Takaoka Kohei, Matsuno Takamichi, Koike Masakazu, Muramoto Naho, Wada Hiroaki, Kuroda Kazuyuki, Shimojima Atsushi
Department of Applied Chemistry, Faculty of Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku-ku, Tokyo, 169-8555, Japan.
Kagami Memorial Research Institute for Materials Science and Technology, Waseda University, 2-8-26 Nishiwaseda, Shinjuku-ku, Tokyo, 169-0051, Japan.
Small. 2025 Feb;21(5):e2405280. doi: 10.1002/smll.202405280. Epub 2024 Oct 11.
The synthesis of mesoporous zeolites has garnered attention with regard to improving their catalytic and adsorption performances. While the hard-templating method provides opportunities to design precisely controlled hierarchical micro- and mesoporous structures, synthesizing mesoporous zeolites without external precipitation requires significant work. This is mainly due to the absence of usable templates other than carbon with hydrophobic surfaces. Herein, it is demonstrated that the CoO template is valuable in preparing mesoporous silicalite-1 and ZSM-5 with a precisely controlled porous structure through hydrothermal synthesis. Unlike conventional carbon templates, the CoO template is relatively hydrophilic, effective in suppressing external precipitation, and is reusable by dissolving in an acidic solution. The crystallization process also differs from that of the carbon template, as the silicate precipitates on a 3D ordered nanoporous CoO scaffold, followed by crystallization and crystal growth. Furthermore, it is unexpectedly observed that the zeolite crystallization is accelerated in the CoO template. The synthetic approach utilizing nanoporous metal oxides opens new doors for the control of the hierarchical structure of zeolites, as well as for the design of metal oxide-zeolite nanocomposite catalysts, due to the potential extensibility of the combination of metal oxides and zeolites.
介孔沸石的合成因其催化和吸附性能的提升而备受关注。虽然硬模板法为设计精确可控的分级微孔和介孔结构提供了机会,但在不产生外部沉淀的情况下合成介孔沸石仍需大量工作。这主要是由于除了具有疏水表面的碳之外,缺乏可用的模板。在此,证明了CoO模板在通过水热合成制备具有精确可控多孔结构的介孔硅沸石-1和ZSM-5方面具有价值。与传统的碳模板不同,CoO模板具有相对亲水性,能有效抑制外部沉淀,并且可通过溶解在酸性溶液中重复使用。结晶过程也与碳模板不同,因为硅酸盐在三维有序纳米多孔CoO支架上沉淀,随后进行结晶和晶体生长。此外,意外地观察到在CoO模板中沸石结晶加速。由于金属氧化物和沸石组合具有潜在的可扩展性,利用纳米多孔金属氧化物的合成方法为控制沸石的分级结构以及设计金属氧化物-沸石纳米复合催化剂打开了新的大门。