胆碱和<sup>*</sup>BEA分子筛在硅锗铝IWR分子筛制备中的协同导向效应

引用本文: 付文华, 袁志庆, 金少青, 刘巍, 王振东, 王传明, 王仰东, 杨为民, 何鸣元. 胆碱和^*BEA分子筛在硅锗铝IWR分子筛制备中的协同导向效应[J]. 催化学报, 2019, 40(6): 856-866. doi: S1872-2067(19)63324-3 shu

Citation: Wenhua Fu, Zhiqing Yuan, Shaoqing Jin, Wei Liu, Zhendong Wang, Chuanming Wang, Yangdong Wang, Weimin Yang, Ming-Yuan He. Cooperative structure-directing effect of choline cation and ^*BEA zeolite in the synthesis of aluminogermanosilicate IWR zeolite[J]. Chinese Journal of Catalysis, 2019, 40(6): 856-866. doi: S1872-2067(19)63324-3 shu

胆碱和^*BEA分子筛在硅锗铝IWR分子筛制备中的协同导向效应

a 中国石化上海石油化工研究院, 绿色化工与工业催化国家重点实验室, 上海 201208;
b 华东师范大学化工与分子工程, 上海市绿色化学与化工过程绿色化重点实验室, 上海 200062
基金项目:
国家重点研发计划（2017YFB0702800）；国家自然科学基金（21802168，21503280，21603277）；中国石化集团.

摘要: 分子筛的制备过程一般需要结构导向剂的参与.结构导向剂主要包括碱（土）金属离子、有机胺或季铵盐为代表的有机模板剂和固体晶种等三类.研究合成凝胶中不同结构导向剂之间的作用对于理解分子筛晶化机理意义重大.以往的研究大都集中在模板剂-模板剂、模板剂-碱（土）金属离子和模板剂-同晶之间的相互作用，迄今尚未有模板剂-异晶之间相互作用研究的报道.
我们研究组首次发现模板剂和异晶在分子筛制备中存在协同导向效应.在硅锗铝IWR分子筛的合成中，我们考察了不同的季铵碱模板剂和铝源，发现只有使用胆碱作模板剂、^*BEA分子筛作铝源才可以成功制得目标分子筛，相同条件下不加入^*BEA分子筛或换用MOR、ZSM-5、MCM-22、USY分子筛及异丙醇铝等铝源都无法合成得到IWR分子筛.这说明^*BEA分子筛在IWR分子筛的制备中起到了其他铝源所不具备的结构导向作用，因此我们称之为合成IWR分子筛的“异晶”.
为了研究胆碱和^*BEA分子筛之间的相互作用，进而揭示模板剂-异晶协同导向制备分子筛的一般规律与反应机理，我们制备了不同晶化时间的IWR分子筛样品，使用X射线粉末衍射（XRD）、扫描电子显微镜（SEM）、紫外-拉曼光谱（UV-Raman）、固体核磁共振（MAS NMR）和N₂物理吸附等手段对这些样品进行了表征.结果显示，加热过程中^*BEA分子筛首先发生溶解解离，72h后该分子筛相完全消失；12h开始出现CDO分子筛相，随着晶化时间延长，CDO分子筛先增多后减少，在24h时达到最大值，120h时消失，说明该分子筛是晶化过程的一个中间相；IWR分子筛在12h开始出现，此后结晶度不断升高，至168h晶化完全.
在上述表征的基础上，我们提出了模板剂-异晶协同导向制备IWR分子筛的晶化机理.IWR分子筛的晶化分为以下5个步骤：（1）^*BEA分子筛溶解解离得到硅铝4元环、5元环和6元环等结构单元；（2）胆碱诱导形成硅锗5元环结构单元；（3）硅锗5元环组装生成CDO分子筛；（4） CDO分子筛溶解解离形成硅锗5元环；（5）^*BEA分子筛导向的结构单元与胆碱导向的结构单元重组生成IWR分子筛.其中，步骤3和4是一对可逆反应，且可与步骤5同时进行；随着反应物原料的不断消耗，步骤5占据主导，从而导致CDO分子筛完全消失和IWR分子筛的结晶完成.由于胆碱只导向生成5元环结构单元，而构成IWR分子筛骨架结构的4元环和6元环只能由^*BEA分子筛提供，因而模板剂和异晶在反应中都不可或缺，二者起到协同导向的作用.分析发现，^*BEA分子筛与IWR分子筛具有共同的结构单元（4、5、6元环）和一定的结构相似性是其可以成为异晶、发挥协同导向作用的关键.
上述协同导向法的关键在于模板剂和异晶分别导向生成部分结构单元，再经重组得到目标分子筛.这种方法有望用于合成通过传统水热法难以得到的分子筛，并且为新结构分子筛的开发提供新思路.使用协同导向法制备更多种类分子筛的研究正在进行中.

关键词:

English

Cooperative structure-directing effect of choline cation and ^*BEA zeolite in the synthesis of aluminogermanosilicate IWR zeolite

a State Key Laboratory of Green Chemical Engineering and Industrial Catalysis, Sinopec Shanghai Research Institute of Petrochemical Technology, Shanghai 201208, China;
b Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, China
Received Date: 07 January 2019
Revised Date: 26 January 2019
Fund Project:
This work was supported by the National Key R&

Abstract: In this contribution, we report the cooperative structure-directing effect of choline hydroxide and aluminosilicate ^*BEA zeolite in the synthesis of aluminogermanosilicate IWR zeolites for the first time. ^*BEA zeolites, at variance with any other aluminosilicate zeolites, can serve as heterogeneous seeds for the growth of IWR zeolites and play a cooperative structure-directing role. The crystallization process was investigated using multiple techniques to characterize a series of solid products obtained with various crystallization times. The experiments clearly showed the dissolution of the ^*BEA zeolite and of an intermediate CDO-type structure. A plausible mechanism for the novel cooperative synthesis has been proposed. The crystallization of the IWR zeolite involves several steps, among which the crucial one is believed to be the reassembly of the building units produced from the decomposition of ^*BEA zeolite seeds, induced by choline molecules. Having similar structure and common building units (four-, five-, and six-membered rings) with the IWR zeolite, the ^*BEA zeolite is capable of promoting the reassembly of the building units and can thus play a cooperative structure-directing role. By highlighting the cooperative structure-directing effect of organic molecules and heterogeneous seeds, this study opens up new perspectives for the synthesis of target zeolites that are difficult to prepare by traditional methods. This new synthetic route is also expected to shed light on the discovery of novel zeolites.

Key words:

IWR zeolite
/ Cooperative structure-directing effect
/ Organic structure-directing agent
/ Choline cation
/ Heterogeneous seeds
/ ^*BEA zeolite

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沈阳化工大学材料科学与工程学院沈阳 110142

胆碱和^*BEA分子筛在硅锗铝IWR分子筛制备中的协同导向效应

English

Cooperative structure-directing effect of choline cation and ^*BEA zeolite in the synthesis of aluminogermanosilicate IWR zeolite

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中国化学会秘书处

胆碱和*BEA分子筛在硅锗铝IWR分子筛制备中的协同导向效应

English

Cooperative structure-directing effect of choline cation and *BEA zeolite in the synthesis of aluminogermanosilicate IWR zeolite

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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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

胆碱和^*BEA分子筛在硅锗铝IWR分子筛制备中的协同导向效应

Cooperative structure-directing effect of choline cation and ^*BEA zeolite in the synthesis of aluminogermanosilicate IWR zeolite

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs