%、Ni-SBA-15N900-1%,其中Co-SBA-15N900-1%催化剂的丙烷转化率为33%,丙烯选择性为88%。     

Effect of pore structure of SBA-15 on immobilization of hemoglobin

Immobilization of hemoglobin (Hb) in SBA-15 with various pore sizes by physical adsorption was studied. The structure changes of mesoporous SBA-15 before and after the immobilization of Hb were characterized by N₂ adsorption isotherms, X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and Ultraviolet-visible spectroscopy (UV). The results indicate that SBA-15 is a good support for the immobilization of Hb due to its regular structure, large pore diameter, and high surface area. After immobilization of Hb, the regular structure of SBA-15 is still kept, but the pore diameter, pore volume and surface area decrease. With the increase of pore size, the binding amount and leaching amount of Hb increase. There is a maximum binding amount of Hb up to 355.2 mg/g _SBA-15 when pore size is 8.9 nm. It is suggested that the immobilization of Hb depends significantly on the pore size of SBA-15.     

介孔分子筛SBA-15在催化领域的应用进展

从负载固体酸催化剂、金属和金属氧化物以及手性催化剂三方面综述了介孔分子筛SBA-15在催化领域应用的研究进展;并展望了介孔分子筛SBA-15在催化领域的研究方向。     

SBA-15的改性及催化文冠果油制备生物柴油

以介孔分子筛SBA-15为载体,采用直接合成法和后合成法镀饰Al后再负载碱金属盐KNO₃,制得负载型固体碱催化剂KNO₃-AlSBA-15和KNO₃-Al-SBA-15。用XRD、BET、SEM以及CO₂-TPD对催化剂进行表征。结果表明：在SBA-15上镀饰Al可以保护分子筛的介孔结构;进一步负载KNO₃,能够增强催化剂的碱性。将其应用于催化文冠果油酯交换制备生物柴油,结果显示催化剂KNO₃-Al-SBA-15的催化活性最好,优于传统均相催化剂,所得生物柴油产率可达92%,重复使用多次仍具有较好的催化效果。     

P/SBA-15催化合成十六烷基苯

采用负载磷酸的SBA-15分子筛作为催化剂,以苯和十六碳烯为原料,经烷基化反应合成十六烷基苯。在微型液相固定床反应器上考察了反应温度、空速、体系压力、磷酸负载量以及苯烯摩尔比等反应条件对催化剂性能的影响。研究结果表明,磷酸的适宜负载量约为7%(质量分数),适宜反应条件为反应温度180℃、空速为2.0 h-1、体系压力为2.0 MPa和苯、烯摩尔比为10。在此条件下,十六碳烯的转化率可达到94.5%,十六烷基苯选择性可达93%。催化剂单程寿命达到120 h以上。负载磷酸的SBA-15催化剂呈现较好的催化活性和稳定性。