由于具有独特的孔道结构、高的热稳定性及适宜的酸性,丝光沸石(MOR)被广泛应用于正构烷烃异构化、二甲苯异构化、烷基化、甲苯歧化与烷基芳烃之间的烷基转移以及二甲醚羰基化反应中.但是其单一的微孔孔道结构在催化反应中带来严重的扩散限制,导致微孔内部活性位点利用率低和容易积碳失活等问题,同时也限制了MOR在大分子催化反应中的应用.在分子筛中引入介孔或减小晶粒尺寸是克服扩散限制的有效方法,也成为目前分子筛领域的研究热点.早期的研究中主要通过水蒸气处理、酸处理或碱处理等方法来制备多级孔MOR.但是,对于富铝的MOR,通常需要通过多步处理才能引入介孔.一步法直接制备多级孔MOR是目前的研究热点和难点.虽然文献报道可以采用自制的具有随机分子量分布的阳离子聚合物为模板剂和双亲有机硅表面活性剂OS-12制备多级孔MOR,但是合成的多级孔MOR为具有较窄a-b截面的纳米纤维或纳米棒状MOR,其12元环主孔道中的扩散限制没有得到有效改善.研究者采用N,N,N',N'-四乙基-外,外-二环[2.2.2]辛-7-烯-2,3：5,6-联四氢吡咯二碘铵盐和N,N,N,N',N',N'-六乙基-1,5-戊二胺阳离子为结构导向剂或者多季铵盐表面活性剂C18H37N+(Me)2C6H12N+(Me)2CH2C6H4CH2N+(Me)(C4H7CH2OH)为封端剂合成了具有三维纳米尺寸的MOR.然而这些纳米MOR的合成使用了结构复杂、价格昂贵的模板剂或表面活性剂.因此,开发简便、经济的MOR纳米晶合成路线仍是一个巨大挑战.本文通过在凝胶中添加少量四乙基氢氧化铵(TEAOH)和商业化表面活性剂,在低温下采用一步水热法成功制备了20–50 nm颗粒自组装的多级孔MOR (MOR-M),这是多级孔MOR合成中无c轴优势生长的首例报道.采用X射线衍射、X射线荧光光谱、扫描电镜、透射电镜、N2物理吸附、核磁共振、热重及NH3程序升温脱附等多种表征手段对合成样品的物理化学性质进行了研究.考察了合成参数对产物形貌和孔结构的影响,发现TEAOH的加入和较低的晶化温度是合成MOR-M的关键因素,而表面活性剂的作用则是进一步抑制晶粒的过度生长.仅添加双季铵盐表面活性剂C12-2-12时得到的为c轴优势生长的纳米片状多级孔MOR.与常规MOR相比, MOR-M具有较短的扩散路径、较大的外比表面积和丰富的介孔结构,在大分子苯和苯甲醇苄基化反应中表现出较常规MOR和具有更长c轴长度的纳米片状MOR更高的活性和目标产物选择性.在二甲醚羰基化制备乙酸甲酯的反应中, MOR-M亦表现出较高的活性及抗失活性能,积碳速率显著下降.
The present study reports a novel strategy to fabricate nanocrystal‐assembled hierarchical MOR zeolites. This is the first demonstration of hierarchical MOR without preferential growth along the c‐axis, which facilitates mass transfer in the 12‐membered ring channels of MOR zeolite for the conversions involving bulky molecules. The facile method involves the combined use of tetrae‐thylammonium hydroxide (TEAOH) and commercial surfactants, in which TEAOH is essential for the construction of nanocrystal assemblies. The surfactant serves as a crystal growth‐inhibiting agent to further inhibit nanocrystalline particle growth, resulting in enhanced mesoporosity. The hierarchical MOR assembled particles, constructed of 20–50‐nm crystallites, exhibit superior cata‐lytic properties in the alkylation of benzene with benzyl alcohol compared with the control sample, as the hierarchical MOR possesses a larger external surface area and longer c‐axis dimension. More importantly, the material shows improved activity and stability in the dimethyl ether carbonylation to methyl acetate reaction, which is a novel route to produce ethanol from syngas.
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