High Proton Conductivity and Spectroscopic Investigations of Metal–Organic Framework Materials Impregnated by Strong Acids

Strong toluenesulfonic and triflic acids were incorporated into a MIL-101 chromium(III) terephthalate coordination framework, producing hybrid proton-conducting solid electrolytes. These acid@MIL hybrid materials possess stable crystalline structures that do not deteriorate during multiple measurements or prolonged heating. Particularly, the triflic-containing compound demonstrates the highest 0.08 S cm(-1) proton conductivity at 15% relative humidity and a temperature of 60 °C, exceeding any of today's commercial materials for proton-exchange membranes. The structure of the proton-conducting media, as well as the long-range proton-transfer mechanics, was unveiled, in a certain respect, by Fourier transform infrared and (1)H NMR spectroscopy investigations. The acidic media presumably constitutes large separated droplets, coexisting in the MIL nanocages. One component of proton transfer appears to be related to the facile relay (Grotthuss) mechanism through extensive hydrogen-bonding interactions within such droplets. The second component occurs during continuous reorganization of the droplets, thus ensuring long-range proton transfer along the porous structure of the material.