Synthesis of MCM-41 from coal fly ash by a green approach: influence of synthesis pH

The present study reports a green synthesis method for preparing pure (free of fly ash) and ordered MCM-41 materials from coal fly ash at room temperature (25 degrees C) during 24 h of reaction. It was shown that the impurities in the coal fly ash were not detrimental to the formation of MCM-41 at the tested conditions. The influence of initial synthesis pH on material properties of calcined MCM-41 samples was investigated by various techniques such as XRF, XPS, XRD, FTIR, DR-UV-vis, solid state NMR, N2 physisorption, TG-DTA, SEM and TEM. The experimental results showed that the amount of trace elements such as Al, Na, Ti and Fe incorporated into the sample increased with synthesis pH value. More aluminum species were incorporated with tetrahedral coordination in the framework under a high pH value. The particle size of the sample decreased with the synthesis pH value. Samples synthesized at high pH values had a larger pore size and were more hydrothermally stable than those at low pH values. From thermal analysis, it was observed that the synthesized MCM-41 samples showed a high thermal stability. These properties made the synthesized MCM-41 suitable for further processing into more useful materials in a wide range of applications.     

Synthesis and characterization of super-microporous material with enhanced hydrothermal stability

Super-microporouos silicon material with high hydrothermal stability denoted as MCM-41-T has been prepared from mesoporous MCM-41 by high temperature treatment. The structural and chemical property of MCM-41-T has been characterized by X-ray diffraction, transmission electron microscopy, N₂ adsorption-desorption, infrared spectroscopy and ²⁹Si MAS NMR. The characteristic results show that Si-OH groups are forced to condense by high temperature treatment, and the pore size of MCM-41-T is around 1.5 nm in the super-microporous range. Compared with the original material MCM-41, the hydrothermal stability of MCM-41-T has been significantly enhanced.     

用稻壳灰为硅源合成有序介孔二氧化硅材料的研究

用稻壳灰为硅源,用十六烷基三甲基溴化铵作为模板剂,在酸性或碱性条件下均成功地合成了有序介孔SiO2材料MCM-41.利用XRD、N2吸附曲线、SEM、TEM等测试方法分别对稻壳灰及介孔SiO2样品进行了表征.结果表明,稻壳灰为非晶体,呈粒状的多孔结构,其比表面积为250m2/g;在酸性条件下合成的MCM-41具有周期性规则排列的介孔结构,最可几孔径为2.4nm,比表面积为1100m2/g.     

Effect of preparation technique on the properties of Mo-containing Al-MCM-41

The Al-MCM-41 has been used as support to prepare Mo-containing catalysts. The 12- molybdophosphoric heteropoly acid (HPMo) is used as initial compound. The catalysts are synthesized by two different methods: incipient impregnation with aqueous solution of the acid and mechanochemical synthesis. The samples were tested in the reaction of the thiophene hydrodesulfurization after activation with mixture H₂ + H₂S. The effect of the preparation method of the catalysts on their physicochemical and catalytic properties has been studied. A partial destruction of the loaded compound is observed in mechanochemically treated sample whereas the aggregates are formed from the particles of different size in the impregnated sample. The specific surface area of the sample prepared by mechanical–chemical treatment decreases 2–3 times, while the total pore volume is about four times lower. The HDS activity is higher on the impregnated sample than on the mechanochemically treated one.     

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.     

