模板法制备TiO2介孔材料的研究进展

TiO2介孔材料在催化、吸附及分离等领域具有十分重要的应用,是当今介孔材料研究的热点之一。本文综述了介孔材料的分类,概述了模板法制备TiO2介孔材料的机理及不同类型的模板剂在TiO2介孔材料制备中的应用,指出了模板剂脱除过程中存在的问题,并对介孔材料的研究和应用前景进行了展望。     

镧(Ⅲ)对SBA-15分子筛改性研究

借助水热法,利用三嵌段共聚物聚(1,2-亚乙基二醇)-嵌段-聚(丙二醇)-嵌段-聚(1,2-亚乙基二醇)为模板剂,正硅酸四乙酯为硅源,强酸性条件下制备了分子筛SBA-15.分别以水及水+乙醇为介质采用LaCl₃溶液与煅烧的主体材料SBA-15分子筛固-液相交换法,制备了La-(SBA-15)复合材料.利用化学分析、粉末XRD、N₂吸附技术、IR评价了制备方法的有效性及对SBA-15分子筛孔结构的影响.结果表明,镧已并入SBA-15分子筛中,SBA-15内表面上的硅羟基团是镧进入的主要位置,部分客体在分子筛孔道内.制得的材料La-(SBA-15)保持高度有序的介孔二维六角结构,不改变载体SBA-15的介孔孔道结构.此外,考察了La-(SBA-15)产物的发光现象.     

模板剂对合成硅铝酸盐介孔材料的影响

为探究模板剂在合成介孔材料过程中的关键作用,本文以偏铝酸钠和水玻璃为导向剂,采用水热法在不同模板剂条件下合成硅铝酸盐介孔材料。利用X射线衍射仪(XRD),扫描电子显微镜(SEM)以及比表面积测定仪(N₂吸附/脱附)对合成样品进行表征分析,研究了模板剂种类、质量浓度及煅烧脱除模板剂温度对合成硅铝酸盐介孔材料的孔结构、形貌及性能参数的影响。研究表明,6种不同模板剂合成的硅铝酸盐介孔材料均存在明显短程有序结构,最佳模板剂为F108(PEO₁₃₃-PPO₅₀-PEO₁₃₃),质量浓度为0.04 g/mL,煅烧温度550 ℃时合成的硅铝酸盐介孔材料的结构参数达到最优。     

单分散短棒状介孔二氧化硅的制备

在温和碱性条件下,以十六烷基三甲基溴化铵为模板剂,正硅酸乙酯为硅源,平平加Os-25为助剂,制备出轴向尺寸为200nm左右,径向尺寸在60-80nm范围内的单分散短棒状纳米介孔二氧化硅MCM-41．研究了CTAB用量、平平加Os-25的用量、反应时间等因素对介孔形貌和纳米粒子分散性的影响．结果表明,适量的非离子表面活性剂平平加Os-25具有助模板剂的作用,可以有效地提高纳米介孔粉体的有序性．平平加Os-25与十六烷基三甲基溴化铵的摩尔比在0．02-0．06范围内,可以得到有序性好、分散性好的短棒状介孔二氧化硅MCM-41．     

介孔炭作为加氢脱硫催化剂载体材料的研究

以介孔硅SBA-15为模板,焦糖和呋喃醇为碳源,通过多种浇注法制备介孔炭材料.采用低温氮吸附、透射电镜和X射线小角衍射分析模板及介孔炭的织构.结果显示合成的介孔炭成功地复制了SBA-15的结构.以制备的介孔炭作载体担载钴钼合成了加氢脱硫催化剂,利用X射线能谱、透射电镜能量分布谱及一氧化氮化学吸附评估了催化剂的活性及活性点分布,结果表明介孔炭担载的催化剂活性高于活性炭担载的同类催化剂.     

