Ce-MCM-48立方介孔分子筛结构的光谱表征

在碱性条件下,以混合模板剂pH调节水热合成了掺入铈的介孔分子筛Ce-MCM-48,并采用XRD,DRUV-Vis(紫外-可见漫反射),FTIR,XRF结合BET等测试手段对样品进行表征.实验结果表明,采用本方法所合成的掺铈介孔材料仍保持立方介孔的有序结构,同时适量的铈的掺入和pH调节使分子筛的有序性及吸附性能得到改善,晶胞参数增大,孔径更均一,孔壁增厚.从而可推出Ce-MCM-48的热稳定性、水热稳定性、催化活性及择形选择性可得到提高.掺入的铈以四配位状态高度分散在介孔的有序结构当中.红外光谱表明不同量的铈的掺入对骨架硅的各种振动扰动程度不同.     

介孔分子筛Al-MCM-41的合成与催化异构化性能

采用正硅酸乙酯(TEOS)为硅源,九水硝酸铝为铝源,十六烷基三甲基溴化胺(CTMABr)为模板剂,在室温条件下合成了介孔Al-MCM-41分子筛.通过XRD、N2等温吸附、SEM、FTIR等分析测试手段表征了分子筛的介孔结构和表面性质.结果表明所合成的分子筛有良好的介孔结构和较高的有序度,并且有较高的比表面积(达到816 m2·g-1)和窄的孔径分布.采用程序升温的焙烧方式、凝胶Al/Si比最大范围控制在0.06～0.13有利于合成高度有序的介孔Al-MCM-41分子筛.评价结果表明,所合成的Al-MCM-41分子筛对桥式四氢双环戊二烯(endo-TCD)异构化反应合成挂式异构体exo-TCD及金刚烷具有较高的催化活性和极高的选择性.     

以MCM-22分子筛为前驱体制备MCM-36分子筛

以MCM-22分子筛为前驱体,对原料配比和合成步骤等参数进行调变,探索了MCM-36分子筛的合成规律。通过X射线衍射、扫描电镜和N2吸附-脱附等表征方法对所合成的MCM-36分子筛物理化学性质进行表征。结果表明,以MCM-22为前驱体,溶胀原料质量配比为1∶3∶1.2时,MCM-36分子筛介孔和微孔比表面积最大。     

Cu/HMOR催化二甲醚羰基化合成乙酸甲酯: 催化剂制备方法的影响 (cited: 2)

采用氨蒸发法、尿素水解法、离子交换法及浸渍法制备HMOR负载的Cu催化剂, 考察其催化二甲醚(DME)羰基化合成乙酸甲酯(MA)性能. 结果表明离子交换法制得Cu/HMOR催化剂在Cu的金属中心和酸性分子筛载体的共同作用下具有较好催化反应活性. 在210 oC、1.5 MPa、空速4883 h^-1,DME转化率为95.3%,MA选择性为94.9%. 对催化剂进行N2物理吸附、X射线衍射、NH₃程序升温脱附和CO程序升温脱附等表征发现,离子交换法制得Cu/HMOR催化剂具有较高比表面、大量弱酸及一定中强酸、适中的CO吸附强度,提高了CO插入DME羰基化反应活性.     

MCM-41水分吸附特性的调控研究

本文以介孔分子筛MCM-41为研究对象,通过合成与后改性法,调控其孔径、表面性质以及平衡阳离子种类。通过X射线衍射、液氮吸附对介孔材料结构进行结构分析,采用动态水分吸附仪研究其水分吸附特性,并结合吸附等温线热力学模型进行分析。研究结果表明:铝嫁接有效提高MCM-41在低湿度下吸附量,并且随着嫁接浓度的增大而增加;通过阳离子置换强化了低湿度环境下MCM-41的吸附量,不同阳离子置换后的强化效果:Mg~(2+)+Li~+Na~+。热力学模型分析表明阳离子置换后的吸附剂表面均一,且具有较好的亲水性。     

铈铕掺杂氯硅酸镁钙体系的相对光谱功率分布与色坐标定位

采用高温固相反应法合成铈铕掺杂氯硅酸镁钙系列粉体,利用X射线衍射(XRD)对晶体结构加以鉴定,并对其荧光光谱进行了测试和分析.通过光谱功率校准曲线,推演出样品的相对光谱功率分布,进而对粉体发光色坐标进行计算和表征.实验结果表明,合成粉体为面心立方晶体Ca8Mg(SiO4)4Cl2,铈铕单掺氯硅酸镁钙样品在紫外光激发下分...     

