Thermal-Response Proton Conduction in Schiff Base-Incorporated Metal-Organic Framework Hybrid Membranes under Low Humidity Based on the Excited-State Intramolecular Proton Transfer Mechanism

Stimulus-responsive proton conduction materials have attracted enormous interest as a new kind of "smart material". It is desirable to develop the appropriate stimulus signal and high proton-conducting materials with an excellent proton-conducting switch ratio (gamma), but it remains a great challenge. Here, it can be found for the first time that 4-((2-hydroxybenzylidene)amino)-benzenesulfonic acid (HBABSA) has obvious thermal isomer-ization when porous solids act as matrixes at the ambient temperatures, which is different from that in the crystalline state at 77 K. Therefore, we proposed a host-guest metal-organic framework (MOF) composite, namely, MOF-808 incorporated with HBABSA (HBABSA@MOF-808), which has a proton -conducting switch ratio (gamma) of 16 between 338 and 343 K due to the thermally induced isomerization of HBABSA molecules in the MOF pores. The strong binding between the keto-type HBABSA and MOF at the relatively low temperatures can efficiently suppress the proton conduction, while the enol-type one provides more mobile protons for conduction at the high temperatures due to the excited-state intramolecular proton transfer mechanism. Further, the HBABSA@MOF-808 as a filler is blended into polyvinyl alcohol and poly(2-acrylamide-2-methyl-1-propane sulfonic acid) to form hybrid membranes. The hybrid membrane with the highest content of the MOF composite displays a high proton conductivity of 5.57 x 10-3 S center dot cm-1 under 353 K and 57% RH along with a good switch ratio of 5.4. The development of thermal-response proton-conducting MOF materials is opening up a unique pathway for remote control, thermal sensing, intelligent batteries, and other fields.