杂原子介孔Co-MCM-41分子筛的制备及其吸附脱氮性能

采用水热法合成了介孔MCM-41和Co-MCM-41分子筛,并利用XRD、FT-IR、低温N₂吸附-脱附和NH₃-TPD等方法对合成的分子筛进行了表征。考察了晶化时间、晶化温度、陈化时间对合成介孔Co-MCM-41分子筛的影响,确定较适宜的合成条件为陈化时间1 h,晶化温度110 ℃,晶化时间2 d。XRD 和FT-IR表征结果说明,Co原子已经进入MCM-41的骨架。MCM-41和Co-MCM-41的平均孔径均为2.82 nm,BET比表面积分别为986.42和 637.69 m²/g,孔容分别为0.762 1和0.537 2 m³/g。NH₃-TPD的表征结果表明,MCM-41和Co-MCM-41的酸性都较弱,但Co-MCM-41的酸性明显强于MCM-41。在此基础上,利用合成的MCM-41和Co-MCM-41吸附脱除氮含量为1 737.35 μg/g的模拟燃料中的喹啉。喹啉分子尺寸的模拟结果为0.711 6 nm × 0.500 2 nm,说明其可以很容易地进入MCM-41和Co-MCM-41的介孔孔道中。Co-MCM-41分子筛的氮脱除率明显高于MCM-41,这是由于其较强的酸性及与喹啉之间的化学吸附,而且,Co-MCM-41吸附脱氮具有较好的再生性能。     

铈掺杂的介孔分子筛的水热合成与结构性能

以硅酸钠、硝酸铈铵为原料,十六烷基三甲基溴化铵为模板剂,通过水热法合成铈掺杂的介孔分子筛CeMCM-41.分别采用X射线粉末衍射(XRD)、透射电子显微镜(TEM)、红外光谱(FT-IR)、紫外-可见分光光度计(UV-Vis)和N2吸附-脱附等技术对产物的晶相、结构、形貌、比表面积和孔径进行表征.同时研究硅铈物质的量比对合成材料结构性能的影响.实验结果表明:水热条件下成功合成出铈掺杂的MCM-41介孔分子筛,其比表面积为480.5～1 295.2m2/g,平均孔径在2.70～6.29 nm之间.随着稀土元素铈的掺杂量的增加,CeMCM-41介孔分子筛的比表面积和孔体积变小,介孔有序性变差.     

杂原子介孔Co-MCM-41分子筛的制备及其柴油深度吸附脱碱氮性能

以硝酸钴为钴源,采用水热法合成了MCM-41和不同Co含量的Co-MCM-41分子筛,并利用XRD、FT-IR和低温N2吸附-脱附等方法对合成的分子筛进行表征。当加入的Co/Si物质的量比达到0.1时,依然能够成功合成具有规整有序的介孔结构的Co-MCM-41。MCM-41和Co-MCM-41静态吸附脱除0#柴油中碱氮的实验结果表明,Co/Si物质的量比为0.06的Co-MCM-41(2)分子筛的吸附容量最大,达到5.324 mg(N)/g分子筛,明显高于MCM-41分子筛的吸附容量2.532 mg(N)/g,说明Co进入MCM-41分子筛骨架后显著提高了分子筛的吸附脱除碱氮能力。当加入的Co/Si物质的量比大于0.06时,分子筛吸附脱除柴油中碱氮的能力反而下降,这是由于加入过多Co会使其以Co3O4形式高度分散在分子筛孔道中,堵塞了吸附活性位,使其无法与碱性氮化物接触造成吸附脱氮能力下降。动态吸附脱除0#柴油中碱性氮化物的结果表明,每克CoM CM-41(2)分子筛可将35 m L柴油的碱氮从147.54μg/g吸附脱除到10μg/g以下,吸附容量为4.2 mg(N)/g(吸附剂),由于动态吸附的接触时间较短使MCM-41失去了吸附脱氮能力,说明Co-MCM-41(2)对柴油中的碱氮具有较好的选择性。     

负载Co介孔分子筛催化热解乙醇制备纳米碳管

以硅酸钠为原料,CTAB为模板剂,水热法合成MCM-41介孔分子筛,采用浸渍法制备负载钴的介孔分子筛(Co/MCM-41),并将其作为催化剂,CVD法热解无水乙醇制备CNTs.利用XRD、TEM、比表面积和孔径分布测定和Raman光谱等方法对所合成的介孔分子筛和纳米碳管进行了表征.结果表明:所制备的Co/MCM-41样品具有典型的MCM-41的介孔结构;当热解反应温度为750℃下所制备出的纳米碳管的品质最好.     

