A Humidity‐Induced Large Electronic Conductivity Change of 107 on a Metal‐Organic Framework for Highly Sensitive Water Detection.

The electronic conductivity (EC) of metal–organic frameworks (MOFs) is sensitive to strongly oxidizing guest molecules. Water is a relatively mild species, however, the effect of H2O on the EC of MOFs is rarely reported. We explored the effect of H2O on the EC in the MOFs (NH2)2‐MIL‐125 and its derivatives with experimental and theoretical investigations. Unexpectedly, a large EC increase of 107 on H2SO4@(NH2)2‐MIL‐125 by H2O was observed. Brønsted acid–base pairs formed with the −NH2 groups, and H2SO4 played an important role in promoting the charge transfer from H2O to the MOF. Based on H2SO4@(NH2)2‐MIL‐125, a high‐performance chemiresistive humidity sensor was developed with the highest sensitivity, broadest detection range, and lowest limit of detection amongst all reported sensing materials to date. This work not only demonstrated that H2O can remarkably influence the EC of MOFs, but it also revealed that post‐modification of the structure of MOFs could enhance the influence of the guest molecule on their EC to design high‐performance sensing materials. [ABSTRACT FROM AUTHOR]