A CuI Cluster‐Based Covalent Metal‐Organic Framework as a Photocatalyst for Efficient Visible‐Light‐Driven Reduction of CO2. Issue 6 (30th January 2023)

• Record Type: Journal Article
• Authors: Cui, Jinxian; Fu, Yaomei; Song, Jian; Meng, Bo; Zhou, Jie; Zhou, Ziyan; Su, Zhongmin
• Is Part Of: ChemSusChem. Volume 16:Issue 6(2023)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2023-01-30
• Subjects: CO2 valorization -- copper -- metal-organic frameworks, photocatalysis -- reduction; Green chemistry -- Periodicals; Sustainable engineering -- Periodicals; Chemistry -- Periodicals; Chemical engineering -- Periodicals; 660
• DOI: 10.1002/cssc.202202079
• Languages: English
• ISSNs: 1864-5631

Abstract

Abstract: The application of solar energy to convert CO2 into high‐value chemicals and fuels has been considered a highly desirable approach to relieving the greenhouse effect and energy crisis. However, the exploration of appropriate photocatalysts remains a major challenge. Combining the respective advantages of covalent organic frameworks and metal−organic frameworks to construct covalent metal−organic frameworks (CMOFs) can be a valid strategy to provide efficient, reliable, and eco‐friendly photocatalysts. In this study, a Cu I cluster‐based CMOF (JNM‐2) is used as a photocatalyst for CO2 photoreduction under visible‐light irradiation. JNM‐2 exhibits remarkable efficiency in photocatalytic CO2 reduction with high production rates of HCOOH (9019 μmol g −1 h −1 ) and CO (835 μmol g −1 h −1 ). The active center, reaction intermediates, and product generation pathways are elucidated by in situ DRIFTS and DFT calculations. This work demonstrates the tremendous possibilities of CMOFs as photocatalysts for CO2 reduction and provides profound insights into the mechanism of CO2 conversion into HCOOH/CO by using a molecularly accurate structural model. Abstract : CMOF it : A Cu I cluster‐based covalent metal‐organic framework is used for photocatalytic conversion of CO2 into HCOOH under visible‐light illumination. The catalytic active site, reaction intermediates, product formation pathways and CO2 photoreduction mechanism are investigated in depth by a combination of in situ diffuse‐reflectance infrared Fourier transform spectroscopy and density functional theory.