负载型ZrOx/MCM-41分子筛催化α,β-不饱和醛的MPV还原反应的研究

采用Zr（NO3）4为Zr源,水为溶剂,浸渍法制备了负载型ZrOx/MCM-41介孔分子筛催化剂,考察了其在以异丙醇为氢源,苯甲醛为模型反应物,经氢转移法还原为苯甲醇的反应（MPV反应）中的催化性能,同时对样品进行XRD、N2吸附-脱附、IR、UV等表征分析,并与水合ZrO2、骨架掺杂Zr-MCM-41进行对比研究。结果表明：ZrOx/MCM-41分子筛性能最为优异,负载范围为2.5%～20%时,Zr负载量对性能影响较不明显,最佳负载量为5%;焙烧温度对性能影响较明显,最佳焙烧温度是300℃,以300℃焙烧8h的5%ZrOx/MCM-41分子筛为催化剂,在76℃、反应8h后,苯甲醛的转化率为88%,苯甲醇的选择性〉99%。该类催化剂具有较好的抗水性、抗活性组分流失性和再生性能。ZrO2负载于MCM-41上时可能形成表面Si-O-Zr-OH基团,其可能是该催化剂性能优异的主要原因,催化剂表面少量存在的NO3^-可能增加了其酸性,使其活性进一步提高。     

Ti负载对硅基MCM-41结构的影响

采用后期浸渍的方法合成了Ti负载硅基MCM-41,并利用XRD、FT-IR、29 Si MAS NMR及N2吸附-脱附等表征手段和苯乙烯的催化氧化反应,系统研究了Ti负载对MCM-41结构和催化性能的影响.研究结果表明:Ti负载后MCM-41结构有序度下降,但仍具有良好的有序结构.Ti进入MCM-41的骨架形成Ti-O-Si键,随着Ti负载量的增加,部分Ti以TiO2的形态存在.与Si-MCM-41相比,Ti负载后MCM-41的孔结构产生变化,比表面积减小,孔径分布变窄.当Ti负载到硅基MCM-41时,其具有明显的催化性能.     

SO2-4/ZrO2/MCM-41催化合成柠檬酸三丁酯的研究

水热合成了介孔材料MCM-41,并以其为载体负载固体超强酸SO2-4/ZrO2,通过XRD和N2吸附/脱附对制备的SO2-4/ZrO2/MCM-41催化剂进行表征,认为MCM-41负载SO2-4/ZrO2后,仍为长程有序的六方孔道结构.在固定床反应器中,以柠檬酸和正丁醇为原料,研究该催化剂合成柠檬酸三丁酯的活性.对反应条件进行了考察,得出最佳反应条件:温度140 ℃,空速1.0 h-1,醇酸物质的量比为4.5.在此条件下,柠檬酸的酯化率最高可达94.5%.48 h的寿命实验结果表明,该催化剂具有较好的稳定性.     

Zr-SBA-15催化肉桂醛MPV转移加氢性能

以正硅酸乙酯和硝酸氧锆为原料，采用一锅法制备了不同Zr/Si物质的量比的Zr-SBA-15催化剂，借助N2物理吸附、X射线粉末衍射、NH3-程序升温脱附、吡啶-原位红外等考察了Zr/Si物质的量比对Zr-SBA-15结构、织构、表面酸性质及催化肉桂醛Meerwein-Ponndorf-Verley（MPV）转移加氢性能的影响；结合催化剂表征与催化肉桂醛MPV转移加氢性能评价结果，探讨了Zr-SBA-15结构、织构及表面酸性质对其催化肉桂醛MPV转移加氢性能的影响机制。结果表明，所制备的Zr-SBA-15催化剂均呈现规整的六方介孔结构特征，表面酸中心以L酸为主。随Zr/Si物质的量比增加，Zr-SBA-15催化剂的最可几孔径逐渐减小，L酸量持续增加，B酸量变化不大，肉桂醛转化率呈现先增加后趋于稳定的趋势，目标产物肉桂醇选择性增加，副产物1-苯丙烯-2-丙基醚选择性下降。在Zr/Si物质的量比为0.1时，Zr-SBA-15催化剂显示最优的催化性能，肉桂醛转化率为96.2 %，目标产物肉桂醇选择性达到95.2 %，经7次循环后催化剂仍保持90%以上的肉桂醛转化率和95%以上的肉桂醇选择性。     

利用TRPO-煤油/盐酸-ZrOCl_2萃取体系的第三相制备ZrO_2介孔材料

首次利用TRPO-煤油/HCl-Zr(Ⅳ)萃取体系中负载Zr(Ⅳ)的第三相作为模板和Zr(Ⅳ)源,采用冷冻的方法成功地制备了ZrO2介孔材料。并利用TG-DTA,TEM,XRD,N2吸附-脱附等方法对所制得的材料进行表征。     

介孔分子筛MCM-41的合成探索

以正硅酸乙酯(TEOS)为硅源、十六烷基三甲基溴化铵(CTAB)为模板剂,利用水热合成法制备了介孔氧化硅MCM-41,并采用TEM、XRD、N2吸附-脱附等测试手段对产物进行了表征。结果表明,合成的介孔材料为高质量的MCM-41。     

镁热还原法制备多孔硅碳复合负极材料

分别以介孔二氧化硅(SBA-15和 MCM-48)和硅藻土为硅源,通过镁热还原制备多孔硅,然后向多孔硅中注入有机碳前躯体,经过高温碳化处理得到多孔Si/C复合负极材料。采用X射线衍射仪、Raman光谱仪、场发射扫描电子显微镜和N2吸附脱附测试仪对合成的材料分别进行了表征,研究了多孔 Si/C 复合材料的电化学性能。结果表明：镁热还原介孔二氧化硅可以得到多孔硅材料,碳加入到多孔硅材料中可以有效提高材料的电子电导率,可明显改善材料的循环稳定性。同时多孔结构可以有效缓解硅基材料充放电过程中的体积应力,提高材料的循环稳定性。以SBA-15、MCM-48和硅藻土为硅源制备得到的3种多孔Si/C复合材料在200 mA/g电流密度下循环30次之后的可逆容量分别为712、664、463 mA·h/g。     

Zr-SBA-15催化肉桂醛的MPV转移加氢性能

以正硅酸乙酯和硝酸氧锆为原料,采用一锅法制备了不同Zr/Si物质的量比的Zr-SBA-15催化剂,借助N_2物理吸附、XRD、NH_3-TPD、吡啶-原位红外光谱考察了Zr/Si物质的量比对Zr-SBA-15结构、织构、表面酸性质及催化肉桂醛Meerwein-Ponndorf-Verley(MPV)转移加氢性能的影响;探讨了Zr-SBA-15结构、织构及表面酸性质对其催化肉桂醛MPV转移加氢性能的影响机制。结果表明,Zr-SBA-15催化剂均呈现规整的介孔结构特征,表面酸中心以L酸为主。随Zr/Si物质的量比增加,Zr-SBA-15催化剂的最可几孔径逐渐减小,L酸量持续增加,B酸量变化不大,肉桂醛转化率呈现先增加后趋于稳定的趋势,目标产物肉桂醇选择性增加,副产物1-苯丙烯-2-丙基醚选择性下降。在Zr/Si物质的量比为0.10时,Zr-SBA-15催化剂显示最优的催化性能,肉桂醛转化率为96.2%,目标产物肉桂醇选择性达到95.2%,经7次循环后催化剂仍保持90%以上的肉桂醛转化率和95%以上的肉桂醇选择性。     

MCM-48固载杂多酸催化剂的孔结构与催化性能研究

以MCM-48介孔分子筛为载体、HSiW(硅钨杂多酸)为活性组分,采用浸渍法制备负载型催化剂HSiW/MCM-48。以XRD、N_2吸附-脱附、NH_3-TPD对样品进行表征,以油酸的酯化反应为探针测试样品的催化性能,并考察了HSiW负载量对催化剂结构和性能的影响。研究结果表明:HSiW/MCM-48催化剂保持MCM-48的三维立方相介孔结构,但随HSiW负载量增加,HSiW/MCM-48催化剂介孔的长程有序性逐渐下降,比表面积和孔容同时减小;催化剂在油酸的酯化反应中呈现出良好的催化性能;当HSiW负载量达20%时,催化活性较高,油酸甲酯的收率高达80.5%。     

ZrO2掺杂介孔活性炭材料的制备及除磷性能研究

以废弃甘蔗渣为碳源制备了ZrO_2掺杂介孔活性炭材料,并对其除磷性能进行了研究。采用FT-IR、XRD、SEM和N2吸附-脱附实验对材料进行了表征,结果表明,该材料成片状,具有高比表面积和介孔结构。吸附实验结果表明,锆的最佳掺杂量为甘蔗渣质量的10%,理论最大吸附容量为41.41 mg/g(308 K)。材料对磷酸盐的吸附符合准二级动力学模型和Langmuir模型,且为吸热过程,包含物理吸附和化学吸附,遵循静电吸附和离子交换机制。     

Adsorption Behavior of Molybdenum on Modified Mesoporous Zirconium Silicates

In this study, mesoporous MCM-41 has been modified by the incorporation of zirconium ion as a rapid, simple, and inexpensive method for modification. The adsorbent is characterized using powder X-ray diffraction and nitrogen adsorption-desorption isotherm data. The distribution coefficient of molybdenum ion on the mesoporous zirconium silicates has been enhanced with the increase of the zirconium in the framework of the adsorbent. The adsorption behavior of molybdenum on the Zr10MCM-41 adsorbent has been studied and the experimental adsorption isotherm is successfully described by the Langmuir model. The effect of pH and adsorption kinetics have also been studied by batch method. The adsorption capacity is very high in the pH range of 2–3 and decreases with increasing of the pH value.     

