Metal Nanoparticles@Covalent Organic Framework@Enzymes: A Universal Platform for Fabricating a Metal–Enzyme Integrated Nanocatalyst

Abstract

Cascade catalysis that combines chemical catalysis and biocatalysis has received extensive attention in recent years, especially the integration of metal nanoparticles (MNPs) with enzymes. However, the compatibility between MNPs and enzymes, and the stability of the integrated nanocatalyst should be improved to promote the application. Therefore, in this study, we proposed a strategy to space-separately co-immobilize MNPs and enzymes to the pores and surface of a highly stable covalent organic framework (COF), respectively. Typically, Pd NPs that were prepared by in situ reduction with triazinyl as the nucleation site were distributed in COF (Tz-Da), and organophosphorus hydrolase (OPH) was immobilized on the surface of Tz-Da by a covalent method to improve its stability. The obtained integrated nanocatalyst Pd@Tz-Da@OPH showed high catalytic efficiency and reusability in the cascade degradation of organophosphate nerve agents. Furthermore, the versatility of the preparation strategy of COF-based integrated nanocatalyst has been preliminarily expanded: (1) Pd NPs and OPH were immobilized in the triazinyl COF (TTB-DHBD) with different pore sizes for cascade degradation of organophosphate nerve agent and the particle size of MNPs can be regulated. (2) Pt NPs and glucose oxidase were immobilized in COF (Tz-Da) to obtain an integrated nanocatalyst for efficient colorimetric detection of phenol.

Metalated covalent organic frameworks: from synthetic strategies to diverse applications

“…Very recently, Pt@Tz-Da@GOx that was decorated by Pt nanoparticles and glucose oxidase was prepared by Jiang and co-workers via a stepwise post-treatment of the Tz-Da COF. 330 In a buffer solution at pH = 8, glucose oxidase converts glucose to gluconic acid and H 2 O 2 ; Pt subsequently catalyzes the reaction of phenol with the chromogenic substrate 4-aminoantipyrine in the presence of H 2 O 2 , causing the solution to turn red. The absorbance at 505 nm is linearly related to the phenol concentration in the range of 12.5-300 mM.…”

Research Progress on Lignocellulosic Biomass Degradation Catalyzed by Enzymatic Nanomaterials

“…Dendritic nanospheres have highly open mesoscopic channels, coenzymes, and corresponding enzymes that are successfully immobilized, and in situ heterogeneous regeneration of nicotinamide adenine dinucleotides is realized. In addition, metal nanoparticles, organophosphorus hydrolase, and glucose oxidase are immobilized on the pores and surfaces of a highly stable covalent organic skeleton (COF) [100] . The stability of the immobilized enzyme was improved and the immobilized enzyme showed high catalytic efficiency and reuse performance.…”

“…In addition, metal nanoparticles, organophosphorus hydrolase, and glucose oxidase are immobilized on the pores and surfaces of a highly stable covalent organic skeleton (COF). [100] The stability of the immobilized enzyme was improved and the immobilized enzyme showed high catalytic efficiency and reuse performance. Zuhair et al [101] studied the immobilization of lipase to biodiesel by ZIF-67 (gradient mesoporous molecular sieve), ZIF-8, and HKUS-1 (mesoporous molecular sieve).…”

Enzyme-Graphene Nanometal biohybrid Architectures as Highly Efficient Multifunctional Catalysts for Cascade Reactions

“…A very fancy approach combining metal nanoparticles with enzymes in the same solid material has been described for chemoenzymatic cascade processes. [30][31][32][33] A recent technology developed by our group has allowed to synthesize nanobiohybrid systems at room temperature in aqueous media where stable, smallsized, monodispersed metallic nanoparticles are in situ synthesized induced by an enzyme scaffold. [34][35][36][37][38][39] In comparison with other methods where metal nanoparticles are directly support on the solid phase, in this strategy enzyme acts a key role in the in situ synthesis of the nanoparticles, controlling their growth (being able to produce nanoparticles with very small size) and morphology.…”