Humidity-Independent Artificial Olfactory Array Enabled by Hydrophobic Core–Shell Dye/MOFs@COFs Composites for Plant Disease Diagnosis

As a class of important artificial olfactory system, the colorimetric sensor array possesses great potential for commercialization due to its cost-effectiveness and portability. However, when applied to practical applications, the humidity interference from ambient environment and dissatisfactory sensitivity for trace target VOCs are largely unsolved problems. To overcome the problems, we developed a series of dye/MOFs@COFs gas-sensing materials with core–shell structure using a hydrophobization strategy by encapsulation of dye/metal–organic frameworks (MOFs) into hydrophobic covalent organic frameworks (COFs). Benefiting from the hydrophobic property of the COF shell, the dye/MOFs@COFs composites were endowed with excellent humidity-resistance even under 100% relative humidity (RH). Moreover, due to the uniform distribution of dyes on the porous MOFs, the dye/MOFs@COFs sensors also exhibited improved sensitivity at the sub-ppm level, compared with conventional dye sensors. On basis of the excellent humidity-resistance and improved sensitivity, an artificial olfactory array based on dye/MOFs@COFs composites was proven to be a successful practical application in early and accurate detection of wheat scab (1 day after inoculation) by monitoring its released VOC markers. The synthetic strategy for core–shell dye/MOFs@COFs is applicable to a wide range of colorimetric sensor arrays, endowing them with excellent humidity-resistance and sensitivity for the feasibility of practical applications.