两步晶化法制备介孔材料及其催化性能研究

采用两步晶化法,由MCM-22沸石前驱体合成了一种介孔材料.通过XRD、N2吸附-脱附、TEM、27A lMAS NMR以及吡啶吸附红外光谱等技术对样品进行了表征.结果显示所合成的样品不是微孔沸石与介孔材料的混合物,而是含强酸性中心、水热稳定性良好的新型介孔分子筛.利用异丙苯的裂解反应、苯和1-十二烯烃的烷基化反应,评价了其对大分子的酸催化活性,并与常规介孔材料MCM-41进行了比较.在350℃时,所合成的介孔材料和常规介孔材料MCM-41对异丙苯的裂解转化率分别为68.98%和48.80%.在210℃苯和1-十二烯烃的烷基化反应时,所合成的介孔材料和MCM-41对1-十二烯烃的转化率分别约为95.20%和86.89%,产物直链烷基苯的选择性分别约为88.11%和90.06%.结果表明所合成的介孔材料对大分子的酸催化性能优越于常规介孔材料MCM-41.     

介孔分子筛MCM-41的制备及其对Cr6+的吸附

以鞍山铁尾矿为硅源,CTAB为模板剂,采用水热法合成出介孔分子筛MCM-41。采用XRD、BET、HRTEM对样品进行了表征。将该介孔分子筛MCM-41应用于水中Cr6+离子的吸附,研究了吸附时间、吸附剂用量、初始浓度对分子筛吸附性能的影响,并探讨了吸附过程的表观吸附动力学模型及吸附等温模型。结果表明,增加吸附时间、吸附剂用量、初始浓度有利于分子筛对Cr6+离子的吸附。Cr6+的吸附过程遵循二级表观吸附动力学模型;在吸附剂表面的吸附遵循Langmuir吸附等温线模型。     

介孔分子筛孔尺寸表征方法比较

MCM-41是由表面活性剂十六烷基三甲基溴化铵为模板剂经水热合成，550℃煅烧5h制备的规则硅质六方介摘要孔材料；Ti-MCM-41是在MCM-41的基础上，将Ti离子涂敷引入到MCM-41的介孔中合成的。该类材料孔尺寸的表征方法有N2吸附、透射电镜TEM、SAXS等，其中N2吸附、透射电镜是传统的介孔尺寸的表征方法，SAXS是近年新的介孔尺寸的表征方法。比较了Ti-MCM-41材料的孔尺寸的表征方法，得出：SAXS得到的Ti-MCM-41孔径与TEM照片的结果符合较好，但与N2吸附的结果偏差较大。SAXS、TEM、N2吸附-脱附等温线给出的Ti-MCM-41的平均孔径分别为2.00nm、2.15nm、3.60nm。     

介孔分子筛MCM-41的合成方法与晶化条件

介孔材料MCM-41具有规则孔道结构,在多相催化、吸附分离、复合材料、纳米组装等领域有着重要的学术研究与应用价值.其可以通过长链季铵盐、伯胺、双子胺或聚氧乙烯类表面活性剂胶束的模板作用,在多种不同的条件下合成.综述了MCM-41介孔分子筛近年来所取得的进展,介绍和讨论了各种合成工艺方法,归纳和分析了影响其合成的主要因素.     

EDTA修饰MCM-41的合成及其对水中Cu2+的吸附研究

采用微波法合成了介孔分子筛氨丙基修饰的MCM-41(MCM-41-(CH2)3NH2),将其与EDTA反应,制得MCM-41-(CH2)3NH2-EDTA,利用XRD、FT-IR、低温N2吸附对其进行了表征,并考察了其对水中Cu2+的吸附性能及材料的化学稳定性.结果表明,产物在弱酸弱碱条件下稳定存在,且有较大的吸附量,在适宜条件下吸附符合Langmuir模型,最大吸附量为33.22mg/g,吸附半衰期为2.04min.最后对其吸附Cu2+的机理进行了分析.     

MCM-41介孔分子筛和纳米TiO2/MCM-41的合成与结构表征

以工业水玻璃为硅源,表面活性剂十六烷基三甲基溴化铵为结构模板剂,利用室温晶化法合成出MCM-41介孔分子筛,并以钛酸丁酯为前驱体,通过溶胶凝胶法及液相沉积法对介孔分子筛MCM-41进行纳米TiO2的组装。运用XRD、FT-IR、N2吸附-脱附等表征手段对其结构特征和氧化钛分散状态进行了研究,结果表明：TiO2与MCM-41端基硅氧键反应形成Ti-O-Si键;纳米TiO2不仅进入孔道,较均匀地修饰了介孔分子筛MCM-41的孔壁,而且使介孔分子筛MCM-41仍保持有序的孔道结构。     