多酸-介孔分子筛复合材料的制备、表征及光催化活性

采用浸渍法将具有光催化活性的多金属氧酸盐(polyoxometalate,POM)磷钨酸和硅钨酸负载到介孔分子筛MCM-41,制备了H3PW12O40/MCM-41和H4SiW12O40/MCM-41两种复合材料,以红外光谱(FT-IR)、X射线衍射(XRD)、N2吸附、高分辨透射电镜(HRTEM)等分析手段对所合成的多酸-分子筛复合材料进行了表征,并以农药百草枯的光催化降解考察了复合材料的光催化活性。所合成的复合材料同时保留了母体多酸的Keggin特征结构和载体MCM-41分子筛均匀的六方孔道结构,比表面积超过200m2.g-1。用于农药百草枯的光催化降解实验表明,两种复合材料均具有较高的光催化活性。在365nm紫外光辐照下,以H3PW12O40/MCM-41和H4SiW12O40/MCM-41为催化剂催化反应14h后,百草枯(10mg.L-1)的降解转化率分别达到92.0%和87.6%,反应符合一级化学动力学模型,半衰期分别为3.7和4.6h。     

Ni_2P/介孔分子筛催化剂的原位漫反射红外光谱研究

以介孔分子筛MCM-41,MCM-48,SBA-15,SBA-16为载体,硝酸镍为镍源,磷酸氢二铵为磷源,通过浸渍法制备了含有磷化镍前体的介孔分子筛样品,然后在氢气气氛中进行程序升温还原,得到了磷化镍/介孔分子筛催化剂.采用原位漫反射红外光谱法,用CO作为探针分子,对样品的吸附特征进行了研究.结果表明,在介孔分子筛表面CO存在着较弱的物理吸附.在Ni2P/MCM-41催化剂样品表面有四种CO的吸附态:(1)在2055cm-1处形成的Ni(CO)4物种的吸附,(2)在2 091cm-1处的配位不饱和Niδ(0<δ<1)物种上的吸附,(3)在2 127 cm-1处的Ni+物种上的吸附,(4)在2 198～2 202 cm-1范围内的P物种上的吸附.在Ni2P/MCM-48,Ni2P/SBA-15,Ni2P/SBAZ-16催化剂样品表面有二种CO的吸附态:在2 051～2 055cm-1处的Ni(CO)4吸附和在2 093～2 096 cm-1处的配位不饱和Niδ+(0<δ<1)物种上的吸附.     

H_3PW_(12)O_(40)/MCM-48的制备及其光催化降解农药(英文)

以介孔分子筛MCM-48为载体,采用水热法制备了负载磷钨酸H3PW12O40(HPW)的多金属氧酸盐催化剂HPW/MCM-48。利用傅里叶变换红外光谱(FT-IR)、小角度X射线粉末衍射(XRD)、氮气吸附检测和高分辨透射电子显微镜(HRTEM)对其结构进行了表征,并以农药吡虫啉和百草枯为对象,考察了所制备的HPW/MCM-48的光催化降解活性。结果表明,采用水热法制备的催化剂保持了MCM-48的介孔分子筛结构和HPW的Keggin结构,比表面积783.35m2·g-1,孔体积1.46cm3·g-1,平均孔径2.76nm,相比于母体HPW,HPW/MCM-48的比表面积大大增加;在365nm紫外光下反应14h后,20mg剂量HPW/MCM-48催化剂能使50mL,10mg·L-1吡虫啉和百草枯的降解率分别达57.38%和63.79%,而HPW对两种农药的降解率在25%左右,空白组降解率均低于5%,说明负载后HPW对两农药的降解活性显著增强。动力学考察表明,HPW/MCM-48对农药降解过程符合一级动力学方程,对吡虫啉和百草枯这两种农药的降解速率常数Ka分别为0.089和0.117h,半衰期t1/2为7.8和5.9h。     

沉淀方法及铈掺杂对铜锰氧化物催化剂催化氧化CO性能的影响

研究了铈掺杂及沉淀方法对铜锰氧化物催化剂的结构特性及室温催化氧化CO性能的影响. 使用X射线衍射、N₂吸附脱附、等离子体发射光谱、程序升温还原、紫外可见漫反射以及X射线光电子能谱等手段对各催化剂进行了表征. 发现掺杂少量的铈于铜锰氧化物催化剂中,CeO₂相高度分散并能阻止催化剂的烧结和团聚,所制得的催化剂的颗粒较小,氧化还原性能提高,比表面增大,并形成了较多的活性位点,使其对CO的催化氧化性能明显提高.     

MAS NMR studies of nanoporous matrices filled with sodium nitrite

The sodium nitrite NaNO2 incorporated into MCM-41 molecular sieves with pore sizes of 20, 26, and 37 Å has been investigated by 23Na magic-angle spinning NMR spectroscopy. It has been demonstrated that the structure of the crystalline phase of the nitrite in a confined geometry is similar to the structure of bulk nitrite NaNO2. The direct proof of the diffuse melting of sodium nitrite in the pores has been obtained. The NMR signal of the molten sodium nitrite phase has been observed at temperatures close to the completion of the melting.     

