Synthesis of MCM–41 mesoporous molecular sieves containing heteroatoms and their catalytic activity

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--乙基己)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, 比表面积较高(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.     

SnO（Sn）/泡沫镍整体催化剂的制备和催化活性

以泡沫镍为载体制备一系列活性组分为SnO和Sn的整体催化剂,测定了催化剂对邻苯二甲酸二(2-乙基己)酯(DOP)合成反应的催化活性,研究了电镀电流密度、电镀温度和焙烧处理对催化性能的影响,以及整体催化剂的寿命和失活的原因.结果表明,所制备的SnO(Sn)/泡沫镍整体催化剂对DOP的合成有很好的催化活性和选择性.用整体催化剂Sn/Ni-3(300)催化DOP的合成反应,在1h的反应时间内邻苯二甲酸酐的转化率达到96.75%;反应平衡时合成的产物中DOP的选择性达到97%以上.SnO(Sn)/泡沫镍整体催化剂使用后很容易从反应体系中分离,不需要任何处理即可重复使用多次.     

Synthesis of SnO(Sn)/Ni foam monolithic catalysts and their catalytic activity

以泡沫镍为载体制备一系列活性组分为SnO和Sn的整体催化剂,测定了催化剂对邻苯二甲酸二(2-乙基己)酯(DOP)合成反应的催化活性,研究了电镀电流密度、电镀温度和焙烧处理对催化性能的影响,以及整体催化剂的寿命和失活的原因. 结果表明,所制备的SnO(Sn)/泡沫镍整体催化剂对DOP的合成有很好的催化活性和选择性.用整体催化剂Sn/Ni-3(300)催化DOP的合成反应,在1h的反应时间内邻苯二甲酸酐的转化率达到96.75%;反应平衡时合成的产物中DOP的选择性达到97%以上.SnO(Sn)/泡沫镍整体催化剂使用后很容易从反应体系中分离,不需要任何处理即可重复使用多次.     

AZO@TiO_2导电晶须制备工艺优化及其应用

采用正交试验法对AZO@TiO_2导电晶须的制备工艺进行了优化。通过改变包覆比(Ti/Zn)、掺杂比(Al/Zn)、pH值、煅烧温度4大因素,结合反应产物的测试表征,得出合成AZO@TiO_2导电晶须的最佳工艺条件。实验范围内的最佳制备方案为包覆比(Zn/Ti)35%(at,原子比,下同),掺杂比(Al/Zn)4%,煅烧温度600℃,pH=10,该工艺条件下制备的AZO@TiO_2导电晶须表面电阻率为7.6452kΩ·cm,白度为67.8。制得的AZO@TiO_2导电晶须添加到纺丝溶液中,采用湿法纺丝制备具有良好导电性能的聚丙烯腈(PAN)白色复合导电纤维。     

金属掺杂对纳米管TiO2光催化性能的影响

利用水热法,以Degussa P-25TiO2粉末为原料,AlCl3、Fe(NO3)3·9H2O和ZnCl2为掺杂剂合成金属掺杂纳米管TiO2,并采用透射电镜(TEM)、X射线衍射(XRD)、X射线光电子能谱(XPS)和BET比表面积分析对催化剂进行表征。结果表明,掺杂金属分别以Al 3+、Fe3+和Zn2+的形式存在。随着煅烧温度的增高,样品的比表面积逐渐降低,锐钛矿含量先增大后减小;金属掺杂后,催化剂比表面积略有降低,锐钛矿含量略有增大。考察紫外光催化臭氧化工艺中TiO2降解腐植酸标志物的催化效果,结果表明,450℃煅烧未掺杂纳米管TiO2对腐植酸的催化降解效率为44%,较P-25TiO2粉末提高了11%;金属掺杂后催化效果提升明显,550℃煅烧Fe掺杂纳米管TiO2的催化效果最为显著,腐植酸去除率达77%。     

Al掺杂Ni(OH)2的结构及充放电性能

为了改善Ni(OH)2的电化学性能,提高锌镍电池的充放电效率,用简便的化学共沉淀法合成了Al掺杂的Ni(OH)2.用XRD、FTIR表征了合成掺杂Al的Ni(OH)2样品的晶体结构及IR光谱特征;测试了用Al掺杂的Ni(OH)2为正极活性物质的Zn/Ni实验电池的充放电性能.研究结果表明:所合成的Al掺杂Ni(OH)2具有α-Ni(OH)2的晶体结构;Al掺杂Ni(OH)2活性物质在充放电过程中转移电子数目大于1,Al掺杂Ni(OH)2作为正极活性物质的Zn/Ni试验电池的第二次循环放电比容量为362.9mAh/g.     