磁性MCM-41对单宁酸的吸附性能研究

采用溶胶-凝胶法结合水热法,以纳米铁酸镍为磁核制备出具有核壳结构的MCM-41/NiFe_2O_4。通过氮气吸附脱附(BET)、X射线衍射(XRD)、红外光谱(FT-IR)、振动样品磁强计(VSM)等手段对样品进行表征。结果表明,磁性MCM-41的比表面积为853.33m2/g,介孔平均孔径为3.34nm。通过静态吸附单宁酸实验,探究磁性MCM-41的吸附机理。结果表明,磁性MCM-41吸附单宁酸符合准二级动力学模型、主要进行单分子层吸附。     

配合物[Mn(phen)2]2+修饰的MCM-41的合成与表征

分别以γ－氨丙基和甲基丙烯酸丙酯基修饰介孔分子筛MCG－41内孔壁,将引入的有机官能团与金属配位离子[Mn(phen)2Cl]^ 通过配位键成键首次合成了锰（II）配位化合物修饰的MCM－41（MCM－ap-Nm(phen)2,MCM-Mn(phen)2)。通过XRD,FTIR,77K氮气吸附－脱附,UV－VIS漫反射光谱和Mn^2 电子顺磁共振谱（ESR）表征了复合物MCM－ap-Mn(phen)2和MCM－mp-Mn(phen)2,由于有机基团对MCM－41孔壁的修饰,使复合物的结晶度降低,增加的有机基团和配合物使红外光谱有所改变,BET比表面积,孔空和最可几孔径均下降,γ－氨丙基或甲基丙烯酸丙酯基与Mn^2 的配位而使其UV－VIS漫反射吸收光谱的在短波长的吸收加强,室温下Mn2 电子顺磁共振表明Mn(II)配位环境几乎没有变化。γγ     

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.     

氢氯噻嗪／MCM-41载药体系的制备与缓释作用研究

用微波辐射法合成介孔分子筛MCM-41，采用浸渍法将利尿药物氢氯噻嗪组装到介孔分子筛MCM-41孔道中，用XRD、低温N2吸附、IR对MCM-41及药物组装体进行了表征；研究了组装体的载药量、载药时间、在体外人工胃液中的释放等。结果显示合成的分子筛MCM-41具有规则的孔径结构，比表面积为1211m^2/g；分子筛MCM-41作为药物的载体具有较短的载药时间（t=26h），较大的载药量48％（m（药物）/优（载体）），较低的释放速率，表明制得了氢氯噻嗪／MCM-41缓释释放体系。     

Steam-assisted crystallization of TPA+-exchanged MCM-41 type mesoporous materials with thick pore walls

Hierarchical MCM-41/MFI composites were synthesized through ion-exchange of as-made MCM-41 type mesoporous materials with tetrapropylammonium bromide and subsequent steam-assisted recrystallization. The obtained samples were characterized by powder X-ray diffraction (XRD), UV–vis diffuse reflectance spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis, FT-IR, ¹H–¹³C CP/MAS and nitrogen adsorption–desorption. The XRD patterns show that the MCM-41/MFI composite possesses both ordered MCM-41 phase and zeolite MFI phase. SEM and TEM images indicate that the recrystallized materials retained the mesoporous characteristics and the morphology of as-made mesoporous materials without the formation of bulky zeolite, quite different from the mechanical mixture of MCM-41 and MFI structured zeolite. Among others, lower recrystallization temperature and the introduction of the titanium to the parent materials are beneficial to preserve the mesoporous structure during the recrystallization process.     

TiO_2在MCM-41内表面单层及双层分散的结构表征

首次以有机物钛酸丁酯为前驱体,合成了ＴｉＯ２呈单层分散状态（Ｔｉ／Ｓｉ＝０.２０）或双层分散状态（Ｔｉ／Ｓｉ＝０．３９）的介孔分子筛ＭＣＭ－４１（Ｓｉ／Ａｌ＝３５）,并以 ＸＲＤ,ＦＴＩＲ,Ｎ２吸附－脱附,固体ＵＶ－ｖｉｓ 漫反射等表征手段对其结构特征和氧化钛分散状态进行了研究．结果表明： ＴｉＯ２在介孔分子筛ＭＣＭ－４１孔道中分散, ＭＣＭ－４１骨架结构结晶度降低,但是附着二层ＴｉＯ２后,仍能保持长程有序结构; ＴｉＯ２与ＭＣＭ－４１孔道表面的ＳｉＯ２以化学键连接,生成Ｓｉ－Ｏ—Ｔｉ键;无论是单层还是双层分散的 ＴｉＯ２在 ＭＣＭ－４１内孔壁均匀分散;且由于ＴｉＯ２粒子的减小使其对紫外光的吸收发生明显的蓝移现象．     

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.     

