有序介孔材料的合成及应用

自从1992年Mobil公司的研究人员选用烷基季铵盐阳离子表面活性剂作为模板剂,首次合成了介孔氧化硅分子筛M41S系列以来,中孔SiO2纳米粒子(MSNs)始终吸引研究人员,因为介孔材料具有大比表面积、高孔道规整度和孔径分布范围集中等优点,而且具有优良的结构可设计性。结合国内外研究成果,主要介绍了介孔SiO2材料的不同合成方法,如溶胶-凝胶法、微波辅助技术、化学蚀刻技术和模板法等,并简单介绍了其应用,对其未来的发展前景进行了展望。     

有机粘土合成的介孔材料

有机粘土合成的介孔材料(MSCs)是用有机物或聚合物有机改性的粘土凝胶经过水热结晶，使得插层的粘土片层随机分散在聚合物基体中，然后焙烧脱去有机模板而制得。介孔半径的大小与聚合物质量百分含量及分子量大小有关。该类介孔材料可应用于加氢脱硫催化剂载体、分子的选择吸收、聚合物基纳米复合材料等领域。本文介绍了MSCs的制备方法及应用。     

纳米CeO2-TiO2复合介孔材料的制备与性能

以TiCl4为原料,Ce（SO4）2-4H2o为掺杂剂,采用水热法制备了CeO2-TiO2和介孔材料,并利用X-射线衍射、透射电镜和N2吸附脱吸附实验等对样品进行了表征。光催化性能实验证明适量CeO2掺杂对TiO2的光催化效果有很大程度的提高,但是当掺杂量超过一定比例后反而会降低光催化效果,并且样品的焙烧时间和温度对样品的光催化效果也有一定的影响。     

介孔炭材料应用于电化学催化的研究进展

由于介孔炭材料具有高比表面、均一可调的孔径尺寸和形貌、良好的导电性和化学稳定性等优点,已被广泛应用到催化、吸附、分离和电化学储能等领域.近年来,多组分的掺杂与复合使介孔炭材料拥有可调变的功能性,已成为材料领域研究的一个热点.本文首先介绍介孔炭材料的合成,包括软模板法、硬模板法和无模板法等.接着论述介孔炭及其复合材料在电...     

TiO2介孔材料合成及应用

TiO2介孔材料因其在光催化、催化剂载体、传感器、电化学器件等方面具有种种潜在的用途而备受关注，已经成为材料科学一个崭新的研究方向。综述了介孔TiO2的合成方法及应用等方面的研究成果。     

软模板法制备纳米TiO2介孔材料

以三嵌段共聚物EO20PO70EO20(P123)为模板剂,异丙醇钛(简称TTIP)为无机钛源,在适量强酸的催化作用下,由软模板法合成出TiO2介孔材料的前驱体凝胶后,经老化、煅烧得到了TiO2介孔材料.分别利用X射线衍射仪、高分辨率透射电子显微镜以及比表面积与孔径分析仪对制得的TiO2介孔材料的结构、形貌、比表面积和孔径进行了表征,并探讨了煅烧温度对介孔形成的影响.结果表明:通过调整原料的比例,在400℃下煅烧可得到局部结晶有序、比表面积大的纳米TiO2介孔材料.     

三维有序介孔结构氧化钼制备及催化性能

以三维有序介孔分子筛KIT-6为模板剂制备碳模板, 七钼酸铵为钼源, 采用超声辅助下的真空浸渍法, 合成了三维(3D)有序介孔、蠕虫状介孔MoO₃。采用TEM、HRTEM、SAED、XRD、TG/DT、N₂吸脱附等对材料物理性能进行了表征。采用H₂-TPR、甲苯和一氧化碳完全氧化等对催化性能进行了评价。研究发现: 制备的三维有序介孔MoO₃为正交相晶体结构, 比表面积194 m²/g; 在转化率分别为50%、90%、100%时, 甲苯的起燃温度分别为203℃、215℃、225℃; CO起燃温度分别为114℃、158℃、180℃。3D-MoO₃优良的催化性能与高比表面和三维有序介孔架构密切相关。     

