Polyoxometalates coupled covalent organic frameworks as highly active photothermal nanoreactor for CO2 cycloaddition

作者：Tian Wang, Yunqing Zhu, Wei Wang, Junfeng Niu, Zhiyi Lu, Peilei He · 发表于：Nano Research · 年份：2024 · DOI：10.1007/s12274-024-6626-1 · 被引用次数：38 · 研究领域：Covalent Organic Framework Applications、Carbon dioxide utilization in catalysis、CO2 Reduction Techniques and Catalysts

Covalent organic frameworks (COFs)-based nanoreactors have attracted broad interest in many fields due to their void-confinement effects. However, the inherent drawback of conventional nanoreactors is the lack of internal active sites, which limits their widespread utilization. Herein, we report the construction of hierarchical COF (EB-TFP) nanoreactor with pre-synthesized polyoxometalates (POM, [PV2W10O40]5− (PV2W10)) clusters encapsulated inside of COF (POM@COF). PV2W10@EB-TFP anchors nucleophilic-group (Br− ions) and PV2W10 anion cluster within the COF framework via electrostatic interactions, which not only simplifies the reaction system but also enhances catalytic efficiency. The reaction performance of the PV2W10@EB-TFP nanoreactor can be tuned to achieve excellent catalytic activity in CO2 cycloaddition reaction (CCR) for ∼ 97.63% conversion and ∼ 100% selectivity under visible light irradiation. A mechanistic study based on density functional theory (DFT) calculations and in-situ characterization was also carried out. In summary, we have reported a method for achieving the uniform dispersion of POM single clusters into COF nanoreactor, demonstrating the potential of POM@COF nanoreactor for synergistic photothermal catalytic CO2 cycloaddition.