Lamellar Nanocomposite Based on a 1D Crayfish-like Ce^III-Substituted Phospho(III)tungstate Semiconductor and Polyaniline Used as a High-Performance Humidity Sensing Device

In order to meet people's demand for intelligent management of daily life and health, manufacturing and developing humidity monitoring equipment with convenience, high sensitivity, easy miniaturization, and low cost is particularly important in the era of rapid development of artificial intelligence and the Internet of Things. Polyaniline (PANI) is an attractive humidity sensing material due to its designable functional properties. However, PANI modified polyoxometalates (POMs) for humidity sensing are still rare. As a proof of concept, a novel moisture sensing composite material was obtained based on PANI and a novel 1D rare-earth-substituted phospho(III)tungstate [H₂N(CH₃)₂]₉Na₃H₆[Ce₂(H₂O)₃W₅O₁₃(C₂O₄)][HP^IIIW₉O₃₃]₂[(HP^III)₂W₁₅O₅₄]·42H₂O (1). Notably, the anion structure of 1 contains trivacant Keggin-type [B-α-HP^IIIW₉O₃₃]^8- and Dawson-like [(HP^III)₂W₁₅O₅₄]^10- subunits linked by a heterometallic [Ce₂(H₂O)₃W₅O₃₂(C₂O₄)]^30- cluster. Furthermore, the 1/PANI composite shows a typical semiconductive characteristic with a "band-like" conductive mechanism. The fabricated 1/PANI-based humidity sensing device exhibits a broad sensing range (11∼97% relative humidity), fast response/recovery time (3.45 s/3.24 s), good repeatability, and long-term stability (over 3 months). Additionally, the possible sensing mechanism is proposed. This work offers an enormous possibility for the design of high-performance humidity sensing materials through POM material chemistry.