不同偶联剂对介孔分子筛MCM-41的表面修饰及对MCM-41/环氧树脂性能的影响

使用2种硅烷偶联剂(KH550和KH792)对介孔分子筛MCM-41进行表面改性,采取氮气吸附-脱附、FTIR和TGA等进行表征,并采用原位聚合法制备了MCM-41/环氧树脂复合材料,研究了偶联剂种类和MCM-41用量等对复合材料固化过程及性能的影响。结果表明:硅烷偶联剂可与MCM-41表面的硅羟基反应,在分子筛内外表面接枝上功能化基团。经表面修饰的MCM-41比表面积下降为原来的1/5,KH550在MCM-41表面接枝率仅为KH792的一半。KH550与MCM-41外表面反应得更充分,KH792对MCM-41孔道内壁的修饰效果更强。固化动力学结果表明:KH792的功能化基团有伯胺和仲胺,与环氧树脂具有更高的反应活性,但不利于环氧大分子进入孔道,仅以球形粒子的形式添加在环氧树脂中;KH550表面修饰的MCM-41可使环氧大分子进入孔道内形成互穿结构。KH550表面修饰体系更多体现出MCM-41多孔的特征,形成了有机-无机互穿结构的复合体系,大幅度提高了储能模量和玻璃化转变温度。KH792表面修饰体系则呈常规球形纳米粒子的特征,其储能模量和玻璃化转变温度较纯环氧树脂有所提高但幅度不大。     

The investigation of MCM-48-type and MCM-41-type mesoporous silica as oral solid dispersion carriers for water insoluble cilostazol

Objective: To explore the suitable application of MCM-41 (Mobil Composition of Matter number forty-one)-type and MCM-48-type mesoporous silica in the oral water insoluble drug delivery system.

Methods: Cilostazol (CLT) as a model drug was loaded into synthesized MCM-48 (Mobil Composition of Matter number forty-eight) and commercial MCM-41 by three common methods. The obtained MCM-41, MCM-48 and CLT-loaded samples were characterized by means of nitrogen adsorption, thermogravimetric analysis, ultraviolet-visible spectrophotometry, scanning electron microscopy, transmission electron microscopy, differential scanning calorimetry and powder X-ray diffractometer.

Results: It was found that solvent evaporation method was preferred according to the drug loading efficiency and the maximum percent cumulative drug dissolution. MCM-48 with 3D cubic pore structure and MCM-41 with 2D long tubular structure are nearly spherical particles in 300–500?nm. Nevertheless, the silica carriers with similar large specific surface areas and concentrating pore size distributions (978.66?m²/g, 3.8?nm for MCM-41 and 1108.04?m²/g, 3.6?nm for MCM-48) exhibited different adsorption behaviors for CLT. The maximum percent cumulative drug release of the two CLT/silica solid dispersion (CLT-MCM-48 and CLT-MCM-41) was 63.41% and 85.78% within 60?min, respectively; while in the subsequent 12?h release experiment, almost 100% cumulative drug release were both obtained. In the pharmacokinetics aspect, the maximum plasma concentrations of CLT-MCM-48 reached 3.63?mg/L by 0.92?h. The AUC_0–∞ values of the CLT-MCM-41 and CLT-MCM-48 were 1.14-fold and 1.73-fold, respectively, compared with the commercial preparation.

Conclusion: Our findings suggest that MCM-41-type and MCM-48-type mesoporous silica have great promise as solid dispersion carriers for sustained and immediate release separately.     

Preparation of TiO2/Al-MCM-41 mesoporous materials from coal-series kaolin and photodegradation of methyl orange

TiO₂/Al-MCM-41 mesoporous materials were prepared via sol-gel method by loading titania onto Al-MCM-41 mesoporous molecular sieve by hydrothermal treatment from coal-series kaolin as raw material. The TiO₂/Al-MCM-41 mesoporous materials were characterized by XRD, FT-IR, HRTEM, N₂ adsorption-desorption and the photocatalytic degradation of methyl orange solution under visible light irradiation. The results showed that the TiO₂/Al-MCM-41 mesoporous materials possessed a high surface area of 369.9–751.3 m²/g and a homogeneous pore diameters of 2.3–2.8 nm. The titania crystalline phase was anatase, and the particles size of TiO₂ increased with TiO₂ content. The Al-MCM-41 mesoporous materials exhibited excellent photodegradation activity under visible-light irradiation for methyl orange.     