介孔材料Co-MCM-41的合成及其吸附脱除各种碱性氮化物

采用水热法合成了MCM-41和不同Co/Si物质的量比的Co-MCM-41介孔材料,并采用XRD、FT-IR和低温氮气吸附-脱附方法对样品进行了表征。FT-IR及XRD表征结果说明,Co原子已经进入了介孔材料的孔壁。合成的MCM-41及Co/Si(物质的量比)为0.18以下的Co-M CM-41都具有六方有序排列的介孔结构。当加入的Co/Si(物质的量比)为0.22时,样品的(100)峰完全消失,不具备六方有序排列的介孔结构,说明以硝酸钴为钴源合成Co-MCM-41的最大Co加入量为Co/Si(物质的量比)为0.18左右。与MCM-41相比,各Co-MCM-41样品的XRD(100)峰随着Co加入量的增加逐渐变宽变弱,比表面积和孔容变小,平均孔径增大。当加入的Co/Si物质的量比大于0.06时,Co-MCM-41的介孔孔道中存在少量聚集态的Co3O4。利用合成的Co-MCM-41吸附脱除氮含量为1737.35μg/g模拟燃料中的碱性氮化物喹啉、苯胺或吡啶,结果表明,所有样品的吸附脱氮效果顺序为苯胺吡啶喹啉。Co-MCM-41(0.06)的吸附容量和氮脱除率明显要高于其他样品,对苯胺、吡啶和喹啉的吸附容量分别为42.17、35.66和29.18 mg(N)/g,去除率分别为82.38%、73.53%和61.11%。添加到模拟燃料中的芳烃化合物萘、苯或甲苯对其吸附脱氮没有影响,表明介孔材料Co-MCM-41对各种含氮化合物的吸附主要是N原子与Co的配位络合吸附,而不是π-π络合作用。采用焙烧或乙醇溶剂洗涤再生后的Co-MCM-41(0.06)恢复了吸附脱氮能力,说明其具有较好的再生性能。     

Co-MCM-41和Co-MCM-48分子筛的合成与表征及其对临CO2乙烷脱氢反应的催化性能

 合成了Co-MCM-41和Co-MCM-48分子筛,并用X射线衍射、红外光谱和紫外-可见漫反射光谱等技术对样品进行了表征. 结果表明,部分Co离子掺杂进入了各分子筛的骨架中,在Co-MCM-41分子筛中只含有Co(Ⅱ),而在Co-MCM-48分子筛中只含有Co(Ⅲ). 分子筛中Co离子的价态不同是导致它们反应性能差异的根本原因.     

KIT-1介孔分子筛的化学修饰及吸附性能

介孔分子筛MCM-41具有较大、可调的孔径和较高的比表面积，其骨架组成具有较强的可调变性．为该材料的应用提供了很大的空间。但全硅MCM-41分子筛在潮湿空气中，即使在室温条件下也会发生水解反应，使其介孔结构遭到破坏。前人已针对MCM-41分子筛稳定性不足的问题相继合成了稳定性较高的介孔分子筛KIT-1,     

含钴介孔分子筛催化热解乙醇制备纳米碳管

以CTAB为模板剂,硅酸钠、氯化钴为原料,通过水热法合成含钴介孔分子筛(Co-MCM-41)。以所合成的Co-MCM-41做催化剂,采用化学气相沉积(CVD)法催化热解乙醇制备纳米碳管。通过XRD、FT-IR、TEM、N2吸附-脱附和Raman光谱等分析手段对所合成的介孔分子筛和纳米碳管进行了表征。结果表明:合成的Co-MCM-41样品具有MCM-41的介孔结构,比表面积较大且介孔有序性较好。以所合成的含钴介孔分子筛催化热解乙醇制备出管径均匀、管壁较厚、顶端开口的多壁纳米碳管。     