复合介孔材料的结构与催化性能

以三嵌段共聚物P123为模板剂、正硅酸乙酯为硅源,在强酸和水热条件下合成了介孔分子筛SBA-15,用胺丙基三乙氧基硅烷对分子筛进行功能化。运用X射线衍射、傅里叶红外光谱,N_2吸附-脱附以及透射电子显微镜等手段对功能化前后的介孔分子筛进行了表征。以甘氨酸法制备草甘膦工艺为模型反应进行的催化性能分析表明:该介孔分子筛对该反应具有较高的催化性能。     

纳米镍/介孔二氧化硅复合材料的组装及结构和性质 Ⅰ : 纳米镍/介孔二氧化硅复合材料的制备及结构表征

利用介孔组装,可以进行纳米复合材料结构和功能设计。通过溶胶-凝胶方法,采用混合、浸泡和氢热还原工艺,获得纳米镍/介孔二氧化硅复合材料。运用DSC、XRD、XPS、TEM等手段对纳米镍/介孔二氧化硅复合材料进行表征。结果表明,纳米金属Ni颗粒的尺寸由介孔SiO₂的结构和孔径分布决定,受还原温度和成分等影响,在8~20nm范围变化,浸泡法更容易获得纳米金属颗粒均匀分布的复合材料。由于SiO₂介孔结构连通,纳米Ni表面存在氧化,纳米颗粒存在于介孔中形成壳结构。介孔二氧化硅基体中添加稀土元素Ce,有利于增强介孔基体骨架强度,限制纳米颗粒聚集长大。      

软模板法制备高比表面CeO_2-ZrO_2介孔结构材料及其表征

以非离子表面活性剂P123为模板剂,ZrOCl2.8H2O和Ce(NO3)3.6H2O为原料,制备出高比表面的CeO2-ZrO2复合氧化物介孔材料;研究制备CeO2-ZrO2介孔材料的主要影响因素,确定最佳合成参数;分析了CeO2-ZrO2介孔材料的形成和结构。     

Synthesis of mesoporous Co/Ce-SBA-15 materials and their catalytic performance in the catalytic oxidation of benzene

Cerium-containing SBA-15 mesoporous materials, with different Ce/Si molar ratios, were synthesized by a direct hydrothermal synthesis method and further modified by impregnation with 10, 15 and 20 wt.% Co. Characterizations by powder X-ray diffraction (XRD), N₂ sorption, inductively coupled plasma (ICP) and UV-vis spectroscopy were carried out. The small-angle XRD and N₂ sorption characterizations showed that these Co supported materials have less-ordered mesoporous structures with partial blockage of pores, and their specific surface area, pore volume and pore size were relatively lower than those of unsupported cerium-containing SBA-15. Spinel Co₃O₄ constituted the predominant cobalt phase in the prepared catalysts, and CeO₂ was also detected. All the Co supported catalysts exhibited high catalytic activity in the oxidation of benzene.     

Catalytic wet peroxide oxidation of phenol solutions over CuO/CeO2 systems

Three 5% CuO/CeO(2) catalysts were synthesized by sol-gel, precipitation and combustion methods, followed by incipient wetness impregnation with copper nitrate. The samples were characterized by XRD, TPR, BET and tested for the catalytic wet peroxide oxidation of a phenol solution (5 g/L). The reaction took place in a batch reactor at atmospheric pressure, in a temperature range of 60-80°C, during 4h. Phenol conversion, H(2)O(2) consumption, pH and chemical oxygen demand were determined. The reaction temperature and the catalyst loading did improve the phenol and the H(2)O(2) conversions. The effect on the selectivity towards complete mineralization was less marked, with levels among 60-70%. Stepwise addition of H(2)O(2) was also tested.     