Preparation of mesoporous Al-MCM-41 with stable tetrahedral aluminum using ionic liquids as a single template

Mesoporous Al-MCM-41 materials were synthesized using room temperature ionic liquid 1-cethyl-3-methylimidazolium bromide ([C₁₆mim]Br) as a single template and characterized by X-ray diffraction, N₂ adsorption-desorption, ICP-AES, ²⁷Al MAS NMR and TEM technique. These mesoporous materials exhibit hexagonal p6m pore architectures, and possess high surface area and narrow pore distribution. All aluminum in as-synthesized samples exists in tetrahedral coordination. Upon calcination nearly all aluminum still remains the tetrahedral coordination even when the Si/Al ratio is as low as 15. This indicates that the tetrahedral aluminum of Al-MCM-41 is stable.     

氟化MCM-41的制备及超声触发释药性能研究

采用微波法制备了MCM-41,并将其与NH4F反应制得氟化MCM-41(F-MCM-41),采用浸渍法将抗肿瘤药物5-氟尿嘧啶(5-FU)分别组装到MCM-41和氟化MCM-41中。采用XRD、FT-IR、低温N2吸附和TG对MCM-41、氟化MCM-41和药物组装体进行了表征,考察了常规条件和超声条件下组装体在人工模拟胃液中的药物释放行为。结果表明,药物组装体超声条件下的药物释放速率明显优于常规释放。     

Synthesis of MCM-41 nanoparticles from stem of common reed ash silica and their application as substrate in electrooxidation of methanol

In this work, stem of common reed ash (SCRA) is introduced as a new source of silica in the preparation of mesoporous materials. Mesoporous silicate MCM-41 nanoparticles were synthesized hydrothermally using sodium silicate prepared from SCRA as a silica source. The characterization of MCM-41was carried out by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), N\(_{2}\) adsorption/desorption (BET) and transmission electron microscopy (TEM). SEM shows that MCM-41 nanoparticles are sphere-like with size in the range of 30–50 nm with some degree of agglomeration. TEM image of the synthesized sample shows the open framework structure of MCM-41. A type IV isotherm can be observed from adsorption/desorption curves, which is the characteristic of mesoporous materials. The prepared MCM-41 nanoparticles were used as substrate to facilitate the oxidation of methanol through the modification with an electroactive species. The modification was achieved by impregnation of MCM-41 pores with \(\hbox {Ni}^{2+}\) ions (Ni-doped MCM-41). A modified carbon paste electrode (CPE) was prepared by mixing Ni-doped MCM-41 with carbon paste (NiMCM-41CPE). Cyclic voltammetry of NiMCM-41CPE shows an increment in current density of methanol oxidation in comparison with CPE in alkaline solution. Moreover, a decrease in the overpotential of methanol oxidation occurred on the surface of modified electrode. The effects of some parameters such as scan rate and methanol concentration are also investigated on the behaviour of NiMCM-41CPE. Also, the heterogeneous electron transfer rate for the catalytic reaction (k) of methanol is calculated.     

A low cost synthesis of fly ash-based mesoporous nanocomposites for production of hydrogen by photocatalytic water-splitting

An economical and feasible route was used to synthesize the fly ash-based mesoporous CdS/Al-MCM-41 nanocomposites via an alkali fusion step to extract of the silicon and aluminum sources from fly ash, and a templating step to assemble nanocomposites at room temperature. The low angle X-ray diffraction and high resolution transmission electron microscopy results indicated that the mesoporous Al-MCM-41 was formed with average pore size of about 3.0 nm and the CdS clusters were assembled in the channels of Al-MCM-41. The results of ultraviolet–visible (Vis) diffuse reflectance spectra and the fluorescence emission spectra revealed that the nanocomposites show a strong absorption edge at 521 nm and a weak photoluminescence peak at 398 nm. The activities of hydrogen production were evaluated by photocatalytic water-splitting under Vis light irradiation, and the CdS/Al-MCM-41 nanocomposites showed the highest H₂ evolution in amount of 3.3 mL/g during the reaction time for 6 h due to the synergistic effect between CdS clusters and mesoporous Al-MCM-41 matrix. A mechanism of photocatalytic H₂ production was proposed.     

