CsCu₂I₃ Nanoparticles Incorporated within a Mesoporous Metal-Organic Porphyrin Framework as a Catalyst for One-Pot Click Cycloaddition and Oxidation/Knoevenagel Tandem Reaction.

ABSTRACT: Metal-organic frameworks (MOFs) and metal halide perovskites are currently under much investigation due to their unique properties and applications. Herein, an innovative strategy has been developed combining an iron-porphyrin MOF, PCN-222(Fe), and an in situ-grown CsCu₂I₃ nontoxic lead-free halide perovskite based on an earth-abundant metal that becomes incorporated within the MOF channels [CsCu₂I₃@PCN-222(Fe)]. Encapsulation was designed to decrease and control the particle size and increase the stability of CsCu₂I₃. The hybrid materials were characterized by various techniques including FE-SEM, elemental mapping and line scanning EDX, TEM, PXRD, UV-Vis DRS, BET surface area, XPS, and photoemission measurements. Hybrid CsCu₂I₃@PCN-222(Fe) materials were examined as heterogeneous multifunctional (photo)catalysts for copper(I)-catalyzed alkyne-azide cycloaddition (CuAAC) and one-pot selective photo-oxidation/Knoevenagel condensation cascade reaction. Interestingly, CsCu₂I₃@PCN-222(Fe) outperforms not only its individual components CsCu₂I₃ and PCN-222(Fe) but also other reported (photo)catalysts for these transformations. This is attributed to cooperation and synergistic effects of the PCN-222(Fe) host and CsCu₂I₃ nanocrystals. To understand the catalytic and photocatalytic mechanisms, control and inhibition experiments, electron paramagnetic resonance (EPR) measurements, and time-resolved phosphorescence were performed, revealing the main role of active species of Cu(I) in the click reaction and the superoxide ion (O₂^•-) and singlet oxygen (¹O₂) in the photocatalytic reaction.

SUBMITTER: Daliran S 

PROVIDER: S-EPMC9940116 | biostudies-literature | 2022 Aug

REPOSITORIES: biostudies-literature