Li Gen, Hu Yunqi, Liu Zhaojun, Sha Yanlei, Zhao Chenyang, Liu Honghai, Fan Xinye, Wan Pingyu, Zhao Hongjuan, Liu Hongtao
State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, P. R. China.
Petrochemical Research Institute, Petrochina Company Limited, Beijing 100195, P. R. China.
Langmuir. 2025 Jul 22;41(28):18895-18902. doi: 10.1021/acs.langmuir.5c02498. Epub 2025 Jul 11.
The introduction of mesoporosity is of great importance because mass-transportation limitations within microporous systems hinder their catalytic performance. The direct formation of mesoporosity in zeolite is generally achieved through the use of an additional and expensive organic template, which limits its industrial applications. In this investigation, we reported a facile procedure for synthesizing zeolite Beta with micromesoporosity, in which tetraethylammonium hydroxide (TEAOH)/crystal seeds (CS) worked as the micropore-directing agents, assisted by simple citric acid (CA) containing hydroxyl carboxylic groups. The working mechanism of TEAOH/CS/CA was proposed on the basis of various characterization methods. Oxalic acid was employed as an additional template to further elucidate the formation mechanism of the mesopores. The formation mechanism is proposed that CA with hydroxyl carboxylic groups can interact with aluminosilicate and TEAOH simultaneously to form a semimicelle, leading to the final mesostructure. The resultant mesoporous material was tested in the esterification reaction of benzyl alcohol and acetic acid. Improved activity and selectivity were observed as a result of the introduction of intracrystalline mesopores, suggesting the superiority of the CA-assisted zeolite Beta. This novel procedure provides a simple procedure for obtaining zeolite Beta with hierarchical pores, which can enable the economic and environmentally friendly production of hierarchical zeolites for industrial applications.
介孔的引入非常重要,因为微孔体系内的传质限制会阻碍其催化性能。沸石中介孔的直接形成通常通过使用额外的昂贵有机模板来实现,这限制了其工业应用。在本研究中,我们报道了一种合成具有微介孔的β沸石的简便方法,其中氢氧化四乙铵(TEAOH)/晶种(CS)作为微孔导向剂,并由含有羟基羧酸基团的简单柠檬酸(CA)辅助。基于各种表征方法提出了TEAOH/CS/CA的作用机制。使用草酸作为额外的模板来进一步阐明介孔的形成机制。提出的形成机制是,具有羟基羧酸基团的CA可以同时与铝硅酸盐和TEAOH相互作用形成半胶束,从而导致最终的介观结构。将所得的介孔材料用于苄醇和乙酸的酯化反应测试。由于晶内介孔的引入,观察到活性和选择性得到提高,这表明CA辅助的β沸石具有优越性。这种新颖的方法为获得具有分级孔道的β沸石提供了一种简单的方法,这能够实现用于工业应用的分级沸石的经济且环境友好的生产。