高等学校化学学报 ›› 1997, Vol. 18 ›› Issue (4): 519.

• 论文 • 上一篇    下一篇

合成温度对中孔分子筛M41S材料结构转变的影响──不同结构材料的表征

陈晓银, 丁国忠, 陈海鹰, 李全芝   

  1. 复旦大学化学系, 上海, 200433
  • 收稿日期:1996-04-08 出版日期:1997-05-24 发布日期:1997-05-24
  • 通讯作者: 李全芝.
  • 作者简介:陈晓银, 男, 33岁, 博士后.
  • 基金资助:

    国家自然科学基金;中国博士后科学基金

Effect of Synthesis Temperature on Structural Transformation of Mesoporous Molecular Sieve M41S Materials──Characterization of Different Structural Materials

CHEN Xiao-Yin, DING Guo-Zhong, CHEN Hai-Ying, LI Quan-Zhi   

  1. Department of Chemistry, Fudan University, Shanghai, 200433
  • Received:1996-04-08 Online:1997-05-24 Published:1997-05-24

摘要: 分别用氮气吸附-脱附测定、激光傅立叶红外(FTIR)、29Si和37Al固态魔角核磁共振(MASNMR)和微分热重(DTG)等手段表征了低表面活性剂浓度及低表面活性剂与硅原子摩尔比的十六烷基三甲基溴化钦与硅酸钠体系中不同温度形成的不同中孔M41S和微孔ZSM-5沸石.研究发现,合成温度从100℃提高至135℃,MCM-41的固体颗粒变细,孔壁厚增加而中孔表面积和体积降低.合成温度从135℃提高至150℃,由热稳定的六角相转化形成的层状M41S层间移去表面活性剂后,层面倒塌而失去中孔结构,红外骨架谱中出现双环振动谱带,同时层板硅羟基相互凝聚导致29SiMASNMR港失去精细结构.合成温度再提高至≥165℃,骨架硅羟基高度凝聚,Q3/Q4比大为降低,红外光谱中双环振动峰增强且位移至548cm-1,层状M41S转化为ZSM-5沸石.DTG结果显示,不同结构的分子筛的形成来自于在不同温度下CTMAB与硅酸根物种间的不同相互作用.

关键词: 中孔六角MCM-41, 中孔层状M41S, 微孔ZSM-5沸石, 结构表征

Abstract: For the synthesis system containing cetyltrimethylammonium bromide and sodiumsilicate at low surfactant concentrations and low Sur/Si ratio, the pore and local unit structures of mesoporous M4lSand microporous zeolite ZSM-5, which are obtained in the samesystem at different synthesis temperatures, have been characterized by means 0f N, adsorption-desorption measurments, FTIR, 29Si and 27Al MAS NMRand DTG-The experimentalresults indicate that when synthesis temperature increases from 100℃ to 135℃, the sizes ofmaterials are governed by small crystallites, the pore wall thickness increases but the mesoporous surface areas as well as the volume of materials decrease.When synthesis temperature increases from 135℃ to 150℃, the layers of lamellar M4lSmaterial, obtained fromhexagonal MCM-41 collapse and mesoporous structure disappears due to the removal of thesurfactants by calcination, which are in agreement with experimental findings of XRD.Meanwhile, the double ring vibration band near 598 cm-1 appears in the FTIRspectra.Thesilanols between layers are condensed, resulting in the loss of fine structure in29Si MASNMRspectra.When further increasing synthesis temperature to 165℃, the silanols of framework are highly condensed, resulting in the decrease of Q3/Q4 ratlo greatly.The intensity of double ring vibration band increases and its vibration position shifts to 548 cm-1.Thus, the lamellar M4lSis transformed to zeolite ZSM-5.The DTGresults suggest that theformations of different materials result from the different interactions between surfactantsand silicate species under different temperatures.

Key words: Mesoporous hexagonal MCM-41, Mesoporous lamellar M41S, Microporous zeolite ZSM-5, Structural characterization

TrendMD: