A porous metal-organic framework (MOF), [Ni2(dobdc)(H 2O)2] 6H2O (Ni2(dobdc) or Ni-MOF-74; dobdc4-=2,5-dioxido-1,4-benzenedicarboxylate) with hexagonal channels was synthesized using a microwave-assisted solvothermal reaction. Soaking Ni2(dobdc) in sulfuric acid solutions at different pH values afforded new proton-conducting frameworks, H+@Ni2(dobdc). At pH1.8, the acidified MOF shows proton conductivity of 2.2×10 -2Scm-1 at 80°C and 95% relative humidity (RH), approaching the highest values reported for MOFs. Proton conduction occurs via the Grotthuss mechanism with a significantly low activation energy as compared to other proton-conducting MOFs. Protonated water clusters within the pores of H+@Ni2(dobdc) play an important role in the conduction process.
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