COF-inspired fabrication of two-dimensional polyoxometalate based open frameworks for biomimetic catalysis

The development of highly efficient and robust biomimetic catalysts is an essential and feasible strategy to overcome the intrinsic drawbacks of natural enzymes. Inspired by the synthetic strategy of covalent organic frameworks, we adopted a covalent-bond-driven strategy to prepare polyoxometalate (POM) based open frameworks (NKPOM-OFs = Nankai University POM-OFs) with abundant Mo&z.dbd;O groups that can mimic the active center of sulfite oxidase. Four 2-dimensional (2D) NKPOM-OFs were designed and synthesized via the condensation reaction of linear amino-containing POMs with planar tetra-aldehyde monomers. Benefitting from the high crystallinity, the structures of 2D POM-OFs can be successfully determined from structural simulations. The results unveiled that NKPOM-OFs possessed 2D staggered stacking layered structures with the sql topology. All these NKPOM-OFs exhibited high crystallinity and stability and demonstrated outstanding performance to serve as biomimetic catalysts of sulfite oxidase with good recyclability. Notably, exfoliation of NKPOM-OFs under ultrasonic treatment can significantly boost the catalytic activity with almost two times faster reaction rates. This study not only enriches the facile and versatile synthesis strategy for POM-OFs but also provides new biomimetic platforms for biocatalysis. The development of highly efficient and robust biomimetic catalysts is an essential and feasible strategy to overcome the intrinsic drawbacks of natural enzymes.