Achieving Superprotonic Conduction in Metal-Organic Frameworks through Iterative Design Advances.

Two complementary design strategies, isomorphous ligand replacement and heterocycle doping, have been applied to iteratively enhance the proton conductivity of a metal-organic framework, β-PCMOF2. The resulting materials, PCMOF21/2(Pz) and PCMOF21/2(Tz) (Pz = 1H-pyrazole, Tz = 1H-1,2,4-triazole), have their proton conduction raised almost 2 orders of magnitude compared to β-PCMOF2. The bulk conductivities of these materials are over 10-1 S cm-1 at 85 °C and 90% relative humidity (RH), while maintaining the parent MOF structure. A solid state synthetic route for doping 1-D channels is also presented.