Encapsulating perovskite quantum dots into 3D COF for visible light-driven CO2 reduction
摘要
Lead halide perovskite quantum dots (LHP QDs) have been revealed to possess great potential in photocatalytic applications including CO2 reduction, which however suffer from poor stability. Herein, a high crystalline hydrazine-linked three-dimensional (3D) covalent organic framework, USTB-17, was fabricated from the reaction between 12-connected building block and 4-connected 3,5,7-tetrakis(4-aldophenyl)-adamantane. Post-modification with Ni2+ affords the metallic framework USTB-17(Ni) followed by sequential deposition of the CH3NH2PbI3 (MAPbI3) perovskite QDs into its pores, generating the USTB-17(Ni)@MAPbI3 composite. Powder X-ray diffraction analysis together with theoretical simulations and transmission electron microscopy discloses the crystalline nature of USTB-17, USTB-17(Ni), and USTB-17(Ni)@MAPbI3 with an unprecedented non-interpenetrated hpt topology. The close contact of QDs inside the COF pores with the Ni catalytic site locating at the pore surface of COF allows a rapid transfer of the photogenerated electrons in QDs to the Ni catalytic sites, enhancing the photocatalytic activity for CO2 reduction. This endows USTB-17(Ni)@MAPbI3 with efficient photocatalysis performance for photocatalytic CO2 reduction with CO generation rate of 365 µmol g−1 h−1 and CO selectivity up to 96% under visible-light irradiation, 7 times higher than that of USTB-17(Ni). After four cycles of reactions, the photocatalytic CO generation rate remains almost unchanged, demonstrating its excellent cycle stability.