短10元环孔道片状垂直交错ZSM-5分子筛合成

引用本文: 展恩胜, 熊志平, 周燕, 李名润, 王鹏飞, 樊卫斌, 申文杰. 短10元环孔道片状垂直交错ZSM-5分子筛合成[J]. 催化学报, 2020, 41(7): 1132-1139. doi: 10.1016/S1872-2067(20)63573-2 shu

Citation: Ensheng Zhan, Zhiping Xiong, Yan Zhou, Mingrun Li, Pengfei Wang, Weibin Fan, Wenjie Shen. Perpendicular intergrowth ZSM-5 plates with shortened 10-MR pores[J]. Chinese Journal of Catalysis, 2020, 41(7): 1132-1139. doi: 10.1016/S1872-2067(20)63573-2 shu

短10元环孔道片状垂直交错ZSM-5分子筛合成

a 中国科学院大连化学物理研究所, 催化基础国家重点实验室, 辽宁大连 116023;
b 中国科学院山西煤炭化学研究所, 煤转化国家重点实验室, 山西太原 030001;
c 中国科学院大学, 北京 100049
基金项目:
国家自然科学基金（21773229）.

摘要: 分子筛酸性位位于其亚纳米孔道中,赋予其独特的择型催化特性,在烃类催化转化中有重要应用.但传统分子筛的晶体尺寸通常在微米尺度,因此狭长的孔道结构使得分子与活性位的接触受到扩散限制.通过控制分子筛晶体生长习性,选择性暴露分子筛孔道开口晶面,截短分子筛孔道长度,可以有效解决扩散问题.例如通过控制ZSM-5分子筛沿b轴的生长,合成了具有单晶胞层厚度(2 nm)的二维片层状分子筛,有效的促进了分子扩散、大大提高了其在甲醇转化中的寿命.但这类ZSM-5分子筛的合成需要使用特殊的多头季铵盐模版剂,且一般SiO2/Al2O3比大于100,不利于其实际应用推广.本文开发了一种使用简单有机胺模版剂(TEDA)合成片状垂直交错结构ZSM-5的新方法,并采用电子显微分析对所制ZSM-5分子筛晶体生长方向进行了表征,测试了其催化甲醇制汽油反应性能.
结果表明,所得ZSM-5具有良好的结晶性和典型微孔分子筛吸附特征,微孔表面积和微孔体积分别为251 m²/g和0.12cm³/g.电镜结果表明,其晶体结构特征为:一簇平行子片垂直生长于一个母片上的交错结构,母片呈现异于常见六边形MFI的八边形结构,大小约3-5 μm,子片大小约1-2 μm,子片和母片的厚度均约为100-200 nm.母片平行于MFI晶体的(010)平面,因此母片表面暴露直孔道开口,且其直孔道长度约100-200 nm.子片与母片连接处的选区电子衍射(电子束沿[010]方向入射)与母片的选区电子衍射完全一致,子片垂直于[100]方向,且子片相互间以平行方式排列,这些证据均说明子片在母片上的生长方式很可能是外延生长,而非粒子堆积机理.因此,子片平行于MFI的(100)晶面,表面暴露之字形孔道开口,且之字形孔道长度约100-200 nm.
进一步通过表征不同水热晶化时间的样品,研究了其可能的生长机制.结果表明,水热晶化72 h后,XRD图出现微弱的MFI晶体特征衍射峰,SEM显示有少量片状晶体生成,但无交错结构;晶化96 h后,XRD衍射峰增强,片状结构比例增加,且有交错结构出现;晶化120 h后,XRD呈现完美的MFI晶体衍射结构,SEM图显示均匀的交错片状结构.72和96 h的样品均为无定形物和片状(或交错片状)物共存,说明片状(或交错片状)结构的形成不是同步进行的;样品从开始结晶到完成结晶所需的时间较长,不同于分子筛结晶中常见的自催化结晶方式.我们推测,交错片状ZSM-5的形成发生在无定形物与溶液相界面处,遵循匀相成核机理.
该方法得到的ZSM-5分子筛SiO₂/Al₂O₃约为40,且固体核磁表明,ZSM-5中Al主要以骨架四配位形式存在,HZSM-5催化剂上四配位Al的比例高达95%以上,因此其骨架有丰富的酸性位.甲醇制汽油反应性能显示,在363℃,0.4 MPa条件下,甲醇转化量240 g时催化剂仍未失活,表现出典型纳米ZSM-5分子筛的高稳定性特征,这可能归结于片状ZSM-5具有短的(100-200 nm)直孔道或之字形孔道,可以有效促进反应物和产物的扩散,抑制积碳的生成.

关键词:

English

Perpendicular intergrowth ZSM-5 plates with shortened 10-MR pores

a State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China;
b State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, Shanxi, China;
c University of Chinese Academy of Sciences, Beijing 100049, China
Received Date: 11 November 2019
Fund Project:
This work was supported by the National Natural Science Foundation of China (21773229).

Abstract: ZSM-5 plates with a perpendicular intergrowth structure was synthesized by using a simple amine as the structure directing agent under hydrothermal conditions, in which the mother plate and the perpendicularly standing plates oriented along the (010) and (100) planes of MFI crystals, respectively. During the crystallization process, the mother plate was initially formed on the surface of the amorphous solid gel, while a set of parallel plates perpendicularly grew on its surface, via a homogeneous nucleation mechanism. The mother plate and the perpendicular plates had a similar thickness of 100-200 nm and were characterized by considerably shortened straight and zigzag 10 member ring pores, respectively. This unique intergrowth structure greatly facilitated the diffusion of the reactive molecules in HZSM-5 crystals during methanol conversion to hydrocarbons.

Key words:

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短10元环孔道片状垂直交错ZSM-5分子筛合成

English

Perpendicular intergrowth ZSM-5 plates with shortened 10-MR pores

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短10元环孔道片状垂直交错ZSM-5分子筛合成

English

Perpendicular intergrowth ZSM-5 plates with shortened 10-MR pores

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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