Facile Preparation of Fluoroalkyl End-Capped Vinyltrimethoxysilane Oligomer/Sand Composites Possessing Superoleophilic/Superhydrophobic Characteristic: Application to Oil/Water Separation and Selective Removal of Fluorinated Aromatic Compounds from Aqueous Methanol Solution

Fluoroalkyl end-capped vinyltrimethoxysilane oligomer [RF-(CH2-CHSi(OMe)3)n-RF: n = 2, 3, RF = CF(CF3)OC3F7: RF-(VM)n-RF], was applied to the facile preparation of the corresponding oligomer/sand (Ottawa sand: OS) composites [RF-(VM-SiO3/2)n-RF/OS] through the sol-gel reaction of the oligomer in the presence of micro-sized OS particles (590 - 840 μm) under alkaline conditions at room temperature. FE-SEM (Field Emission Scanning Electron Micrograph) images showed that the obtained composites consist of the RF-(VM-SiO3/2)n-RF oligomeric nanoparticles and the micro-sized OS particles. Interestingly, the RF-(VM-SiO3/2)n-RF/OS composites thus obtained can provide the superoleophilic/superhydrophobic characteristic on the composite surface, applying to the separation of not only the mixture of oil/water but also the W/O emulsion to isolate the transparent colorless oil. The fluorinated oligomeric OS composites were also found to be applicable to the selective removal of fluorinated aromatic compounds from an aqueous methanol solution. Especially, it was demonstrated that the fluorinated OS composites can supply a higher efficient and smooth separation ability for the separation of the mixture of oil and water than that of the corresponding fluorinated micro-sized controlled silica gel (μ-SiO2) composites (average particle size: 9.5 μm), which were prepared under similar conditions. In addition to the separation of oil/water, the fluorinated OS composites provided higher and more selective removal ability for the fluorinated aromatic compounds from aqueous solutions than that of the μ-SiO2 composites.

Metal-Free,Site-Selective C-H Fluorination of Heteroarenes Under Visible Light

The site-selective C-H fluorination of heteroarenes is a straightforward approach to accessing valuable heteroaryl fluorides but remains a formidable challenge.Herein,we report a general strategy for visible-light-induced C-H fluorination of heteroarenes via the merger of N-F fluorinating reagents and silane.Electron paramagnetic resonance experiments provide evidence for the homolytic cleavage of the N-F bond under blue light-emitting diode irradiation,which is the key step in the process.This transformation is metal-free,photocatalysts-free,and site-selective under mild reaction conditions(ambient temperature,visible-light irradiation,tolerant to H2O).The robustness of this protocol has also been highlighted by late-stage modification of complex and medicinally relevant molecules.