磁性MCM-41分离回收RT培司废水中四甲基氢氧化铵的研究

硝基苯法合成RT培司(4-氨基二苯胺)的废水色度高、组分复杂、催化剂四甲基氢氧化铵(TMAOH)难以分离回收。提出采用磁性MCM-41对RT培司废水中有机副产物进行选择性吸附分离。制备的磁性MCM-41样品采用X射线衍射仪(XRD)、透射电子显微镜(TEM)、扫描电子显微镜(SEM)、N₂吸附-脱附和振动样品磁场计(VSM) 等手段进行表征。结果表明, 磁性MCM-41颗粒的粒径范围为200~300 nm, BET比表面积约为655.2 m²/g, 孔径分布为0.5~4 nm, 内核铁酸镍的存在使磁性MCM-41具有超顺磁性。吸附研究表明磁性MCM-41对RT培司废水中吩嗪、偶氮苯和苯胺等有机物具有良好吸附作用, 经5次吸附磁分离后, RT培司废水中四甲基氢氧化铵能够达到回用要求, 吸附后的磁性MCM-41在外加磁场下极易分离。     

高结晶规则大孔硅的制备和应用

ＦＳＭ－１６,ＭＣＭ－４１和ＳＢＡ－１５等具有高规则二维六角晶格的多孔硅可用不同硅源和表面活性剂合成,其孔径可达１０,１５或３０ｎｍ,可用具有不同熔基链长的表面活性剂和膨胀剂控制。其结晶规则性随孔径的增大而降低。用层状硅土Ｋａｎｅｍｉｔｅ制备的ＦＳＭ－１６和来自水玻璃的ＭＣＭ－４１,其表面阴离子度比用四甲氧基硅烷（ＴＭＯＳ）制备的ＳＢＡ－１５高得多。如将在等电点以下呈阴离子性的生物酶插入硅孔,则由于离子间的相互作用和氢键结合力,可得到结合得十分稳定的生物／无机陶瓷结合体。以此结合体为有机酸化反应的催化剂,反应的活性很高。     

杂原子MCM-41分子筛的合成和催化性能

采用水热合成法合成了金属原子(Zn,Ni,Fe,Al,Cu,Ce)掺杂的MCM-41介孔分子筛(简称T-MCM-41),并将其应用于邻苯二甲酸二(2-乙基已)酯(DOP)的合成反应,研究了不同原子的掺杂对T-McM-41的结构,比表面积和孔径、酸性及催化性能的影响.结果表明,所制备的T-McM-41仍然具有六方有序排列结构,比表匝f积较高(550-900 m2/g)、孔径大(3 nm左右),杂原子的引入使T-MCM-41产生了酸中心,从而使其对DOP的合成具有很好的催化活性和选择性.用T-MCM-41(T=Zn,Fe,Al,Cu)催化DOP的合成反应,在5 h的反应时间内苯酐的转化率可以达到95.5%以上,DOP的选择性可达到96.5%以上.T-MCM-41催化剂具有很好的稳定性,Al-MCM-41在重复使用5次后仍具有较好的催化活性.     

室温下介孔分子筛MCM-41的合成与表征

在室温下 ,以十六烷基三甲基溴化铵 (CTABr)为模板剂 ,正硅酸乙酯和水玻璃为硅源 ,通过水热法分别合成出了性能优良的介孔分子筛MCM 4 1,并采用XRD、N2 吸附脱附、FTIR、SEM、热重等手段对合成的样品进行了分析表征。其结果表明 ,合成的固体产物具有MCM 4 1特有的六方排列的孔道结构 ,并且具有较高的有序度、比表面积、孔容和热稳定性     