Effect of CeO2 doping on catalytic activity of Fe2O3/gamma-Al2O(3) catalyst for catalytic wet peroxide oxidation of azo dyes

In order to find a catalyst with high activity and stability for catalytic wet peroxide oxidation (CWPO) process under normal condition, with Fe(2)O(3)/gamma-Al(2)O(3) and Fe(2)O(3)-CeO(2)/gamma-Al(2)O(3) catalysts prepared by impregnation method, the effect of CeO(2) doping on the structure and catalytic activity of Fe(2)O(3)/gamma-Al(2)O(3) for catalytic wet peroxide oxidation of azo dyes at 25 degrees C and atmospheric pressure is evaluated using BET, SEM, XRF, XRD, XPS and chemical analysis techniques, and test results show that, better dispersion and smaller size of Fe(2)O(3) crystal can be achieved by adding CeO(2), and the content of chemisorbed oxygen can also be increased on the surface of catalyst. CWPO experimental results indicate that azo dyes in simulated wastewater can be efficiently mineralized and the catalytic activity of Fe(2)O(3)-CeO(2)/gamma-Al(2)O(3) can be increased by about 10% compared with that of Fe(2)O(3)/gamma-Al(2)O(3) because of the promotion of the structural and redox properties of the ferric oxide by ceria doped. Leaching tests indicate that Fe(2)O(3)/gamma-Al(2)O(3) and Fe(2)O(3)-CeO(2)/gamma-Al(2)O(3) are stable with a negligible amount of irons found in the aqueous solution after reaction for 2h. It can therefore be concluded from results and discussion that in comparison with Fe(2)O(3)/gamma-Al(2)O(3), Fe(2)O(3)-CeO(2)/gamma-Al(2)O(3) is a suitable catalyst, which can effectively degrade contaminants at normal temperature and atmospheric pressure.     

Facile synthesis,characterization and low-temperature catalytic performance of Au/CeO2 nanorods

Au/CeO₂ nanorods of ~ 15 nm in diameter and 100–400 nm in length have been synthesized through an efficient and simple method, and subsequently the novel low-temperature catalytic performance of Au/CeO₂ nanorods for CO oxidation is found. The composites are characterized by transmission electron microscopy, X-ray diffraction as well as X-ray photoelectron spectroscopy. It is found that the Au nanoparticles with an average diameter of 8 nm are distributed uniformly on the surface of CeO₂ nanorods. The possible formation mechanism of Au/CeO₂ nanorods has been discussed. The T₅₀ depicting the catalytic activity for CO oxidation can reach 62.1 °C, which is much lower than that of CeO₂ nanorods or Au/CeO₂ powders. In addition, Au/CeO₂ nanorods exhibit excellent stability as catalysts for CO oxidation.     

介孔Fe-SiO2复合材料的制备及吸附协同催化性能

采用原位一步合成法,在含有模板剂、AlCl₃和H₂O的弱酸性反应体系中,引入Si源和Fe源,通过原位共沉积的方式,成功制备出Fe修饰的介孔SiO₂（Fe-SiO₂）复合材料。采用XRD、N₂吸附、FTIR、UV-vis、SEM和EDS等手段表征了介孔Fe-SiO₂复合材料样品的结构、形貌和化学组成;将所获得的介孔Fe-SiO₂复合材料用于吸附和协同催化去除水体中有机污染物亚甲基蓝（MB）;考察了Fe源添加量对介孔Fe-SiO₂复合材料结构和性能的影响。研究结果表明:合成体系中rFe:Si ≤ 0.05（摩尔比）时,所得Fe-SiO₂介孔材料保留了介孔孔道的高度有序性和大比表面积（860~889 m2·g-1）,Fe在介孔Fe-SiO₂复合材料中主要以四配位骨架掺杂的形式存在;当rFe:Si=0.1时,其比表面积下降为526 m2·g-1,Fe以骨架内和骨架外氧化物的形式共存于介孔Fe-SiO₂复合材料中。所有介孔Fe-SiO₂复合材料在去除MB的实验中均表现出很大的吸附容量和优良的多相类芬顿催化能力。其中,rFe:Si=0.05时所获得的介孔Fe-SiO₂复合材料样品性能最佳,对高浓度MB（250 mg·L-1）的吸附和催化总量达到213 mgg-1。      

