Singlet oxygen (1 O2 ) is ubiquitously involved in various photocatalytic oxidation reactions; however, efficient and selective production of 1 O2 is still challenging. Herein, we reported the synthesis of nickel porphyrin-based covalent organic frameworks (COFs) incorporating functional groups with different electron-donating/-withdrawing features on their pore walls. These functional groups established a dedicated outer-sphere microenvironment surrounding the Ni catalytic center that tunes the activity of the COFs for 1 O2 -mediated thioether oxidation. With the increase of the electron-donating ability of functional groups, the modulated outer-sphere microenvironment turns on the catalytic activity from a yield of nearly zero by the cyano group functionalized COF to an excellent yield of 98 % by the methoxy group functionalized one. Electronic property investigation and density-functional theory (DFT) calculations suggested that the distinct excitonic behaviors attributed to the diverse band energy levels and orbital compositions are responsible for the different activities. This study represents the first regulation of generating reactive oxygen species (ROS) based on the strategy of outer-sphere microenvironment modulation in COFs.
The increasing demands of energy and environmental concerns have motivated researchers to cultivate renewable energy resources for replacing conventional fossil fuels. The modern energy conversion and storage devices required high efficient and stable electrocatalysts to fulfil the market demands. In previous years, we are witness for considerable developments of scientific attention in Metal-organic Frameworks (MOFs) and their derived nanomaterials in electrocatalysis. In current review article, we have discussed the progress of optimistic strategies and approaches for the manufacturing of MOF-derived functional materials and their presentation as electrocatalysts for significant energy related reactions. MOFs functioning as a self-sacrificing template bid different benefits for the preparation of metal nanostructures, metal oxides and carbon-abundant materials promoting through the porous structure, organic functionalities, abundance of metal sites and large surface area. Thorough study for the recent advancement in the MOF-derived materials, metal-coordinated N-doped carbons with single-atom active sites are emerging candidates for future commercial applications. However, there are some tasks that should be addressed, to attain improved, appreciative and controlled structural parameters for catalytic and chemical behavior.
Dinuclear Co-based catalysts are used for the coupling reaction of epoxides and CO2 in the presence of a cocatalyst. The easily recyclable catalysts efficiently complete the coupling of CO2 with various epoxides into industrially important cyclic carbonates at low catalyst loading and displayed high catalytic activity under relatively low CO2 pressure and solvent-free conditions. The maximum TON (168 600) and TOF (3333 h-1) obtained in this work are the highest among the reported Co-complexes.