金属掺杂对纳米管TiO2光催化性能的影响

利用水热法,以DegussaP-25TiO2粉末为原料,AlCl3、Fe(NO3)3·9H2O和ZnCl2为掺杂剂合成金属掺杂纳米管TiO2,并采用透射电镜(TEM)X射线衍射(XRD)、X射线光电子能谱(XPS)和BET比表面积分析对催化剂进行表征。结果表明,掺杂金属分别以Al3+ 、Fe3+和Zn2+的形式存在。随着煅烧温度的增高,样品的比表面积逐渐降低,锐钛矿含量先增大后减小;金属掺杂后,催化剂比表面积略有降低,锐钛矿含量 略 有 增 大。考 察 紫 外 光 催 化 臭 氧 化 工 艺 中TiO2降解腐植酸标志物的催化效果,结果表明,450℃煅烧未掺杂纳米管TiO2对腐植酸的催化降解效率为44%,较P-25TiO2粉末提高了11%;金属掺杂后催化效果提升明显,550℃煅烧Fe掺杂纳米管TiO2的催化效果最为显著,腐植酸去除率达77%。     

超支化PNP铬系催化剂的合成及对乙烯齐聚的催化性能EI北大核心CSCD

以正己胺为核的1.0G超支化大分子(R6-1.0G)、氯代二苯基膦和CrCl3(THF)3为原料,合成了一种新型的超支化PNP铬系催化剂(R6-Cat)。红外光谱、核磁共振氢谱和紫外光谱证实合成产物的结构与理论结构相符。在合成的基础上,对该催化剂催化乙烯齐聚的性能进行了研究。考察了溶剂种类、反应温度、Al/Cr比、反应压力等条件对该催化剂催化乙烯齐聚性能的影响。结果表明,当以甲苯为溶剂,甲基铝氧烷(MAO)为助催化剂时,该催化剂表现出良好的催化乙烯齐聚性能。随着反应温度和Al/Cr比的增加,催化活性先升高后降低;而催化活性随着反应压力的增加而增大。当反应温度为35℃、Al/Cr比为500、反应压力为1.0 MPa时,催化活性可达2.02×104 g/(mol Cr·h),聚合产物主要是C8以下的低碳烯烃,含量高达92%以上。相同条件下,其催化乙烯齐聚的活性高于与其结构类似但烷基链长度不同的超支化PNP铬系催化剂。     

ZnO增强MxCo3-xO4电催化析氧性能研究

氢能因热值高、燃烧产物无污染等优良特性,成为目前新型能源研究的焦点,有望成为化石能源的理想替代品。电催化水分解作为最具前景的氢气制备方法,包含两个半反应:析氧反应(OER)和析氢反应(HER)。其中OER目前主要采用贵金属作为催化剂,但其高成本极大地限制了电催化产氢的工业化。基于Co 3O 4的Co基掺杂氧化物具有成本低廉、催化活性高且稳定性强等优良特性。目前对于Co基掺杂氧化物的研究主要集中于探究掺杂不同金属元素(Zn,Ni,Fe等)对其催化活性的影响,极少研究掺杂惰性氧化物对其催化活性的影响。合成了一种CoFeNiZn复合氧化物,且具有优良的电催化活性和稳定性。在1 mol/L KOH的电解液中,10 mA/cm 2的电流密度下,CoFeNiZn复合氧化物过电势(η10)为310 mV,塔菲尔斜率(Tafel slope)为40 mV/dec,相比原始CoFeNi氧化物(η10为400 mV)过电势降低了90 mV。CoFeNiZn催化剂催化性能的提高主要是由于以惰性ZnO作为基质可有效地分散催化活性物质,并充分暴露CoFeNi氧化物的催化活性位点。这一基于催化材料掺杂非活性物质提高催化剂催化活性的发现可以为现有催化剂开发提供新的思路。     

Fe掺杂NiCo-LDH的制备及OER催化性能

层状双金属氢氧化物(LDH)因具有组成和结构易于调变等优势而被广泛用作析氧反应(Oxygen evolution reaction,OER)催化剂.通过溶剂热法合成了由二维纳米片组成的花状结构的NiCo-LDH材料,并利用Fe离子对其进行刻蚀,合成了 Fe掺杂的NiCo-LDH.在OER催化性能测试中,与未刻蚀的NiCo-LDH相比,在电流密度为10 mA·cm-2时,Fe掺杂的NiCo-LDH材料的过电位仅为273 mV,塔菲尔斜率为98 mV·dec-1,OER性能显著提升.此外,所合成的Fe掺杂的NiCo-LDH材料还表现出良好的长期稳定性,经过16 h的连续测试,其OER催化活性仍然能保持在80％.Fe离子刻蚀使NiCo-LDH纳米片具有较多的边缘缺陷,能够提供更多的边缘位点作为活性中心;并且Fe离子的引入改变了NiCo-LDH的电子结构,增加了 LDH的层间距离,从而有效改善了催化剂的催化活性和动力学性能.     

