The study investigates the impact of cation intercalation on the microenvironment of water confined within Ti3C2Tx MXene, a two-dimensional transition metal carbide. Using Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and four-point probe measurements, the researchers examine how different cations (K+, Cs+, Na+, Li+, Mg2+) affect the hydrogen bonding of water molecules and the electrical properties of the MXene films. The results show that the nature of the cation significantly influences the amount and type of water confined between the MXene layers. Chaotropic cations (K+, Cs+) reduce the amount of water and prevent the formation of a water bilayer, while kosmotropic cations (Li+, Na+, Mg2+) increase the water content and can form a bilayer at higher humidities. The changes in water content correlate with variations in the interlayer spacing and resistivity, highlighting the potential for tuning the microenvironment to enhance electrochemical performance.The study investigates the impact of cation intercalation on the microenvironment of water confined within Ti3C2Tx MXene, a two-dimensional transition metal carbide. Using Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and four-point probe measurements, the researchers examine how different cations (K+, Cs+, Na+, Li+, Mg2+) affect the hydrogen bonding of water molecules and the electrical properties of the MXene films. The results show that the nature of the cation significantly influences the amount and type of water confined between the MXene layers. Chaotropic cations (K+, Cs+) reduce the amount of water and prevent the formation of a water bilayer, while kosmotropic cations (Li+, Na+, Mg2+) increase the water content and can form a bilayer at higher humidities. The changes in water content correlate with variations in the interlayer spacing and resistivity, highlighting the potential for tuning the microenvironment to enhance electrochemical performance.