This study investigates how the microenvironment of water confined between layers of Ti₃C₂Tₓ MXene is influenced by the intercalation of different cations. Using Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), and resistivity measurements, the researchers explore how cation intercalation affects the hydrogen bonding and structural properties of water in the MXene interlayer space. The results show that the nature of the aqueous microenvironment is strongly dependent on the type of cation intercalated. For example, cations such as Li⁺, Na⁺, and Mg²⁺, which are more strongly hydrated, lead to stronger hydrogen bonding in the water molecules, while cations like K⁺ and Cs⁺, which are less hydrated, result in weaker hydrogen bonding. The study also reveals that the interlayer spacing of the MXene increases with humidity, and this change is influenced by the type of cation present. The resistivity of the MXene films is also affected by the intercalated cations, with higher resistivity observed for cations that lead to stronger hydrogen bonding. The findings demonstrate that cation intercalation can be used to tune the microenvironment of water in MXene interlayers, which has implications for the electrochemical performance of MXene-based materials in energy storage and catalytic applications. The study highlights the importance of understanding the interaction between cations and water in confined spaces, as this can significantly influence the behavior of electrochemical systems.This study investigates how the microenvironment of water confined between layers of Ti₃C₂Tₓ MXene is influenced by the intercalation of different cations. Using Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), and resistivity measurements, the researchers explore how cation intercalation affects the hydrogen bonding and structural properties of water in the MXene interlayer space. The results show that the nature of the aqueous microenvironment is strongly dependent on the type of cation intercalated. For example, cations such as Li⁺, Na⁺, and Mg²⁺, which are more strongly hydrated, lead to stronger hydrogen bonding in the water molecules, while cations like K⁺ and Cs⁺, which are less hydrated, result in weaker hydrogen bonding. The study also reveals that the interlayer spacing of the MXene increases with humidity, and this change is influenced by the type of cation present. The resistivity of the MXene films is also affected by the intercalated cations, with higher resistivity observed for cations that lead to stronger hydrogen bonding. The findings demonstrate that cation intercalation can be used to tune the microenvironment of water in MXene interlayers, which has implications for the electrochemical performance of MXene-based materials in energy storage and catalytic applications. The study highlights the importance of understanding the interaction between cations and water in confined spaces, as this can significantly influence the behavior of electrochemical systems.