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 (γ), 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 isomerization 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 (γ) 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 × 10 -3 S·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.