Highly Selective Chloromethanes Detection Based on Quartz Crystal Microbalance Gas Sensors with Ba-MOFs

Three new metal-organic frameworks (MOFs), {(CH₃NH₃)₃[Ba₂(TTHA)(NO₃)(H₂O)₂]}·2H₂O (1), {(CH₃NH₃)₄[Ba₃(HTTHA)₂(H₂O)₇]}·3H₂O (2), and [Ba₇(TTHA)₂(NO₃)₂(H₂O)₁₀]·2H₂O (3) (H₆TTHA = 1,3,5-triazine-2,4,6-triamineh-exaacetic acid) have been synthesized and characterized. The sensing properties of 1-3 were explored with regard to volatile organic compounds (VOCs) by the quartz crystal microbalance (QCM) technique. The results indicated that 1 and 2 have a much higher selectivity and response to chloromethanes (CH₂Cl₂, CHCl₃, and CCl₄) compared with H₂O, CH₃OH, CH₃CH₂OH, CH₃CN, (CH₃)₂CO, C₆H₆, C₆H₅CH₃, C₆H₅CH₂CH₃, and C₆H₅Cl at room temperature. Furthermore, 1 and 2 sensing film also exhibits excellent reversibility and stability, and the response and recovery times are almost within 10 s. 3 displays a lower response and poor selectivity to the above VOCs. The significant difference may be caused by their different structural characteristics. The Ba²⁺ ions are all decacoordinated in 1 and 2, while Ba²⁺ ions have more open metal sites in 3. So, the high selectivity and response of 1 and 2 may be due to the exchange of coordination water molecules with chloromethanes and possible electrostatic effects between (CH₃NH₃)⁺ cations and chloromethanes containing more electronegative Cl atoms. DFT calculation results show that the bond energy of Ba-Cl and Ba-O is not much different, so chloromethanes at high concentrations may exchange coordination water to form weak Ba···Cl interactions and show higher response values. 3 has no obvious VOCs selectivity and higher response due to more open sites of Ba²⁺ ions and smaller pore size. This work develops a fast and effective method to detect chloromethanes, providing a new opportunity for designing QCM gas sensors coated with different MOF materials.