A bifunctional zeolitic porous liquid with incompatible Lewis pairs for antagonistic cascade catalysis
A bifunctional zeolitic porous liquid with incompatible Lewis pairs for antagonistic cascade catalysis
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DOI：
10.1016/j.chempr.2021.08.022
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发表时间：
2021-12-09
期刊：
影响因子：
23.5
通讯作者：
Dai, Sheng
中科院分区：
文献类型：
--
作者：
Chen, Hao;Yang, Zhenzhen;Dai, Sheng
多孔液体（PLs）的出现为形成独特的拮抗体系提供了机会，这些拮抗体系能够在一锅中实现由不相容的活性位点促进的级联反应，这是催化领域的一个长期挑战性课题。在此，独特的双功能III型PL为基础的系统，方便地通过组装沸石纳米片与离子液体。通过合理的结构设计，得到了分子筛浓度高、2年后分散稳定、空穴分布丰富、拮抗基团（酸碱位）通过空间位阻控制和电子排斥调节以分离和活性形式参与的PL。这些独特的性质协同工作，实现了级联脱缩醛-Knoevenagel/Aldol缩合反应在一锅与上级催化效率优于传统系统。成功的关键在于形成双功能复合材料，通过表面改性将沸石从非均相转变为均相，以及通过刚性多孔结构确保快速传质。
The emergence of porous liquids (PLs) opened opportunities to form unique antagonistic systems capable of fulfilling cascade reactions promoted by incompatible active sites in one pot, which is a long-term challenging subject in catalysis. Herein, unique bifunctional type III PL-based systems were facilely fabricated via assembly of zeolite nanosheets with ionic liquids. Rational structural design afforded PLs that feature high zeolite concentration, stable dispersion after 2 years, abundant cavity distribution, and involvement of antagonistic groups (acid and base sites) in separated and active form via steric hindrance control and electronic repulsion regulation. These unique properties worked cooperatively to fulfill the cascade deacetalization-Knoevenagel/Aldol condensation in one pot with superior catalytic efficiency outperforming the traditional systems. The key to success lies in the formation of bifunctional composites, transformation of zeolite from heterogeneous to homogeneous via surface modification, and rapid mass transfer ensured by the rigid porous architecture.