Post-treatment of mesoporous material with high temperature for synthesis super-microporous materials with enhanced hydrothermal stability

Super-microporous silicon material with high hydrothermal stability denoted as MCM-48-T has been prepared from mesoporous MCM-48 by high temperature treatment. The structural and chemical property of MCM-48-T has been characterized by variety of techniques such as small-angle X-ray diffraction (XRD), transmission electron microscopy (TEM), N₂ adsorption-desorption, infrared spectroscopy (IR) and ²⁹Si MAS NMR, etc. The results showed that Si-OH groups are forced to condense by the treatment of high temperature and the pore size of MCM-48-T is around 1.03 nm in the super-microporous range. Besides, the ratio of Q⁴/Q³ increases considerably. Compared with the original material (MCM-48), the hydrothermal stability of MCM-48-T has significantly enhanced.     

Stability and textural properties of cobalt incorporated MCM-48 mesoporous molecular sieve

Transition metal cobalt incorporated MCM-48 mesoporous molecular sieves (CoMCM-48) with different Co contents were synthesized hydrothermally at 120 °C for 24 h by directly adding fluoride ions to the initial gel. The resulting materials were characterized by means of XRD, TEM, FT-IR, UV-vis, TPR and N₂ physical adsorption, respectively. The effect of various factors, such as the Si/Co molar ratio, calcination temperature and hydrothermal treatment time, on the crystalline structure and textural properties of CoMCM-48 was investigated in detail. The results show that the CoMCM-48 mesoporous materials with high specific surface area were successfully synthesized. A small amount substitution of Co for Si in MCM-48 did not significantly change the textural properties while the higher cobalt incorporated leads to decrease of the surface area and deterioration of structural regularity. Furthermore, the resulting CoMCM-48 still retained the cubic mesoporous framework even after calcination at 800 °C for 4 h or hydrothermal treatment at 100 °C for 24 h.     

Optical properties of (nanometer MCM-41)-(malachite green) composite materials

Nanosized materials loaded with organic dyes are of interest with respect to novel optical applications. The optical properties of malachite green (MG) in MCM-41 are considerably influenced by the limited nanoporous channels of nanometer MCM-41. Nanometer MCM-41 was synthesized by tetraethyl orthosilicate (TEOS) as the source of silica and cetyltrimethylammonium bromide (CTMAB) as the template. The liquid-phase grafting method has been employed for incorporation of the malachite green molecules into the channels of nanometer MCM-41. A comparative study has been carried out on the adsorption of the malachite green into modified MCM-41 and unmodified MCM-41. The modified MCM-41 was synthesized using a silylation reagent, trimethychlorosilane (TMSCl), which functionalized the surface of nanometer MCM-41 for proper host-guest interaction. The prepared (nanometer MCM-41)-MG samples have been studied by powder X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, low-temperature nitrogen adsorption-desorption technique at 77 K, Raman spectra and luminescence studies. In the prepared (nanometer MCM-41)-MG composite materials, the frameworks of the host molecular sieve were kept intact and the MG located inside the pores of MCM-41. Compared with the MG, it is found that the prepared composite materials perform a considerable luminescence. The excitation and emission spectra of MG in both modified MCM-41 and unmodified MCM-41 were examined to explore the structural effects on the optical properties of MG. The results of luminescence spectra indicated that the MG molecules existed in monomer form within MCM-41. However, the luminescent intensity of MG incorporated in the modified MCM-41 are higher than that of MG encapsulated in unmodified MCM-41, which may be due to the anchored methyl groups on the channels of the nanometer MCM-41 and the strong host-guest interactions. The steric effect from the pore size of the host materials is significant. Raman spectra firmly demonstrated the stable form obtained after the MG incorporation into the nanometer MCM-41. Therefore, nanometer MCM-41 appears to have a good potential for its use as a support for dyes and the (nanometer MCM-41)-MG composite materials may give a wide optical application.     

