Kinetic Stability of MOF-5 in Humid Environments: Impact of Powder Densification, Humidity Level, and Exposure Time.

Metal-organic frameworks (MOFs) are an emerging class of microporous, crystalline materials with potential applications in the capture, storage, and separation of gases. Of the many known MOFs, MOF-5 has attracted considerable attention because of its ability to store gaseous fuels at low pressure with high densities. Nevertheless, MOF-5 and several other MOFs exhibit limited stability upon exposure to reactive species such as water. The present study quantifies the impact of humid air exposure on the properties of MOF-5 as a function of exposure time, humidity level, and morphology (i.e., powders vs pellets). Properties examined include hydrogen storage capacity, surface area, and crystallinity. Water adsorption/desorption isotherms are measured using a gravimetric technique; the first uptake exhibits a type V isotherm with a sudden increase in uptake at ∼50% relative humidity. For humidity levels below this threshold only minor degradation is observed for exposure times up to several hours, suggesting that MOF-5 is more stable than generally assumed under moderately humid conditions. In contrast, irreversible degradation occurs in a matter of minutes for exposures above the 50% threshold. Fourier transform infrared spectroscopy indicates that molecular and/or dissociated water is inserted into the skeletal framework after long exposure times. Densification into pellets can slow the degradation of MOF-5 significantly, and may present a pathway to enhance the stability of some MOFs.

Photoluminescence of n-type CdGeAs2.

Samples of n-type CdGeAs2 were produced by intentional doping with indium, selenium, or tellurium impurities. A near-edge photoluminescence (PL) band from heavily In-doped CdGeAs2 samples shifts to higher energy and becomes broader with increasing electron concentration. The observed shifts in peak energies are compared to predictions for donor-acceptor pair and free-to-bound (electron-acceptor) recombinations including band filling, band tailing, and band gap shrinkage effects due to the high doping levels. For n>2 × 1018 cm-3, the free-to-bound PL transition related to a shallow 120 meV acceptor level is dominant. A lower energy PL band due to deep acceptors and normally seen for p-type samples is the only emission observed from less n-type samples (n∼1016-1017 cm-3) doped with indium, selenium, or tellurium impurities. Transitions involving the deep acceptor level are not present in the PL for heavily In-doped CdGeAs2 crystals, which suggests that the deep acceptor may be a Cd vacancy.