Electrochemical sensor for detecting ultratrace nitroaromatic compounds using mesoporous SiO2-modified electrode

An electrochemical sensor for ultratrace nitroaromatic compounds (NACs) using mesoporous SiO2 of MCM-41 as sensitive materials is reported. MCM-41 was synthesized and characterized by scanning electron microscope, transmission electron microscopy, and small-angle X-ray diffraction. Glassy carbon electrodes modified with MCM-41 show high sensitivity for cathodic voltammetric detection of NACs (including 2,4,6-trinitrotoluene (TNT), 1,3,5-trinitrobenzene (TNB), 2,4-dinitrotoluene, and 1,3-dinitrobenzene) down to the nanomolar level. The high sensitivity is attributed to the strong adsorption of NACs by MCM-41 and large surface area of the working electrode resulting from MCM-41 modification. The voltammetric response is fast, and the detection of NACs can be finished within 14 s. SiO2 nanospheres were similarly used to modify glassy carbon electrodes for electrochemical detection of TNT and TNB. The detection limit of SiO2 nanosphere-modified electrodes is lower than that of MCM-41-modified electrodes, possibly due to the smaller surface area of SiO2 nanospheres than mesoporous MCM-41. The results show mesoporous SiO2-modified glassy carbon electrodes, particularly MCM-41-modified electrodes, open new opportunities for fast, simple, and sensitive field analysis of NACs.     

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。     

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.     

Synthesis and characterization of mesoporous Si-MCM-41 materials and their application as solid acid catalysts in some esterification reactions

Mesoporous MCM-41 has been synthesized by sol–gel method at room temperature possessing good thermal stability, high surface area as well as retention of surface area at high temperature. The MCM-41 neutral framework has been modified and put to practical use by incorporating Al³⁺ in the siliceous MCM-41 framework and supporting 12-TPA (12-tungstophosphoric acid) onto MCM-41 by process of anchoring and calcination to induce Brønsted acidity in MCM-41 to yield Al-MCM-41 and 12TPA-MCM-41, respectively. The synthesized materials have been characterized for elemental analysis by ICP-AES, XRD, SEM, TEM, EDX, FT–IR and TGA. Surface area has been determined by BET method and pore size and pore size distribution determined by BJH method. Surface acidity has been evaluated by NH₃-TPD method. The potential use of Al-MCM-41 and 12TPA-MCM-41 as solid acid catalysts has been explored and compared by studying esterification as a model reaction wherein monoesters such as ethyl acetate (EA), propyl acetate (PA), butyl acetate (BA) and benzyl acetate (BzA) have been synthesized, optimizing several parameters such as catalyst amount, reaction time, reaction temperature and mole ratio of reagents.     

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.     

Organo-functionalized mesoporous supports for Jacobsen-type catalyst: Laponite versus MCM-41

In order to exploit the different textural properties of Laponite and MCM-41, specifically in terms of their external versus internal surface areas, in the covalent anchoring of a chiral Mn(III) salen complex, these materials were functionalized with 3-aminopropyltriethoxysilane (APTES), subsequently activated with sodium ethoxide, and finally used to anchor the Jacobsen catalyst derivative C1. All the materials were characterized by nitrogen elemental analysis, XPS, PXRD, nitrogen adsorption at −196 °C, FTIR and for those with the immobilized complex, they were additionally characterized by Mn AAS. The APTES anchored at the edges of the Laponite single crystals and inside the MCM-41 pores. Moreover, under the same preparative conditions, higher amount of APTES was anchored onto MCM-41 than onto Laponite, which is due to the higher surface area of MCM-41 compared to Laponite, as well as to its more exposed SiO₄ tetrahedra. Activation of the two organo-functionalized materials with sodium ethoxide originated anionic nitrogen groups as deduced by the increase of surface sodium content of these materials and N1s binding energy changes, but led to a small decrease in N bulk content as a result of some APTES leaching. Moreover, for MCM-41 some disruption of the silica framework occurred as a consequence of the basic treatment, as suggested by XPS, PXRD, and nitrogen adsorption study. The APTES functionalized Laponite and MCM-41 materials, as well as the activated analogs, were able to anchor C1 through axial coordination of the metal centre to the grafted surface nitrogen atoms. APTES functionalized MCM-41 presented similar complex content to Laponite analog, what points out for the fact that, at least for the bulky complex used in this work, there was no clear benefit in using a material of high internal area; for the ethoxide activated analogs, Laponite showed the highest complex content of all materials, but MCM-41 was able to anchor the lowest complex quantity, probably as a consequence of damaging effect caused by the basic treatment within its porous structure. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Functionalization of mesoporous MCM-41 for the delivery of curcumin as an anti-inflammatory therapy

