Ultrasensitive ion liquid-CNT vdW heterostructure interface via anion-cation pair switch for SO2 detection

Low dimensional van der Waals (vdW) interface shows great advantages for application in vapor detection, such as ultra-high sensitivity and excellent reversibility. However, detection of non-character REDOX capacity and low atmosphere concentration gas such as SO2 is more challengeable. Inspired by the high efficient gas adsorption performance and versatile ion pair combination of ionic liquids, we constructed a vdW heterostructure interface based polymeric ion liquid/SWCNT sensor with different ionic pairs for SO2 detection. Via the composites tuning of SWCNTs and poly(vinylbenzyl 3-ethylimidazolium)-based ionic liquids (PILs) modified with different anions of chloride (Cl-), boron tetrafluoride (BF4-), hexafluorophosphate (PF6-), and bis(trifluoromethanesulfonimide) ions (Tf2N-), stable vdW heterostructure interface was successfully constructed, as proved by SEM, FTIR, XPS and Raman spectra. Upon SO2 adsorption, the distance between the cation/anion was tuned at the heterostructure interface, which triggered great composite tightness changes and thus electrical signal changes of heterostructure interface due to the reversed electron transfer, proved by XPS, Raman spectra and dynamics simulations. Among the sensors composed of the different anions, PIL-BF4-SWCNT exhibited lowest detection limit 20.4 ppt for SO2, which is the best result ever reported. The sensor also show great selectivity, reversibility and stability, with 3.77% response for 512 ppt SO2 within 14 days. The new strategy will open a new way for selective, ultrasensitive and low power vapor detection in complex environment.