超临界CO_2中MCM-41-g-PHEMA介孔复合物的制备及性能

以甲基丙烯酸羟乙酯(HEMA)为单体,用乙烯基三乙氧基硅烷改性的介孔分子筛MCM-41为载体,偶氮二异丁腈为引发剂,在超临界二氧化碳中通过沉淀聚合,成功合成了聚甲基丙烯酸羟乙酯-二氧化硅介孔复合材料(MCM-41-gPHEMA)。考察了反应物配比、反应时间和反应压力对所制复合物形貌与产率的影响。对所合成的复合物进行红外光谱分析、比表面积、小角X射线衍射、扫描电镜、透射电镜、热重分析等表征。研究了复合物的溶胀性及在不同pH下对牛血清白蛋白(BSA)水溶液的吸附性能与吸附动力学。结果表明,MCM-41-g-PHEMA的孔径约为6.3nm,热稳定性明显提高,复合物对BSA的吸附动力学符合伪二级速率方程,最大吸附量为35mg/g。     

杂多酸固载催化剂的合成及窄分子量纤维素制备的研究

通过水热合成法制备MCM-41型介孔分子筛,采用浸渍法负载磷钨酸于MCM-41介孔分子筛中,煅烧得到新型HPW/MCM-41固载催化剂。利用傅里叶红外光谱(FT-IR)、X射线衍射(XRD)、热重分析(TG)和扫描电镜(SEM)对固载催化剂进行表征;考察催化剂对棉纤维催化降解反应的性能。结果表明,新型HPW/MCM-41固载催化剂即持有了磷钨酸的Keggin结构,同时又保持了分子筛的完整介孔结构,具有催化、筛分双重性能。棉纤维催化降解反应数据显示,磷钨酸负载量、反应温度、催化剂用量、液固比及停留时间均影响HPW/MCM-41降解纤维素的性能。在单因素实验最佳反应条件下,棉纤维素降解产物的分子量分布较为均匀,降解产物的产率较优。     

纳米Au团簇在氧化钛修饰的介孔分子筛MCM-41中的组装

以钛酸丁酯为ＴｉＯ_２前驱体,使ＴｉＯ_２均匀分散于纯硅介孔分子筛ＭＣＭ－４１的介孔孔道内表面,利用ＴｉＯ_２光学性质将ＡｕＣｌ－４还原为Ａｕ（０）并组装于氧化钛修饰的ＭＣＭ－４１孔道中．对所合成的Ａｕ负载的氧化钛修饰的ＭＣＭ－４１进行了ＸＲＤ,ＸＰＳ,Ｎ_２吸附－脱附曲线,及固体ＵＶ－Ｖｉｓ漫反射等多种结构表征．由ＸＰＳ谱和固体ＵＶ－Ｖｉｓ漫反射吸收光谱的ｐｌａｓｍｏｎ吸收峰证明Ａｕ团簇呈现０价的金属状态．     

Esterification of levulinic acid into hexyl levulinate over dodecatungstophosphoric acid anchored to Al-MCM-41

Aluminum-substituted MCM-41 (Al-MCM-41) were hydrothermally synthesised and used as supports to fabricate the mesostructured H₃PW₁₂O₄₀ (HPW) solid acid catalysts via an impregnation method. The influences of various HPW loadings on the structures of the catalysts were verified by X-ray diffraction (XRD), nitrogen physisorption, scanning electron microscopy (SEM), transmission electron microscopy (TEM), ultraviolet–visible (UV–Vis) spectroscopy and Fourier-transform infrared spectroscopy (FT-IR) measurements and their acidities were evaluated by infrared of pyridine adsorption (Py-IR) and temperature-programmed desorption of ammonia (NH₃-TPD) measurements. The optimisation of the reaction conditions for levulinic acid esterification with n-hexanol such as the reaction temperature and time, the reactant molar ratio, and the catalyst dosages was performed to maximise the conversion of levulinic acid. The effects of various HPW loadings on the conversion of levulinic acid were investigated under the optimised and harsh reaction conditions. The reusability of the catalysts was also investigated. The results showed that these catalysts retained the hexagonal mesoporous structure of Al-MCM-41 and the Keggin characteristic of HPW, although their textural parameters decreased with increasing loading of HPW. In particular, the catalysts were found to be efficient in the esterification of levulinic acid with n-hexanol, resulting in hexyl levulinate which could replace the petroleum-derived chemical feedstocks.