Adsorption performance of mesoporous silicas towards a cationic dye. Influence of mesostructure on adsorption capacity

The dye adsorption performance of four mesoporous silicas with different structure and textural properties, MCM-41, MCM-48, SBA-15 and mesocellular silica foam (MCF), was studied and compared by using toluidine blue O (TBO) as dye model in aqueous solution. These materials were characterized by X-ray diffraction (XRD), small-angle X-ray scattering, nitrogen adsorption-desorption analyses, and transmission electron microscopy (TEM). The effect of some parameters such as adsorbent dosage, contact time, temperature, and pH on the TBO removal in aqueous solution was studied. Results showed that adsorption capacity raised when adsorbent dosage, contact time and pH solution were increased while an increase in temperature decreased the adsorption of TBO. Langmuir, Freundlich and Temkin isotherm models were employed to elucidate the adsorption mechanism while the adsorption rate data were analyzed according to the pseudo-first and second-order kinetic models. Results showed that adsorption of TBO onto MCM-48, SBA-15, and MCF fitted well the Freundlich isotherm model while the kinetic studies showed that adsorption process could be better described by the pseudo-second-order model for all mesoporous silicas. Finally, some solvents were evaluated to carried out dye desorption from the TBO-loaded mesoporous silicas founding that acetic acid was the most efficient.     

含氟体系中合成条件对MCM-48分子筛结构性能的影响

在合成过程中引入F~-可以缩短MCM-48分子筛的晶化时间,考察以正硅酸乙酯(TEOS)为硅源、十二烷基三甲基溴化铵(CTAB)为模板剂的合成体系中加入F~-后,n(CTAB)∶n(Si)、晶化时间和晶化温度等合成条件对MCM-48结构性能的影响。XRD、N_2吸附脱附和TEM等表征结果表明,在n(CTAB)∶n(Si)=0.65、晶化温度120℃和反应时间24 h条件下,合成的MCM-48分子筛结晶度较高,比表面积为1 305 m~2·g~(-1),平均孔径3.416 nm,为MCM-48分子筛的适宜合成条件。     

Synthesis of hexagonal and cubic mesoporous silica using power plant bottom ash

An alkali fusion method was adopted to extract silicate species from coal bottom ash in a power plant and the supernatant solution was used for the synthesis of MCM-41, SBA-15, and SBA-16 mesoporous silica materials. The minor impurities present in the bottom ash were not found to be detrimental to the successful formation of mesoporous silica phases. Additional silica from sodium metasilicate was introduced to improve the textural properties for SBA-15 and SBA-16. According to SEM analyses, particle morphology of the samples gradually approaches those prepared using pure chemical as the amount of external silica source increases. XRD analyses confirmed well-ordered mesostructures in all of these silica materials. N₂ adsorption–desorption isotherms of MCM-41 prepared using bottom ash showed a type IV isotherm with a region of steep increase due to capillary condensation, whilst SBA-15 and SBA-16 showed type IV isotherm with H1 and H2 hysteresis loops, respectively. ²⁷Al MAS NMR analysis of MCM-41 synthesized from the supernatant solution reveals that the extracted Al species from bottom ash were tetrahedrally incorporated in the framework. TEM clearly showed the uniform pore structure of the materials prepared using the industrial waste.     

Supporting of Lead Hexacyanoferrate on Mesoporous MCM-41 and its use as Effective Adsorbent for Strontium: Equilibrium,Kinetic, and Thermodynamic Studies

In this study, mesoporous MCM-41 has been modified by supporting of lead hexacyanoferrate (PbHCF) as a new adsorbent for strontium. The lead hexacyanoferrate-loaded mesoporous MCM-41 (PbHCF-MCM-41) was characterized using powder X-ray diffraction (XRD) and nitrogen adsorption-desorption isotherm data, infrared spectroscopy, scanning electron microscopy coupled with energy dispersive X-ray (SEM-EDX) and its strontium adsorption performance in aqueous solution was investigated. The effect of the various parameters like contact time, temperature, the initial pH value of the solution, and the initial concentration of the strontium ion on the adsorption efficiencies of PbHCF-MCM-41 have been studied systematically by batch experiments. Adsorption isotherm of PbHCF-MCM-41 was studied and the fitted results indicated that the Langmuir model could well represent the adsorption process. The maximum adsorption capacity of Sr²⁺ onto PbHCF-MCM-41 was found to be 97.09 mg · g^?1.     