SBA-15介孔分子筛吸附电镀废水中Cu2＋的最佳条件和效果

为了开发新型高效廉价的吸咐材料,利用常压微波辐射法在酸性条件下以三嵌段共聚物（P123）为模板剂,制备了高度有序的SBA．15型介孔分子筛。研究了静态条件下SBA-15对电镀废水中Cu2＋的吸附,探讨了SBA-15用量、废水pH值、吸附时间、吸附温度对去除Cun效果的影响。结果表明：废水pH值为5．0,Cu2＋在0—1...     

SBA-15模板法有序多孔炭膜材料的制备及表征

以介孔分子筛SBA-15为模板剂,聚酰亚胺为前驱体,经共混、成膜、炭化及脱模板过程,制备了有序多孔炭膜材料(OPCM)。通过热失重、红外光谱、电子显微镜和X-射线衍射,分别对前驱体热稳定性、膜表面官能团、微观形貌与微观结构进行了表征。考察了SBA-15脱除前后的炭膜微观结构与形貌,及OPCM气体分离性能。结果显示,当炭化温度为650℃、SBA-15用量为1%时,所制得OPCM的气体分离系数显著高于努森扩散。     

尿素-过氧化氢混合模板法合成介孔二氧化硅

以尿素-过氧化氢为混合模板、正硅酸乙酯为硅源,在酸性条件下,通过溶胶-凝胶过程合成二氧化硅介孔材料。采用煅烧法除去模板剂,用红外光谱、XRD、N2吸附-脱附、HRTEM等分析测试手段对介孔材料的结构和形态进行了表征。结果表明:与以尿素为单一模板相比,采用混合模板剂所合成介孔材料为蠕虫状,孔径分布基本保持不变、比表面积相近(分别为445、431m2/g)、孔径(分别为7.04、8.11nm)和孔体积(分别为0.783、0.874cm3/g)明显增大。     

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。     

粉煤灰合成介孔分子筛SBA-15对稀土元素的吸附

以粉煤灰为原料、EO_(20)PO_(70)EO_(20)(P123)为模板剂,采用碱溶-水热法制备出高度有序的介孔分子筛SBA-15;以3-氨丙基三乙氧基硅烷(APTES)为修饰剂对SBA-15进行表面氨基化。再用膦酰基乙酸(PAA)、二乙烯三胺五乙酸二酐(DTPADA)对其进一步功能化,合成材料PAA-SBA-15和DTPADA-SBA-15。通过小角XRD衍射、全反射红外、和氮气吸附对材料进行了分析和表征,并研究了材料对稀土元素Yb、Ho的吸附性能。结果表明,经过不同官能团修饰的材料依然具有良好的介孔结构;此外吸附结果表明,在pH值为6时,PAA-SBA-15对Ho、Yb的吸附效率分别为89.8%,94.4%;在pH值为2时,DTPADA-SBA-15对Ho、Yb的吸附效率为92.6%,89.0%。     

Equilibrium and Kinetic Adsorption Study of the Removal of Orange-G Dye Using Carbon Mesoporous Material

Mesoporous carbon CMK-3 was synthesized by using SBA-15 silica mesoporous as hard template and characterized through nitrogen adsorption/desorption and low angle X-ray diffraction.As-prepared material with large pores and high surface area was used to remove Orange G dye from aqueous solution.Adsorption experiments were carried out as batch studies at variety of contact times,pH,initial dye concentrations,temperatures and salt concentrations.Langmuir and Freundlich isotherm models were employed to simulate the equilibrium data of anionic dye.It was found that the equilibrium data were well represented by the Langmuir isotherm,yielding maximum monolayer adsorption capacity of 189 mg/g.Experimental data were analyzed using pseudo-first order and pseudo-second order kinetic models and obtained results indicated that kinetics followed a pseudo-second order equation.     

