A Cerium‐Naphthazarin Catecholate MOF as a Heterogeneous Photocatalyst for Selective Functionalization of Alkanes
Abstract
Abstract In this work, we have successfully synthesized a series of novel semiconducting 2D catecholate metal‐organic frameworks (MOFs) based on naphthazarin ligands by utilizing unraveled metal‐acetyl acetonate linkage chemistry. The synthesized MOFs exhibited excellent light absorption properties and chemical stability across various solvents. Its insoluble and stable framework, combined with an optimal band gap, enabled its use as a photocatalyst for organic transformations. For the first time, Ce‐Naph MOF is explored as a heterogeneous catalyst for photocatalytic applications specifically for the selective C–H amination of alkanes, achieving yields of up to 89% under ambient conditions. We propose that the initial metal‐to‐ligand charge transfer in Ce‐Naph MOF, promoted by light, is essential for forming an active alkoxy‐Ce(IV)‐species. This species subsequently undergoes ligand‐to‐metal charge transfer to generate the alkoxy radical, which acts as a hydrogen atom transfer reagent to activate alkanes. Furthermore, Ce‐Naph MOF demonstrated long‐term cyclic stability, maintaining its catalytic activity and structural integrity over five cycles, highlighting its durability as a heterogeneous catalyst. We are confident that this straightforward and practical methodology opens new avenues for industrial applications, significantly advancing the fields of metal catalysis, photocatalysis, and sustainable chemistry.
Article Details
Authors (12)
Sharath Kandambeth
Physical Science and Engineering Division
Rajesh Kancherla
KAUST Catalysis Center (KCC) King Abdullah University of Science and Technology (KAUST) Thuwal Saudi Arabia
Kuntal Pal
KAUST Catalysis Center (KCC) King Abdullah University of Science and Technology (KAUST) Thuwal Saudi Arabia
Taslim Melliti
Functional Materials Design Discovery, and Development (FMD3) Research Group Physical Science and Engineering Division King Abdullah University of Science and Technology (KAUST) Thuwal 23955‐6900 Saudi Arabia
Mostafa Zeama
Functional Materials Design Discovery, and Development (FMD3) Research Group Physical Science and Engineering Division King Abdullah University of Science and Technology (KAUST) Thuwal 23955‐6900 Saudi Arabia
Vinayak S. Kale
Functional Materials Design Discovery, and Development (FMD3) Research Group Physical Science and Engineering Division King Abdullah University of Science and Technology (KAUST) Thuwal 23955‐6900 Saudi Arabia
Issatay Nadinov
Abdulaziz M. Alali
Functional Materials Design Discovery, and Development (FMD3) Research Group Physical Science and Engineering Division King Abdullah University of Science and Technology (KAUST) Thuwal 23955‐6900 Saudi Arabia
Osama Shekhah
Functional Materials Design, Discovery, and Development Research Group (FMD3), Physical Science and Engineering Division
Omar F. Mohammed
Center of Excellence for Renewable Energy and Storage Technologies, Division of Physical Science and Engineering
Magnus Rueping
Division of Physical Sciences and Engineering
Mohamed Eddaoudi