Quantitative characterization of nanoparticle agglomeration within biological media

The electronics industry is one of the world??s fastest growing manufacturing industries. However, e-waste has become a serious pollution problem. This study reports the recovery of e-waste for preparing valuable MCM-48 and ordered mesoporous carbon for the first time. Specifically, this study adopts an alkali-extracted method to obtain sodium silicate precursors from electronic packaging resin ash. The influence of synthesis variables such as gelation pH, neutral/cationic surfactant ratio, hydrothermal treatment temperature, and calcination temperature on the mesophase of MCM-48 materials is investigated. Experimental results confirm that well-ordered cubic MCM-48 materials were synthesized in strongly acidic and strongly basic media. The resulting mesoporous silica had a high surface area of 1,317?m²/g, mean pore size of about 3.0?nm, and a high purity of 99.87?wt%. Ordered mesoporous carbon with high surface area (1,715?m²/g) and uniform pore size of CMK-1 type was successfully prepared by impregnating MCM-48 template using the resin waste. The carbon structure was sensitive to the sulfuric acid concentration and carbonization temperature. Converting e-waste into MCM-48 materials not only eliminates the disposal problem of e-waste, but also transforms industrial waste into a useful nanomaterial.     

Proton conduction in CsHSO4–mesoporous silica composite electrolytes

Novel proton-conducting composites were prepared by incorporating molten CsHSO₄ (CHS) into two types of mesoporous silica, MCM-41 with a one-dimensional (1-D) hexagonal structure and MCM-48 with a three-dimensional (3-D) cubic structure. Their proton conductivities (σ) were measured to examine effects of the incorporation and the dimensionality of the mesopores on their conductivity. Incorporation of proper amounts of MCMs maintained high proton conductivities as high as ~ 10^? 3 S cm^? 1 at temperatures above the superprotonic phase-transition temperature (T_s: 414 K) of CHS and improved the conductivity by 2 to 3 orders of magnitude at temperatures below T_s. In the case of MCM-41, more than 40 mol% mixing, however, caused steep drops in σ in both temperature ranges. On the other hand, the CHS/MCM-48 composite showed a linear increase in σ below T_s and a gradual decrease in σ above T_s with an increase in the MCM-48 content at least up to 60 mol%. X-ray diffraction (XRD) analysis revealed that CHS filled in the MCM mesopores became X-ray crystallographically amorphous and the amount of the amorphous phase increased with an increase in the MCM contents. In the case of the CHS/MCM-48 composites, the activation energy (E_a) for proton conduction below T_s drastically came close to that above T_s by mixing with MCM-48 up to 30 mol%. This indicates that the proton can transport similarly to the conduction mechanism in the superprotonic phase even below T_s. These results suggest that CHS adopts a highly proton-conducting amorphous phase in the mesopores at temperatures below T_s, and that MCM-48 with the 3-D cubic structure is more suitable for formation of high proton-conducting percolation paths.     

氢化物发生原子荧光光谱法测定螺旋藻中无机硒和有机硒

螺旋藻试样经硝酸、高氯酸消解,原子荧光光谱法测定总硒含量;用水浸提螺旋藻试样,经环己烷萃取后,水相采用硝酸、高氯酸消解后,原子荧光光谱法测定无机硒含量,间接测定螺旋藻中有机硒含量。总硒测定精密度在1.05%—2.10%之间,加标回收率在96.6%—102.3%之间;无机硒的浸提率在95.1%—100.7%之间,测定精密度在2.37%—3.70%之间,加标回收率在93.6%—98.4%之间,检出限为0.47mg/kg,满足螺旋藻中有机硒含量的测定。     

Wide range humidity sensing of LiCl incorporated in mesoporous silica circular discs

Lithium chloride (LiCl) incorporated MCM-41 has been synthesised by sol-gel method using tetraethyl orthosilicate as a precursor in basic medium. 5, 10, 15, 20, 25, 30 and 35 wt% of LiCl were incorporated in mesoporous silica to investigate the humidity sensing. With increasing wt% of LiCl broadening of O–H peak is observed in the Fourier Transform Infrared spectra, indicating greater adsorption of hydroxyl groups on porous silica. The surface area of the MCM-41 circular discs was determined by Brunauer?Emmett?Teller (BET). Scanning electron microscopy images suggest that incorporation of LiCl leads to coalescence of grains in mesoporous silica. 25 wt% LiCl incorporated MCM-41 showed a wide range linear response of impedance change for 11%–90% RH exhibiting 3.5-order drop in impedance at a 1 kHz frequency. The Nyquist plots for all compositions showed increased ionic conduction with increasing relative humidity.     

Experimental evidence of the ferroelectric nature of the λ-point transition in liquid water

We studied the dielectric properties of nano-sized liquid water samples confined in polymerized silicates MCM-41 characterized by pore sizes 3–10 nm. Freezing temperature suppression in nanopores helps keep the water samples in liquid form at temperatures well below 0°C and thus effectively study the properties of supercooled liquid water. We report the first direct measurements of the dielectric constant by the dielectric spectroscopy method and demonstrate very clear signatures of the second-order phase transition of ferroelectric nature at temperatures next to the λ-point in the supercooled bulk water in full agreement with the recently developed model of the polar liquid.