巯基改性SBA-15的制备及其对Cr6+的吸附

环境中存在的重金属铬对人体健康有严重的危害, 本研究采用水热共缩聚法制备了一种对Cr ⁶⁺有较高吸附能力的介孔材料SBA-15-SH。经红外光谱证实, 通过使用改性硅源3-巯丙基三甲氧基硅烷, 对SBA-15成功实现了巯基改性。经扫描电子显微镜(SEM)和透射电子显微镜(TEM)观察, 所制备的材料呈棒状, 具有均匀的孔道结构, 孔径约为7 nm。将制备材料用于重金属Cr ⁶⁺的吸附, 研究了吸附时间、环境温度、Cr ⁶⁺溶液pH和初始浓度以及吸附剂用量对吸附剂吸附性能的影响。研究表明: 该材料吸附Cr ⁶⁺的平衡吸附时间约10 min, 吸附过程符合Langmuir方程与伪二级动力学模型。当Cr ⁶⁺溶液pH为4.0、吸附温度在25~45 ℃时, 介孔材料SBA-15-SH对Cr ⁶⁺吸附量最大, 达到6.85 mg/g。将本方法用于自来水和工业废水中Cr ⁶⁺的吸附, 回收率介于95%~105%之间。     

Template synthesis of boron nitride nanotubes in mesoporous silica SBA-15

Nitride nanotubes (BN-NTs) was synthesized by chemical vapor deposition (CVD) using BCl₃ and NH₃ at relatively low temperature within the channels of mesoporous silica SBA-15. TEM images confirmed the existence of BN-NTs. The BN-NTs were of uniform diameter about 7 nm, which was consistent with the channel diameter of the template SBA-15. Using this approach, it is easy to control the diameter of BN-NTs by adjusting the diameter of the channel of mesoporous silica host.     

Characterization and application of Ti-containing mesoporous silica for dye removal with synergistic effect of coupled adsorption and photocatalytic oxidation

Highly ordered mesoporous silica, Santa Barbara Amorphous-15 (SBA-15), and titanium-substituted mesoporous silica (TiSBA-15) materials were successfully synthesized, characterized, and evaluated. The textual and structural properties of the prepared materials with various titanium contents were characterized by inductively coupled plasma-mass spectrometer (ICP-MS), powder X-ray diffraction (XRD) patterns, nitrogen physisorption isotherms, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). A limited content of titanium could be effectively substituted into the framework of SBA-15 without provoking structure change. The adsorptive performance was examined by methylene blue (MB) adsorbed on prepared materials. The isotherm models were analyzed to describe the adsorption behavior of prepared materials. The adsorption isotherms were well-fitted with Langmuir and Freundlich models in the simulation of the adsorption behavior of dyes. The SBA-15 and TiSBA-15 materials were found to be effective adsorbents for MB from aqueous solutions. The photodegradation of MB and total organic carbon (TOC) analysis on solid composites were used to evaluate the catalytical performance of Ti-containing mesoporous silica. The synergistic effect of adsorptive and photocatalytical ability of prepared TiSBA-15 was identified. The regeneration and cyclic performance were also proved. These results revealed that TiSBA-15 could be one effective alternative material for dye removal.     

偕胺肟基螯合氧化硅的合成及其Cu2+亲和性能

以氯化钾为晶体结构导向剂, 以正硅酸乙酯和2-氰乙基三乙氧基硅烷为硅源, 聚(乙二醇)-聚(丙二醇)-聚(乙二醇)三嵌段共聚物为模板剂, 合成了偕胺肟基螯合氧化硅(AO-SBA-15)。通过X射线衍射(XRD)、低温氮气吸附-脱附、傅里叶红外光谱(FT-IR)、Zeta电位分析和元素分析技术对样品的结构、孔性质和螯合官能团等进行了表征。XRD分析结果表明, 偕胺肟基螯合氧化硅材料具有有序的二维六方结构, 通过氮气物理吸附数据计算得到材料的平均孔径和比表面积分别为3.96 nm和435 m²/g。FT-IR分析表明将氰基成功地引入材料中并转化为偕胺肟基螯合官能团, 元素分析发现材料的偕胺肟基含量约为1.6 mmol/g, 此外, Zeta电位分析表明材料呈现电负性。相对未改性的氧化硅材料(SBA-15), AO-SBA-15对铜离子吸附容量提高了2倍; 相对氰基功能化氧化硅(CN-SBA-15), AO-SBA-15吸附容量提高了3.6倍。这表明通过引入偕胺肟基螯合官能团, SBA-15对铜离子的亲和力得到显著提高。     