杂原子介孔Ce-MCM-41分子筛的制备及其吸附脱除甲硫醚性能

以十六烷基三甲基溴化铵为模板剂,正硅酸乙酯(TEOS)为硅源,硝酸铈为铈源,采用水热法合成了杂原子介孔分子筛Ce-MCM-41。XRD和FT-IR表征结果表明,当加入的Ce/Si物质的量比小于0.04时合成了规整有序的介孔结构,并将Ce原子引入到MCM-41骨架中。N₂吸附-脱附测试获得MCM-41和Ce-MCM-41(Ce/Si物质的量比为0.04)的平均孔径分别为2.82和2.46 nm,孔容分别为0.762 1和 0.689 4 m³/g,BET比表面积分别为986.42和756.8 m²/g。NH₃-TPD表征结果表明,Ce-MCM-41的酸性要明显强于MCM-41,但两种分子筛的酸性均较弱。利用合成的MCM-41和Ce-MCM-41吸附脱除甲硫醚浓度为58 μg(甲硫醚)/g的甲硫醚/氮气混合气中的甲硫醚。甲硫醚分子尺寸的模拟结果为0.464 8 nm,可以很容易地进入分子筛的介孔孔道中。由于Ce-MCM-41分子筛具有较多的酸量,其硫吸附容量7.52 mg(S)/g明显高于MCM-41的4.57 mg(S)/g。MCM-41和Ce-MCM-41都具有较好的再生性能,再生3次后硫吸附容量仍可恢复到初始容量的80%,分别为3.52和 5.86 mg(S)/g。     

介孔材料MCM-41的合成与性能表征

在水热条件下用新的合成控制手段得到孔壁较厚的MCM-41介孔分子筛材料,并采用XRD、N2吸附、TG-DTA、SEM和吡啶程序升温脱附等测试手段对合成的MCM-41样品进行表征,结果表明合成的介孔材料结晶度比较高,具有六方排列的孔道结构,孔径分布较窄,BET表面积较大,样品热稳定性高,吡啶-TPD谱图表明样品具有弱的或中等强度的酸性.用MCM-41作为活性组分制备成催化剂,进行微反活性实验,表明其裂化活性较低,但对柴油有较高的选择性.     

MCM-41分子筛担载纳米TiO2复合材料光催化降解罗丹明B

采用溶胶-凝胶法将TiO2担载在介孔MCM-41分子筛上, 制备了不同TiO2含量的系列TiO2/MCM-41复合材料, 利用X射线衍射、N2吸附、紫外-可见光谱和透射电镜等方法对其进行表征. TiO2的晶型为锐钛矿相, 复合材料的比表面积和孔体积随其中TiO2担载量(复合材料中TiO2与MCM-41的质量比)的增加而减小, TiO2的平均粒径随其担载量的增加而增大. 以罗丹明B的光催化降解为探针反应, 评价了TiO2/MCM-41复合材料的光催化降解活性. 结果表明, 在紫外光照射下, 罗丹明B在该复合材料上的光催化降解反应遵循一级反应动力学, 复合材料对罗丹明B的光催化降解活性明显高于商用TiO2 (P-25), 复合材料的光催化降解活性由复合材料的吸附能力和所含TiO2的光催化活性共同决定.     

AlMCM-41介孔分子筛的合成及表征

以拟薄水铝石为铝源、水玻璃为硅源、十六烷基三甲基溴化铵为模板剂,在110℃时水热晶化合成了含Al的MCM-41介孔分子筛.采用X射线衍射(XRD)、N2吸附-脱附、固体29Si、27Al魔角旋转核磁共振技术(MASNMR)、扫描电镜(SEM)及吡啶吸附傅里叶变换红外(FTIR)光谱技术对AlMCM-41分子筛进行了表征.结果表明:AlMCM-41分子筛具有六方排列的孔道结构,同时具有很高的相对结晶度、比表面积和孔容,且孔分布单一;AlMCM-41分子筛中Si原子在骨架内键合的程度更高,使AlMCM-41分子筛具有更好的骨架晶化程度;同时具有四配位骨架铝,使AlMCM-41介孔分子筛具有适当的酸性.     

