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 = 1<i>H</i>-pyrazole, Tz = 1<i>H</i>-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