镧(Ⅲ)对SBA-15分子筛改性研究

借助水热法，利用三嵌段共聚物聚(1，2—亚乙基二醇)—嵌段—聚(丙二醇)—嵌段—聚(1，2—亚乙基二醇)为模板剂，正硅酸四乙酯为硅源，强酸性条件下制备了分子筛SBA—15．分别以水及水 乙醇为介质采用LaCl3溶液与煅烧的主体材料SBA—15分子筛固—液相交换法，制备了La—(SBA—15)复合材料．利用化学分析、粉末XRD、N2吸附技术、IR评价了制备方法的有效性及对SBA—15分子筛孔结构的影响．结果表明，镧已并入SBA—15分子筛中，SBA—15内表面上的硅羟基团是镧进入的主要位置，部分客体在分子筛孔道内．制得的材料La—(SBA—15)保持高度有序的介孔二维六角结构，不改变载体SBA—15的介SLSL道结构．此外，考察了La—(SBA—15)产物的发光现象。     

Synthesis of nano titania particles embedded in mesoporous SBA-15: characterization and photocatalytic activity

Supported nanocrystalline titanium dioxide (TiO2) has been prepared by a post-synthesis step via Ti-alkoxide hydrolysis through the use of mesoporous SBA-15 silica. TiO2/SBA-15 composites with various TiO2 loading have been prepared and characterized by X-ray diffraction, nitrogen adsorption, Fourier transform infrared spectroscopy and diffusive reflective UV-vis spectroscopy. The addition of mesoporous SBA-15 prevents the anatase to rutile phase transformation and the growth of crystal grain. TiO2 did not block the SBA-15 pores, and their surface was fully accessible for nitrogen adsorption. Calcination in air of the composites up to 800 degrees C did not change the nanocrystal phase and slightly increased the domain size from 5.0 to 7.5 nm, indicating that the anatase TiO2 grains in the mesostructures have a relatively high thermal stability and proper pore diameter allows controlling the size of obtained titania particles. The TiO2/SBA-15 composites prepared by this study showed much higher photodegradation ability for methylene blue (MB) than commercial pure TiO2 nanoparticles P-25. Experimental results indicate that the photocatalytic activity of titania/silica mixed materials depends on the adsorption ability of composite and the photocatalytic activity of the titania, and there is an optimal ratio of Ti:Si, too high or low Ti:Si ratio will lower the photodegradation ability of the composites.     

Controlled synthesis of semiconductor PbWO4 nanocrystals inside silica SBA-15 materials

A new flexible approach is developed to synthesize PbWO₄ nanoparticles inside the channels of mesoporous silica SBA-15. Mesoporous SBA-15 silica with 7 nm pores was produced by a hydrothermal process and used as a hard template. PbWO₄ nanoparticles were synthesized and incorporated into the mesoporous silicate support in a low-power ultrasonication condition. The as-synthesized samples were characterized by Raman spectroscopy, diffuse reflectance UV–vis spectroscopy (UV–vis), powder X-ray diffraction (XRD), small-angle X-ray diffraction (SAXRD), nitrogen adsorption and transmission electron microscopy (TEM). It was found that PbWO₄ nanoparticles appeared among the channels of SBA-15. Blue shift was observed in UV–vis absorption spectra due to the quantum size effect of PbWO₄ nanoparticles. This preparation method is also capable of synthesis of various semiconductor nanoparticles with controlled size and morphology inside the channels of mesoporous materials.