Tunable resistance of MOFs films via an anion exchange strategy for advanced gas sensing

Because of their ultra-high surface area, large porosity and excellent structural tailorability, metal-organic frameworks (MOFs) are considered as outstanding candidates among sensing materials for hazardous gas detection. However, most of MOFs-based sensing films show weak film adhesion and low conductivity due to the poor formation ability of MOFs films by traditional sensor fabrication methods as well as the intrinsic insulating character of these MOFs. In this work, we propose a novel strategy to directly grow robust gas-sensing films based on pristine MOFs arrays (ZIF-67 nanosheets) in-situ on the surface of ceramic substrates. To improve the conductivity of MOFs arrays, anion-exchange method is applied to couple Prussian blue analogue (PBA) on the surface of ZIF-67 arrays. Structural characterization revealed that this permutation reaction can significantly improve the conductivity of the MOF films while their sheet-like structures can be mainly remained. Benefiting from the robust structure and improved conductivity, the as-designed ZIF-67/PBA films exhibited superior sensing performances such as good reproducibility, high response value (R_g/R_a=11.7), and fast response/recovery speed (5/182 s) towards triethylamine. This work provides a new strategy to fabricate MOFs gas sensors and paves a new way to modulate the conductivity of MOF films.