Preparation and Optical Properties of (Nanometer MCM-41)-CdS Composite Materials

The nanometer and micrometer molecular sieves MCM-41 were prepared by a hydrothermal method. Cadmium (II) was exchanged into the molecular sieves by ion-exchange, and thioacetamide was then used as a precursor of hydrogen sulfide for sulphidizing the (MCM-41)-cadmium samples to prepare the host-guest composite materials (MCM-41)-CdS. By means of chemical analysis, powder X-ray diffraction, infrared spectroscopy, low temperature nitrogen adsorption-desorption technique, solid state diffuse reflectance absorption spectroscopy and luminescence, the prepared materials were characterized. The chemical analysis shows that the guest is successfully trapped in the molecular sieves. The powder X-ray diffraction suggests that the frameworks of the molecular sieves in the prepared host-guest composite materials are retained during the preparative process. They are intact and the degrees of crystallinity are still very high. The infrared spectra show that the frameworks of the prepared host-guest materials keep intact. The low temperature nitrogen adsorption-desorption studies indicate that the pore volumes, the pore sizes and the surface areas of the prepared composite materials decrease relative to those of the MCM-41 molecular sieve hosts. This shows that the guests are successfully encapsulated in the channels of the molecular sieves. The solid state diffuse reflectance absorption spectra of the prepared host-guest composites show some blue-shifts relative to that of bulk cadmium sulfide, indicating that the guests are trapped in the channels of the molecular sieves. This shows the obvious stereoscopic confinement effect of the molecular sieve host on the nanometer cadmium sulfide guest. The (nanometer MCM-41)-CdS and (micrometer MCM-41)-CdS samples show obvious luminescence.     

Pore curvature effect on the stability of Co-MCM-41 and the formation of size-controllable subnanometer Co clusters

Samples of Co-MCM-41 with different pore diameters have been synthesized using organic templates with different alkyl chain lengths. The reducibility of cobalt in these highly stable samples was investigated by TPR and X-ray absorption spectroscopy. We have found that the reducibility correlates strongly with the pore diameter of the MCM-41, with the cobalt incorporated in the smaller pore MCM-41 being more resistant to complete reduction. It is proposed that the distribution of cobalt ions in the pore wall is affected by both the preparation procedure and the pore diameter. The size of the metallic Co clusters formed after different reducing treatments correlates linearly with the pore size, giving direct evidence for the effect of the radius of curvature on reducibility. Complete cobalt reduction after TPR causes an inverse variation of the cluster size with the pore size, resulting from differences in the density of Co clusters and from differences in the rate of Co migration and aggregation outside the pores of MCM-41 with different pore sizes.     

Synthesis and characterization of highly ordered Ni-MCM-41 mesoporous molecular sieves

Highly ordered Ni-MCM-41 samples with nearly atomically dispersed nickel ions were prepared reproducibly and characterized. Similar to the Co-MCM-41 samples, the pore diameter and porosity can be precisely controlled by changing the synthesis surfactant chain length. Nickel was incorporated by isomorphous substitution of silicon in the MCM-41 silica framework, which makes the Ni-MCM-41 a physically stable catalyst in harsh reaction conditions such as CO disproportionation to single wall carbon nanotubes or CO2 methanation. X-ray absorption spectroscopy results indicate that the overall local environment of nickel in Ni-MCM-41 was a tetrahedral or distorted tetrahedral coordination with surrounding oxygen anions. Hydrogen TPR revealed that our Ni-MCM-41 samples have high stability against reduction; however, compared to Co-MCM-41, the Ni-MCM-41 has a lower reduction temperature, and both the H2-TPR and in situ XANES TPR reveal that the reducibility of nickel is not clearly correlated with the pore radius of curvature, as in the case of Co-MCM-41. This is probably a result of nickel being thermodynamically more easily reduced than cobalt. The stability of the structural order of Ni-MCM-41 has been investigated under SWNT synthesis and CO2 methanation reaction conditions as both require catalyst exposure to reducing environments leading to formation of metallic Ni clusters. Nitrogen physisorption and XRD results show that structural order was maintained under both SWNT synthesis and CO2 methanation reaction conditions. EXAFS results demonstrate that the nickel particle size can be controlled by different prereduction temperatures but not by the pore radius of curvature as in the case of Co-MCM-41.     

Pt/Si-MCM-41介孔结构对低温NO+H2+O2反应的影响

将Pt/Si-MCM-41用于H2选择催化还原(H2-SCR)消除NO的反应. X射线衍射分析、N2吸附/脱附、氢吸附和透射电镜等分析结果表明,介孔Si-MCM-41具有大的比表面积和孔体积有利于活性组分Pt的分散, Pt/Si-MCM-41催化剂在富氧和80000 h-1空速的条件下,其H2-SCR低温活性在100 ℃达到60.1%,优于Pt/Si-ZSM-5和Pt/SiO2催化剂,其选择性在120 可达70%. 当Si-MCM-41的介孔结构被破坏时,H2-SCR反应活性明显下降,最大活性在120 ℃仅为15%. 漫反射红外光谱(DRIFTS)测试表明, —NO3物种是Pt/Si-MCM-41催化剂在H2-SCR反应中的主要中间物种.