催化湿式氧化高浓度对氯苯基异氰酸酯生产废水催化剂的研究

以过渡金属氧化物CuO为主活性组分,通过对ZrO2的复合和掺入电子助剂CeO2的考察,研制出适用于催化湿式氧化处理高浓度对氯苯基异氰酸酯生产废水的复合催化荆.在固定床鼓泡式反应器连续反应装置上对废水进行处理,考察了各组分浸渍液浓度、焙烧温度、焙烧时间等制备条件对催化剂的催化活性的影响,确定了最佳制备条件.结果表明:优化制备的CuO-ZrO2-CeO2/TiO2催化荆,用于处理高浓度对氯苯基异氰酸酯生产废水时具有较好的催化活性,在反应温度T=240℃,反应压力P=6.5MPa,空速=2.0h-1,V(气):V(水)=230:1,进水pH=8条件下CODcr去除率达到96.9%,而在相同反应条件下未加催化剂的湿式氧化CODcr去除率只有40.8%.     

Ni and Cu incorporated mesoporous nanocomposite catalytic materials

Nickel and copper incorporated MCM-41-like mesoporous nanocomposite materials prepared by the direct hydrothermal synthesis and the impregnation procedures showed highly attractive pore structure and surface area results for catalytic applications. The XRD patterns showed that characteristic MCM-41 structure was preserved for the materials synthesized following an impregnation procedure before the calcination step. The surface area of the Cu impregnated material with a quite high Cu/Si atomic ratio (0.19) was 631 m2/g. Very narrow pore size distributions with an average pore diameter of about 2.7 nm were obtained as a result of plugging of some of the smaller pores by Cu nanoballs. For lower metal to Si ratios (for instance for Ni/Si = 0.06) much higher surface area values (1130 m2/g) were obtained. In the case of nanocomposite materials synthesized by the direct hydrothermal route, MCM-41 structure was not destroyed for samples containing metal to Si atomic ratios as high as 0.12. In the case of materials containing Cu/Si and Ni/Si ratios over 0.2 wider pore size distributions and some decrease of surface area were observed.     

Enhanced activity and stability of Cu-Mn and Cu-Ag catalysts supported on nanostructured mesoporous CeO2 for CO oxidation

Cu, Mn and Ag nanoparticles are loaded on nanostructured mesoporous CeO2 as catalysts for CO oxidation. The Cu/CeO2 catalyst exhibits an obvious deactivation after the stability test at 95 degrees C for 60 h. This is caused by carbon deposition as confirmed by FTIR spectroscopy, Raman spectroscopy and thermogravimetry-differential scanning calorimetry-mass spectroscopy (TG-DSC-MS) analysis. It is found that the Cu-Mn or Cu-Ag binary metal catalysts supported on the nanostructured CeO2 exhibit much improved activity and stability in CO oxidation. In ease case, carbon deposition is absent in the similar stability test, due to enhanced oxygen adsorption property.     

多孔Ag/TiO2的制备及其光催化性研究

以工业TiOSO4溶液水解得到的多孔偏钛酸为载体,通过光催化还原法制备了多孔Ag/TiO2光催化剂.用XRD、SEM、EDS及低温氮吸附脱附法对样品进行了表征.以光催化氧化降解亚甲基蓝为目标反应,考察了不同制备条件对样品光催化活性的影响.结果表明,制备的Ag/TiO2为负载有非晶态纳米银粒的锐钛矿型TiO2光催化剂,比表面积高达197m2/g,其光催化活性远优于未载银的TiO2.