Direct use of metal–organic frameworks (MOFs) with robust pore structures, large surface areas, and high density of coordinatively unsaturated metal sites as electrochemical active materials is highly desirable (rather than using as templates and/or precursors for high‐temperature calcination), but this is practically hindered by the poor conductivity and low accessibility of active sites in the bulk form. Herein, a universal vapor‐phase method is reported to grow well‐aligned MOFs on conductive carbon cloth (CC) by using metal hydroxyl fluorides with diverse morphologies as self‐sacrificial templates. Specifically, by further partially on‐site generating active Co3S4 species from Co ions in the echinops‐like Co‐based MOF (EC‐MOF) through a controlled vulcanization approach, the resulting Co3S4/EC‐MOF hybrid exhibits much enhanced electrocatalytic performance toward the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), with overpotentials of 84 and 226 mV required to reach a current density of 10 mA cm−2, respectively. Density functional theory (DFT) calculations and experimental results reveal that the electron transfer between Co3S4 species and EC‐MOF can decrease the electron density of the Co d‐orbital, resulting in more electrocatalytically optimized adsorption properties for Co. This study will open up a new avenue for designing highly ordered MOF‐based surface active materials for various electrochemical energy applications.
The dehydrogenative aryl C-H/N-H cross-coupling is a powerful synthetic methodology to install nitrogen functionalities into aromatic compounds. Herein, we report an electrochemical oxidation induced intermolecular cross-coupling between aromatics and sulfonimides with high regioselectivity through N-radical addition pathway under external-oxidant-free and catalyst-free conditions. A wide variety of arenes, heteroarenes, alkenes and sulfonimides are applicable scaffolds in this transformation. In addition, aryl sulfonamides or amines (aniline derivatives) can be obtained through different deprotection process. The cyclic voltammetry mechanistic study indicates that the N-centered imidyl radicals are generated via proton-coupled electron transfer event jointly mediated by tetrabutylammonium acetate and anode oxidation process.
β-Fluorinated amine is highly desirable for biological
and
pharmaceutical science, because replacing a C–H bond with a
C–F bond can change the physical and chemical properties of
the parent molecule to a large extent but not significantly alter
its overall geometry. Herein, the highly stereoselective nucleophilic
monofluoromethylation of imines have been developed. It is proposed
that the chelated transition state enables the chiral induction by
the dynamic kinetic resolution of the chiral α-fluoro carbanions.
Two unprecedented and complementary synthetic strategies for S-and C-difluoromethylation of 2-substituted benzothiazoles have been developed by taking advantage of the remarkably different reactivity of CF 2 H − and 2-PySO 2 CF 2 − nucleophiles. A variety of structurally diverse difluoromethyl 2-isocyanophenyl sulfides and 2-difluoromethylated benzothiazoles were synthesized with these two new synthetic protocols.
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