Perovskite nanocrystals are embedded into metal-organic frameworks (MOFs) to create composites with high light absorption coefficients, tunable electronic properties, high specific surface area, and metal atom tunability for enhanced photocatalytic carban dioxide (CO2 ) reduction. However, existing perovskite-MOF structures with a large particle size are achieved based on Pb source adsorption into the pores of MOFs, which can significantly break down the porous structure, thereby resulting in a decreased specific surface area and impacting CO2 adsorption. Herein, a novel perovskite-MOF structure based on the synthesis of bimetallic Pb-containing MOFs and post-processing to convert Pb to CsPbBr3 nanocrystals (NCs) is proposed. It is discovered that the additional Pb is not introduced by adsorption, but instead engages in coordination and generates Pb-N. The produced ZIF-8@CsPbBr3 NCs are ≈40 nm and have an ultra-high specific surface area of 1325.08 m2 g-1 , and excellent photovoltaic characteristics, which are beneficial for photocatalytic CO2 reduction. The electronic conversion rate of composites is 450 mol g-1 h-1 , which is more than three times that of pure perovskites. Additionally, the superior reduction capacity is sustained after undergoing four cycles. Density Functional Thoery (DFT) simulations are used to explore the 3D charge density at the ZIF-8@CsPbBr3 NCs interface to better understand the electrical structure.
Keywords: composites; density functional theory calculations; metal-organic frameworks; perovskite nanocrystals; photocatalytic CO2 reduction.
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