TiO2在MCM-41内表面单层及双层分散的结构表征

首次以有机物钛酸丁酯为前驱体,合成了ＴiO2呈单层分散状态（Ｔi/Si=0．２０）或双层分散状态（Ｔi/Si=0．39)的介孔分子筛ＭＣＭ－４１（Si/Al=35）,并以ＸＲＤ,ＦＴＩＲ,Ｎ２吸附－脱附,固体ＵＶ－vis漫反等表征手段对其结构特征的氧化钛分散状态进行了研究,结果表明：ＴiO2在介孔分子筛ＭＣＭ－４１孔道中分散,ＭＣＭ－４１骨架结构结晶度降低,但是附着二层ＴiO2后,仍能保持长程有序结构;ＴiO2与ＭＣＭ－４１骨架结构结果度降低低,但是附着二层ＴiO2后,仍能保持长程有序结构,ＴiO2与ＭＣＭ－４１孔道表面的ＳiO2比化学键连接,生成Ｓi-O-Ti键;无论是单层还是双层分散的ＴiO2在ＭＣＭ－４１内孔壁均匀分散,且由于ＴiO2粒子的减小使其对紫外光的吸收发生明显的蓝移现象。.     

有序介孔氧化硅孔道氧化锰团簇组装研究

以有序介孔氧化硅MCM-41为主体材料,通过浸渍法及后续热处理工艺,在孔道中组装氧化锰的团簇粒子,并对其进行结构表征。通过XRD、HR—TEM、XPS及N2吸附表明氧化锰的团簇粒子已经成功组装到MCM-41有序孔道中。通过对不同孔径有序介孔材料的氧化锰团簇粒子的组装,表明随着孔道中组装量的增加,350nm附近光致发光强度增强,吸收边发生红移,同时1000nm附近吸收带宽化。     

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.     

酰腙类化合物修饰MCM-41吸附Cr(Ⅵ)性能

合成了2-羰基丙酸-4-甲基苯甲酰腙(简称酰腙1)和2-羰基丙酸-4-硝基苯甲酰腙(简称酰腙2)两种酰腙化合物,采用红外光谱法和X射线单晶衍射法对其进行了表征,并将其应用于修饰MCM-41分子筛中。用两种酰腙修饰后的MCM-41分子筛吸附废水中的铬(Ⅵ),考察了吸附时间、溶液pH值、吸附剂用量和温度对吸附效果的影响,同时对吸附过程进行了热力学和动力学拟合。测试结果表明,在吸附时间为40 min,分子筛加入量为0.3 g,溶液pH值为6,溶液温度为20℃时,吸附效果最好,MCM-41-酰腙1和MCM-41-酰腙2对铬(Ⅵ)的去除率分别可以达到97.6%和98.2%。吸附过程是熵减小的放热过程,反应过程分别遵循准一级反应和准二级反应动力学。     

Characterization of Zr-based MCM-41 mesoporous molecular sieves obtained by microwave irradiation or hydrothermal method

Zr-based MCM-41 mesoporous molecular sieves (ZrMCM-41) were successfully synthesized by microwave irradiation method and hydrothermal method, respectively. The obtained samples were characterized by XRD, TEM, FT-IR and N₂ physical adsorption. The results show that the samples synthesized by the two different methods both possess typical hexagonal mesoporous structure of MCM-41 and high specific surface areas (over 800 m²/g). After calcination at 750°C for 3 h or hydrothermal treatment at 100°C for 6 days, the mesoporous structure of the samples still retained, however, the mesoporous ordering is poor. Under the comparable conditions, the reaction time required in the synthesis of ZrMCM-41 by microwave irradiation method was greatly reduced, and microwave irradiation method is eco-friendly and is easy to operate.     

纳米介孔MCM-41-M/偶联剂体系对天然橡胶性能的影响

制备了天然橡胶(NR)/MCM-41-M、NR/偶联剂化学改性纳米介孔MCM-41-M、NR/MCM-41-M/偶联剂复合材料,研究了不同含量的MCM-41-M、不同种类偶联剂对MCM 41-M的改性以及偶联剂的添加方式对NR复合材料性能的影响.结果表明;MCM-41-M在NR中有明显的补强作用,当代替3份炭黑时NR基复合材料的拉伸强度达到最大值,比纯NR提高了12.7%。与MCM-41-M和KH-570直接添加到NR中相比,MCM-41-M经偶联剂KH-570改性使拉伸强度提高了50%。将MCM-41-M用偶联剂KH 570改性后添加到NR中,使NR的玻璃化转变温度升高、玻璃化转变区的损耗角减小、储能模量提高到最大。