Optimization of Porphyrin-Based Metal-Organic Frameworks For Selective Oxidation of Organic Sulfides
Abstract
Porphyrin-based metal-organic frameworks (PMOFs) have been utilized as heterogeneous catalysts for the selective oxidation of organic sulfides. They have emerged as great candidates for catalysis due to their structure tunability, leading to a wide range of chemical properties and topologies. Previous studies primarily focused on using Zr MOFs for the photooxidation of organic sulfides due to their hydrothermal and chemical stability; however, PMOFs with other metal nodes are unexplored for this reaction. This work investigates PMOFs containing Al- (Al-PMOF), Ti- (DGIST-1), Y- (NUPF-2Y), and In- (InPMOF-bs-th) oxo nodes to understand the metal-node effect in the photooxidation of organic sulfides in solution and solvent-free conditions. A correlation between the reaction rate and metal node was observed, favoring nodes containing heavier metals such as indium and yttrium. The correlation between pore volume and sulfoxide selectivity also suggested a possible confinement effect inside PMOF structures, where smaller pores may restrict the generation of sulfone products. The Y-PMOF (NUPF-2Y) was the best-performing catalyst for sulfide oxidation in both organic solvents and under solvent-free conditions, exhibiting a half-life of 2.83 minutes (99 percent selectivity) in methanol and 3.93 minutes (94 percent selectivity) in acetonitrile. Under solvent-free conditions, the NUPF-2Y/textile composite with benzoic acid (BA) additive showed a half-life of 3.91 minutes (89 percent selectivity), making the NUPF2Y/BA/textile composite one of the best materials in its class for the selective oxidation of organic sulfide. This work demonstrates the potential of photoactive MOFs for the oxidation of organic sulfides. With an extensive catalog of ligands and metal nodes, structural optimization of MOFs can be performed to achieve the partial or complete oxidation of various organic sulfides.
Document Details
- Document Type
- Technical Report
- Publication Date
- Dec 16, 2022
- Accession Number
- AD1223851
Entities
People
- Juan C. Gomez
Organizations
- California State University, Los Angeles