3D Printing of Metal-Organic Framework-Based Ionogels: Wearable Sensors with Colorimetric and Mechanical Responses

Soft ionotronics are emerging materials as wearable sensors for monitoring physiological signals, sensing environmental hazards, and bridging the human-machine interface. However, the next generation of wearable sensors requires multiple sensing capabilities, mechanical toughness, and 3D printability. In this study, a metal-organic framework (MOF) and three-dimensional (3D) printing were integrated for the synthesis of a tough MOF-based ionogel (MIG) for colorimetric and mechanical sensing. The ink for 3D printing contained deep eutectic solvents (DESs), cellulose nanocrystals (CNCs), MOF crystals, and acrylamide. After printing, further photopolymerization resulted in a second covalently cross-linked poly(acrylamide) network and solidification of MIG. As a porphyrinic Zr-based MOF, MOF-525 served as a functional filler to provide sharp color changes when exposed to acidic compounds. Notably, MOF-525 crystals also provided another design space to tune the printability and mechanical strength of MIG. In addition, the printed MIG exhibited high stability in the air because of the low volatility of DESs. Thereafter, wearable auxetic materials comprising MIG with negative Poisson's ratios were prepared by 3D printing for the detection of mechanical deformation. The resulting auxetic sensor exhibited high sensitivity via the change in resistance upon mechanical deformation and a conformal contact with skins to monitor various human body movements. These results demonstrate a facile strategy for the construction of multifunctional sensors and the shaping of MOF-based composite materials.