Insights in the Ionic Conduction inside Nanoporous Metal-Organic Frameworks by Using an Appropriate Equivalent Circuit

The conduction of protons and other ions in nanoporous materials, such as metal-organic frameworks (MOFs), is intensively explored with the aim of enhancing the performance of energy-related electrochemical systems. The ionic conductivity, as a key property of the material, is typically determined by using electrochemical impedance spectroscopy (EIS) in connection with a suitable equivalent circuit. Often, equivalent circuits are used where the physical meaning of each component is debatable. Here, we present an equivalent circuit for the ionic conduction of electrolytes in nanoporous, nonconducting materials between inert and impermeable electrodes without faradaic electrode reactions. We show the equivalent circuit perfectly describes the impedance spectra measured for the ion conduction in MOFs in the form of powders pressed into pellets as well as for MOF thin films. This is demonstrated for the ionic conduction of an aprotic ionic liquid, and of various protic solvents in different MOF structures. Due to the clear physical meaning of each element of the equivalent circuit, further insights into the electrical double layer forming at the MOF-electrode interface can be obtained. As a result, EIS combined with the appropriate reference circuit allows us to make statements of the quality of the MOF-substrate interface of different MOF-film samples.

Negative linear compressibility in nanoporous metal-organic frameworks rationalized by the empty channel structural mechanism

Cobalt squarate hydroxide (Co3(C4O4)2(OH)2), zinc squarate tetrahydrate (ZnC4O4·4 H2O) and titanium oxalate trioxide dihydrate (Ti2(C2O4)O3·2 H2O) are nanoporous metal-organic frameworks possessing empty channels in their crystal structures. The crystal structures...