Molecular Engineering and Morphology Control of Covalent Organic Frameworks for Enhancing Activity of Metal-Enzyme Cascade Catalysis.

Metal-enzyme integrated catalysts (MEICs) that combine metal and enzyme offer great potential for sustainable chemoenzymatic cascade catalysis. However, rational design and construction of optimal microenvironments and accessible active sites for metal and enzyme in individual nanostructures are nec...

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Bibliographic Details
Published in:Advanced Science
Main Authors: Zhao, Hao, Zhang, Jialin, Liu, Yunting, Liu, Xinlong, Ma, Li, Zhou, Liya, Gao, Jing, Liu, Guanhua, Yue, Xiaoyang, Jiang, Yanjun
Format: Article in Journal/Newspaper
Language:English
Published: Wiley 2024
Subjects:
covalent organic framework
dynamic kinetic resolution
hollow structure
metal‐enzyme integrated catalysts
microenvironment modulation
Antarc*
Antarctica
Online Access:https://doi.org/10.1002/advs.202400730
https://pubmed.ncbi.nlm.nih.gov/38654621
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11220694/
Description
Summary:Metal-enzyme integrated catalysts (MEICs) that combine metal and enzyme offer great potential for sustainable chemoenzymatic cascade catalysis. However, rational design and construction of optimal microenvironments and accessible active sites for metal and enzyme in individual nanostructures are necessary but still challenging. Herein, Pd nanoparticles (NPs) and Candida antarctica lipase B (CALB) are co-immobilized into the pores and surfaces of covalent organic frameworks (COFs) with tunable functional groups, affording Pd/COF-X/CALB (X = ONa, OH, OMe) MEICs. This strategy can regulate the microenvironment around Pd NPs and CALB, and their interactions with substrates. As a result, the activity of the COF-based MEICs in catalyzing dynamic kinetic resolution of primary amines is enhanced and followed COF-OMe > COF-OH > COF-ONa. The experimental and simulation results demonstrated that functional groups of COFs modulated the conformation of CALB, the electronic states of Pd NPs, and the affinity of the integrated catalysts to the substrate, which contributed to the improvement of the catalytic activity of MEICs. Further, the MEICs are prepared using COF with hollow structure as support material, which increased accessible active sites and mass transfer efficiency, thus improving catalytic performance. This work provides a blueprint for rational design and preparation of highly active MEICs.

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