纳米介孔材料的催化应用前景

介孔材料大的比表面积和规则的孔道结构使其具有很高的活性和极大的吸附容量,大的孔径使其在催化裂化、精细化工等大分子加工领域具有潜在的应用价值。文中介绍了近年来介孔材料在催化领域的应用情况,同时对今后的发展方向和应用前景进行预测和展望。     

Shaping Colloidal Rutile into Thermally Stable and Porous Mesoscopic Titania Balls

High crystallinity and controlled porosity are advantageous for many applications such as energy conversion and power generation. Despite many efforts in the last decades, the direct synthesis of organic–inorganic composite materials with crystalline transition metal oxides is still a major challenge. In general, molecules serve as inorganic precursors and heat treatment is required to convert as‐synthesized amorphous composites to stable crystalline materials. Herein, an alternative approach to the direct synthesis of crystalline polymer–metal oxide composites by using a spherical polyelectrolyte brush as the template system is presented. Pre‐synthesized electrostatically stabilized rutile nanocrystals that carry a positive surface charge are used as inorganic precursors. In this approach, the strong Coulomb interactions between anionic polyelectrolyte brush chains and cationic crystalline rutile colloids, whose surfaces are not capped and therefore reactive, are the key factors for the organic–inorganic crystalline composite formation. Stepwise calcination first under argon and followed with a second calcination in air lead to the complete removal of the polymer template without collapse and porous rutile balls are obtained. The results suggest that any colloids that carry a surface charge might serve as inorganic precursors when charged templates are used. It is expected that this hierarchical route for structuring oxides at the mesoscale is generally applicable.     

TiO2 anatase nanoparticle networks: synthesis, structure, and electrochemical performance

Nanocrystalline anatase TiO(2) materials with different specific surface areas and pore size distributions are prepared via sol-gel and miniemulsion routes in the presence of surfactants. The samples are characterized by X-ray diffraction, nitrogen sorption, transmission electron microscopy, and electrochemical measurements. The materials show a pure anatase phase with average crystallite size of about 10 nm. The nitrogen sorption analysis reveals specific surface areas ranging from 25 to 150 m(2) g(-1) . It is demonstrated that the electrochemical performance of this material strongly depends on morphology. The mesoporous TiO(2) samples exhibit excellent high rate capabilities and good cycling stability.     

介孔泡沫及手性介孔材料的制备与应用

介孔泡沫材料具有超大介孔、开放式孔结构、孔径可调等特点,在催化剂载体、酶固定等领域具有明显的优势.手性介孔材料除了具有常规介孔材料的特点外还具有手性,因此在立体化学领域具有潜在的研究与应用价值.综述了介孔泡沫材料以及手性介孔材料的合成与应用.     

晶态过渡金属氧化物介孔材料的合成进展

过渡金属氧化物介孔材料是继介孔氧化硅之后引起广泛关注的研究热点,而晶态时过渡金属氧化物介孔材料的性质及广泛应用起着决定性的作用.从合成角度综述了硬模板和软模板法制备有序晶态过渡金属氧化物介孔材料的研究进展,并且展望了介孔材料的发展趋势.硬模板法制备的介孔材料比软模板法有更好的有序性,而软模板法合成过程简便,有更好的工业应用前景,但需解决材料的有序介孔结构热稳定性差的难题.     

Ordered mesoporous α-Fe2O3 (hematite) thin-film electrodes for application in high rate rechargeable lithium batteries

Herein is reported the synthesis of ordered mesoporous α-Fe(2)O(3) thin films produced through coassembly strategies using a poly(ethylene-co-butylene)-block-poly(ethylene oxide) diblock copolymer as the structure-directing agent and hydrated ferric nitrate as the molecular precursor. The sol-gel derived α-Fe(2)O(3) materials are highly crystalline after removal of the organic template and the nanoscale porosity can be retained up to annealing temperatures of 600 °C. While this paper focuses on the characterization of these materials using various state-of-the-art techniques, including grazing-incidence small-angle X-ray scattering, time-of-flight secondary ion mass spectrometry, X-ray photoelectron spectroscopy, and UV-vis and Raman spectroscopy, the electrochemical properties are also examined and it is demonstrated that mesoporous α-Fe(2)O(3) thin-film electrodes not only exhibit enhanced lithium-ion storage capabilities compared to bulk materials but also show excellent cycling stabilities by suppressing the irreversible phase transformations that are observed in microcrystalline α-Fe(2)O(3).     

有机模板剂对合成纳米TiO2结构影响规律的研究

以钛酸四丁酯为前驱体,乙醇为溶剂,采用溶胶-凝胶法制备纳米二氧化钛.选择P123作为模板剂考察了不同n(P123)/n(Ti)对TiO2织构性能以及晶粒尺寸的影响.采用碳化的方法使有机物在氩气气氛中高温焙烧后形成的炭层对孔道起支撑作用,防止孔道的塌陷并得到高度晶化的二氧化钛,同时考察了碳化温度和不同模板剂对二氧化钛织构性能的影响规律.结合X射线衍射(XRD)、N2吸附脱附、热分析(TG/DSC)表征手段得到以下结论:物质的量比在0～0.030范围内,P123含量的增加有利于晶粒尺寸的减小和比表面积的增大;碳化过程提高了TiO2的热稳定性,随着碳化温度的升高TiO2比表面积变化不大;P123、P     

模板法制备介孔VN纳米电极材料及其电容性能

以十六烷基三甲基溴化铵(CTAB)为模板剂, 通过高温氨解还原V₂O₅前驱体制得了具有丰富介孔的VN纳米材料, 采用XRD与TEM分析观察样品的结构和形貌, 用N2吸附测试样品的比表面积和孔径分布. XRD分析表明, 介孔VN纳米材料属于立方晶系的晶体结构. TEM和N₂吸附测试结果表明, VN纳米材料的颗粒粒径大约为10 nm, 比表面积为88 m²/g, 有比较丰富的2~6 nm的介孔. 在1 mol/L KOH电解液中进行循环伏安和恒流充放电测试研究其电容性能, 结果显示, VN电极同时具有双电层电容性能和氧化–还原反应的准电容性能, 1 mV/s的扫描速率下能获得517 F/g的比电容; 当扫描速率增大到10 mV/s时, 其比电容仍有275 F/g.     

基于短孔道Zr-Ce-SBA-15固定胃蛋白酶的活性生物催化剂

在不外加无机酸的条件下, 通过水热合成法制备了短孔道六方板状有序介孔材料Zr-Ce-SBA-15 (ZCS). 以ZCS和传统SBA-15为载体对胃蛋白酶进行固定, 并利用N-(2-氨乙基)-3-氨丙基三甲氧基硅烷(AAPTS)对酶固定化材料进行功能化, 以缩小开口孔径从而减少酶泄漏. 采用小角X射线衍射、扫描电镜、透射电镜、氮气吸附和红外光谱对样品进行结构表征. 结果表明, 胃蛋白酶成功固定到介孔孔道中, AAPTS嫁接到材料中且没有破坏介孔结构. 固定化实验表明相比于SBA-15, ZCS对胃蛋白酶具有较快的吸附速度和较强的固定化能力(最大负载量为257.9 mg/g), 短孔道材料能有效地促进分子的扩散传递. 催化活性测定以牛血红蛋白为探针物, 与游离酶相比, 固定酶对牛血红蛋白保持着稳定的活性.