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Abstract The detection of methane is important for industry, environment, and our daily life, but is made challenging by its small size, high volatility, and nonpolar nature. Herein, a tungsten‐capped calix[4]arene‐basedp‐doped conducting polymer with hexafluorophosphate or perchlorate counter‐anions as a transducer is used to detect methane in dry air. The host–guest interaction between calixarene moieties within the polymer chain and methane molecules leads to the resistance variation of the polymer. The experimental limit of detection (LoD) of methane for the polymer‐based sensor is demonstrated to be less than 50 ppm at room temperature, and the extrapolated theoretical LoD of 2 ppm represents exceptional sensitivity to methane. Furthermore, the discrimination of methane from interfering volatile organic compounds is achieved by exploiting a sensor array using complementary chemiresistors and principal component analysis.more » « less
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Abstract Fluid‐like sliding graphenes but with solid‐like out‐of‐plane compressive rigidity offer unique opportunities for achieving unusual physical and chemical properties for next‐generation interfacial technologies. Of particular interest in the present study are graphenes with specific chemical functionalization that can predictably promote adhesion and wetting to substrate and ultralow frictional sliding structures. Lubricity between stainless steel (SS) and diamond‐like carbon (DLC) is experimentally demonstrated with densely functionalized graphenes displaying dynamic intersheet bonds that mechanically transform into stable tribolayers. The macroscopic lubricity evolves through the formation of a thin film of an interconnected graphene matrix that provides a coefficient of friction (COF) of 0.01. Mechanical sliding generates complex folded graphene structures wherein equilibrated covalent chemical linkages impart rigidity and stability to the films examined in macroscopic friction tests. This new approach to frictional reduction has broad implications for manufacturing, transportation, and aerospace.more » « less
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Abstract In contemporary organic synthesis, substances that access strongly oxidizing and/or reducing states upon irradiation have been exploited to facilitate powerful and unprecedented transformations. However, the implementation of light-driven reactions in large-scale processes remains uncommon, limited by the lack of general technologies for the immobilization, separation, and reuse of these diverse catalysts. Here, we report a new class of photoactive organic polymers that combine the flexibility of small-molecule dyes with the operational advantages and recyclability of solid-phase catalysts. The solubility of these polymers in select non-polar organic solvents supports their facile processing into a wide range of heterogeneous modalities. The active sites, embedded within porous microstructures, display elevated reactivity, further enhanced by the mobility of excited states and charged species within the polymers. The independent tunability of the physical and photochemical properties of these materials affords a convenient, generalizable platform for the metamorphosis of modern photoredox catalysts into active heterogeneous equivalents.more » « less
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