Ionic Liquid Droplet Microreactor for Catalysis Reactions Not at Equilibrium
Ionic Liquid Droplet Microreactor for Catalysis Reactions Not at Equilibrium
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用于非平衡催化反应的离子液滴微反应器
DOI：
10.1021/jacs.7b07731
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发表时间：
2017
影响因子：
15
通讯作者：
Yang Hengquan
中科院分区：
文献类型：
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作者：
Zhang Ming;Ettelaie Rammile;Yan Tao;Zhang Suojiang;Cheng Fangqin;Binks Bernard P;Yang Hengquan
我们开发了一种新的策略，更有效地和可控的过程连续酶或均相催化反应的基础上非水皮克林乳液。该策略的一个关键要素是通过在柱反应器中的油中填充含有催化剂的微米尺寸的离子液体（IL）液滴来“自下而上”构建大规模连续流动反应系统。由于反应物连续流入液滴微反应器和产物从液滴微反应器中连续释放，在这样的系统中可以进行催化反应，而没有常规间歇反应中固有的由反应平衡的建立和催化剂分离引起的限制。作为概念的证明，使用该基于IL液滴的流动系统的酶促对映选择性酯交换反应和CuI催化的环加成反应与它们的批处理对应物相比都表现出催化效率的8至25倍增强，并且对于1-苯乙醇的对映选择性酯交换反应具有至少4000小时的耐久性，否则在它们的批处理对应物中无法获得。我们进一步建立了非平衡条件下催化体系的理论模型，不仅支持了实验结果，而且有助于在微观水平上预测反应过程。由于操作简单、高效和适应性强，该策略为酶和均相催化剂的实际应用提供了一个前所未有的平台，即使是在可控的水平上。
We develop a novel strategy to more effectively and controllably process continuous enzymatic or homogeneous catalysis reactions based on nonaqueous Pickering emulsions. A key element of this strategy is “bottom-up” construction of a macroscale continuous flow reaction system through packing catalyst-containing micron-sized ionic liquid (IL) droplet in oil in a column reactor. Due to the continuous influx of reactants into the droplet microreactors and the continuous release of products from the droplet microreactors, catalysis reactions in such a system can take place without limitations arising from establishment of the reaction equilibrium and catalyst separation, inherent in conventional batch reactions. As proof of the concept, enzymatic enantioselective trans-esterification and CuI-catalyzed cycloaddition reactions using this IL droplet-based flow system both exhibit 8 to 25-fold enhancement in catalysis efficiency compared to their batch counterparts, and a durability of at least 4000 h for the enantioselective trans-esterification of 1-phenylethyl alcohol, otherwise unattainable in their batch counterparts. We further establish a theoretical model for such a catalysis system working under nonequilibrium conditions, which not only supports the experimental results but also helps to predict reaction progress at a microscale level. Being operationally simple, efficient, and adaptive, this strategy provides an unprecedented platform for practical applications of enzymes and homogeneous catalysts even at a controllable level.