In this study, mesoporous silica nanoparticles (MSNs) composed of MCM-41 were synthesized and modified with amine groups (i.e., NH₂) to form NH_2/MCM-41, which was loaded with curcumin (CUR) to form CUR@NH₂/MCM-41 to create an efficient carriers in drug delivery systems (DDSs). The three samples (i.e., pure MCM-41, NH₂/MCM-41, and CUR@NH₂/MCM-41) were characterized using X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) surface area, Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), transition electron microscopy (TEM), and a thermogravimetric analyzer (TGA). The study investigated the effect of the carrier dose, CUR concentration, pH, and contact time on the drug loading efficiency (DLE%) by adsorption. The best DLE% for MCM-41 and NH₂/MCM-41 was found to be 15.78 and 80%, respectively. This data demonstrated that the Langmuir isotherm had a greater correlation coefficient (R²) of 0.9840 for MCM-41 and 0.9666 for NH₂/MCM-41 than the Freundlich and Temkin isotherm models. A pseudo-second-order kinetic model seems to fit well with R² = 0.9741 for MCM-41 and R² = 0.9977 for NH₂/MCM-41. A phosphate buffer solution (PBS) with a pH of 7.4 was utilized to study CUR release behavior. As a result, the full release after 72 h was found to have a maximum of 74.1% and 29.95% for pure MCM-41 and NH₂/MCM-41, respectively. The first-order, Weibull, Hixson-Crowell, Korsmeyer-Peppas, and Higuchi kinetic release models were applied to releasing CUR from CUR@MCM-41 and CUR@NH₂/MCM-41. The Weibull kinetic model fit well, with R² = 0.944 and 0.96912 for pure MCM-41 and NH₂/MCM-41, respectively.     

配合物[Fe(bipy)2]3+修饰的MCM-41的合成与表征

以γ－氨丙基修饰介孔分子筛ＭＣＭ－４１内孔壁,将引入的γ－氨丙基与金属配位离子［Ｆｅ（ｂｉｐｙ）_２］^３＋通过配位键首次合成了金属配位化合物修饰的ＭＣＭ－４１（ＭＣＭ－ａｐ－Ｆｅ（ｂｉｐｙ）_２）．通过ＸＲＤ,７７Ｋ氮气吸附－脱附曲线,固体ＵＶ－ｖｉｓ漫反射光谱和循环伏安曲线表征了复合物ＭＣＭ－ａｐ－Ｆｅ（ｂｉｐｙ）_２。由于［Ｆｅ（ｂｉｐｙ）_２］^３＋的引入,使 ＭＣＭ－ａｐ－Ｆｅ（ｂｉｐｙ）_２的结晶度降低, ＢＥＴ比表面积、孔容和最可几孔径急剧下降．γ－氨丙基与Ｆｅ^３＋的配位而使其ＵＶ－ｖｉｓ漫反射吸收光谱与ＭＣＭ－Ｆｅ（ｂｉｐｙ）_２不同;循环伏安特性曲线表明ＭＣＭ－ａｐ－Ｆｅ（ｂｉｐｙ）_２在电化学上比浸渍法制备的ＭＣＭ－Ｆｅ（ｂｉｐｙ）_２稳定．     

Influence of functional silanes on hydrophobicity of MCM-41 synthesized from rice husk

Mesoporous molecular sieve MCM-41 was synthesized from rice husk and rice husk ash, called RH-MCM-41 and RHA-MCM-41. The sol–gel mixtures were prepared with molar composition of 1.0 SiO₂: 1.1 NaOH: 0.13 CTAB: 0.12 H₂O. After calcination, the polarity of MCM-41 still remained on its surface due to the existence of some silanol groups. In this study, both RH-MCM-41 and RHA-MCM-41 were silylated with two different functional silanes trimethylchlorosilane (TMCS) and phenyldimethylchlorosilane (PDMS) in order to reduce the surface polarity. The efficiency of silylation was determined based on the amount of moisture adsorbed using thermogravimetric analysis (TGA). The structure of silylating agents and silica templates were found to be important parameters affecting the hydrophobic property of the MCM-41 surface. The post-grafting silylation with aliphatic silane can decrease the surface polarity better than that with aromatic silane, probably due to less sterric hindrance effect. Thus, the surface hydrophobicity of MCM-41 can be improved by the silylation of small molecular silane on RH-MCM-41.