Adsorption and diffusion in thin films of nanoporous metal-organic frameworks: ferrocene in SURMOF Cu2(ndc)2(dabco)

Phys Chem Chem Phys. 2013 Jun 21;15(23):9295-9. doi: 10.1039/c3cp50578b. Epub 2013 May 9.

Abstract

The adsorption and diffusion of ferrocene (FC) in thin MOF films of type Cu2(ndc)2(dabco) were studied by X-ray diffraction and using a quartz-crystal microbalance (QCM) at different temperatures. A quantitative analysis of the uptake curves in the QCM during loading with FC from the gas phase yields 0.19 FC compounds per pore at a temperature of 305 K and of 0.06 at 335 K, respectively. From an analysis of this temperature dependence we obtain an adsorption enthalpy of -30 kJ mol(-1). A quantitative analysis of the time dependence of the QCM uptake curves yields very small diffusivities on the order of 10(-19) to 10(-17) m(2) s(-1), while the activation energy for diffusion amounts to +90 kJ mol(-1). These results show that using a quartz crystal microbalance for uptake studies in SURMOFs is a valuable tool for investigating very slowly diffusing compounds in nanoporous materials.