Surface Functionalization of Ti₃C₂T_x MXene with Highly Reliable Superhydrophobic Protection for Volatile Organic Compounds Sensing

Two-dimensional (2D) transition-metal carbides (Ti3C2Tx MXene) have received a great deal of attention for potential use in gas sensing showing the highest sensitivity among 2D materials and good gas selectivity. However, one of the long-standing challenges of the MXenes is their poor stability against hydration and oxidation in a humid environment, limiting their long-term storage and applications. Integration of an effective protection layer with MXenes shows promise for overcoming this major drawback. Herein, we demonstrate a surface functionalization strategy for Ti3C2Tx with fluoroalkylsilane (FOTS) molecules through surface treatment, providing not only a superhydrophobic surface, mechanical/environmental stability but also enhanced sensing performance. The experimental results show that high sensitivity, good repeatability, long-term stability, and selectivity and faster response/recovery property were achieved by the FOTS-functionalized when Ti3C2Tx was integrated into chemoresistive sensors sensitive to oxygen-containing volatile organic compounds (ethanol, acetone). FOTS functionalization provided protection to sensing response when the dynamic response of the Ti3C2Tx-F sensor to 30 ppm of ethanol was measured over in the 5 to 80% relative humidity range. Density functional theory simulations suggested that the strong adsorption energy of ethanol on Ti3C2Tx-F and the local structure deformation induced by ethanol adsorption, contributing to the gas-sensing enhancement. This study offers a facile and practical solution for developing highly reliable MXene based gas-sensing devices with response that is stable in air and in the presence of water.