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Fixing the greenhouse gas CO2 through epoxide helps to mitigate worldwide ecological troubles. The applications of metal‐free and solvent‐free catalysts remain a challenge for CO2 catalytic conversion. In this work, an array of quaternary ammonium salts derived from polyethyleneimine with hydroxyl groups ([PEI‐GDMAB‐Cn]Br) were constructed by the reaction of branched PEI with a molecular weight of 10000 and glycidyl alkyl dimethylammonium bromide. A range of experiments were designed to demonstrate that [PEI‐GDMAB‐Cn]Br can be considered as a valid metal‐free and solvent‐free homogeneous catalyst for the CO2‐epoxide cycloaddition reaction. Among of [PEI‐GDMAB‐Cn]Br, [PEI‐GDMAB‐C18]Br catalyzed the model reaction of CO2 and epichlorohydrin under optimized reaction conditions (T=80 °C, 1.0 atm CO2, catalyst 1 mol%, ECH 15 mmol, 16 h) and the conversion achieved at 97.5 %. Moreover, the catalyst exhibited stable reusability and broad substrate applicability, which was used in the following cycle succinctly, because of self‐separated properties by temperature control. The [PEI‐GDMAB‐C18]Br catalyzed reaction process was detected as a pseudo‐first‐order reaction after kinetic studies and an Ea was calculated to be 50.65 kJ/mol. A combinatorial catalytic mechanism of hydrogen bonding and bromide ions is suggested to explain the remarkable catalytic performance of this bifunctional catalyst. [ABSTRACT FROM AUTHOR]

Low humidity detection has been a great challenge in the field of humidity sensing. In recent years, polyelectrolytes have been proven to be promising materials for highly sensitive humidity sensors. In this work, cross-linked poly(ionic liquid)s (PILs) were prepared for low humidity detection. The strong hydrophilicity of PILs contributes to humidity sensing while the cross-linked structure guarantees the stability of the sensing film. The optimized sensor shows high response (48.0) in 5–35% RH, with short response/recovery time (1 s/10 s) and a small humidity hysteresis (0.2% RH). The possible sensing mechanism of the sensors was discussed. • Cross-linked poly(ionic liquid)s were used as low humidity sensitive materials. • The optimized sensor shows high response in 5–35% RH. • The optimized sensor has short recovery time and small humidity hysteresis. • The introduction of glycerol could reduce the impedance of the sensor. [ABSTRACT FROM AUTHOR]