CuCl2 Immobilized on Amino-Functionalized MCM-41 and MCM-48 as Efficient Heterogeneous Catalysts for Dimethyl Carbonate Synthesis by Vapor-Phase Oxidative Carbonylation of Methanol

Pure silica mesoporous molecular sieves MCM-41 and MCM-48 organofunctionalized with 3-aminopropyltrimethoxysilane and N-[(3-trimethoxysilyl)propyl]ethylene-diamine, respectively, were served as supports to immobilize CuCl₂ with conventional impregnation method. The supported copper catalysts showed a considerable enhancement in the reaction rate in heterogeneous vapor-phase oxidative carbonylation of methanol to produce dimethyl carbonate in comparison with that obtained by CuCl₂-supported nonfunctionalized mesoporous silicas under identical conditions. The electronic donation of the amino groups, the accessibility and dischargeability of reactants in the regular mesopores probably account for the good catalytic performance as evidenced by the characteristic studies with XRD, BET, FTIR, TG-DTA, and XPS.     

硅源对纯硅MCM-41介孔分子筛结构性能的影响

分别采用正硅酸乙酯(TEOS)、气相法白炭黑、硅溶胶为硅源,十六烷基三乙基溴化铵(CTEAB)为结构导向剂,在100℃用水热晶化法在碱性(NaOH)介质中反应5d,合成出MCM-41介孔分子筛样品。通过XRD、N2吸附-脱附测试手段对不同硅源合成的样品进行了对比表征分析,实验结果表明,相对于TEOS作为硅源,气相法白炭黑和硅溶胶制得的MCM-41具有较大的孔径(>4nm)和孔容(>1cm3/g)以及高的比表面积(1000m2/g),在制备大孔径的介孔MCM-41时,气相法白炭黑和硅溶胶是两种比较好的硅源。     

MCM-41介孔材料的合成条件和特性对吸附镉离子的影响

以气相氧化硅为硅源,十六烷基三甲基溴化铵(cetyl trimethyl ammonium bromide,CTAB)为模板剂,分别在碱性[氢氧化钠(NaOH),四乙基氢氧化铵,tetraethyl ammonium hydroxide,(C2Hs)4NOH(TEAOH)]和酸性介质条件[盐酸(HCl)]T水热合成了MCM-41有序介孔材料MCM-41-N,MCM-41-T和MCM-41-H.用X射线衍射、氮气吸附-脱附等手段对比分析了合成的3种MCM-41介孔材料的物相、比表面积、孔径、孔体积等,发现酸性介质中合成的介孔材料的孔径最大.在此基础上,利用MCM-41介孔材料对比研究了处理含镉离子(Cd2 )废水的效果和机理,确定了不同介孔材料用量、不同初始pH值条件下MCM-41介孔材料对水中Cd2 的吸附率和吸附量.结果表明:介孔材料用量相同时,溶液pH值的增大有利于提高3种MCM-41介孔材料对水中Cd2 的处理效果.在pH值从7.0到8.0的过程中,其吸附率有1个突变,MCM-41-T的Cd2 吸附率从35.65%提高到62.15%;MCM-41-N的从38.80%提高到69.40%;MCM-41-H的从50.22%提高到73.47%.孔径最大的MCM-41-H对Cd2 的吸附效果最佳,最大吸附率为89.56%,最大吸附容量为8.57 mg/g.吸附溶液pH值的大小和介孔材料的孔径尺寸是决定吸附量大小的关键因素,因此,重点应通过优化合成工艺提高介孔材料的孔径.     

Adsorption of Tetraalkyl Ammonium Hydroxide with Mesoporous Silica

Adsorption of tetraalkyl ammonium hydroxide (TAAH) with mesoporous silica such as MCM-41 and MCM-48 has been investigated. The adsorption of TAAH with the mesoporous silica increases with increase in pH of the aqueous solution. The maximum adsorption amounts of TAAH with the mesoporous silica, determined by Langmuir isotherms, correspond to the relationship between the pore diameter of the mesoporous silica and the molecular size of TAAH, while no significant relationship is observed with both the specific surface area and the amount of silanol group of the mesoporous silica. Mesoporous silica having large pore diameter is applicable to the adsorptive separation of TAAH from the effluent solution.     

MCM-41-HY介孔-微孔复合分子筛的水热合成

以微孔分子筛HY浆液为母液,合成介孔-微孔复合分子筛MCM-41-HY。通过XRD、NH_3-TPD和N_2吸附-脱附等手段对复合材料进行了表征,并对复合分子筛的水热稳定性进行了考察。结果表明,复合分子筛MCM-41-HY具有中孔分子筛MCM-41和微孔HY型沸石的特点,并且与纯MCM-41分子筛相比,复合分子筛的酸强度明显增强,水热稳定性提高。