Langmuir, Vol.27, No.23, 14169-14179, 2011
Effect of Time, Temperature, and Kinetics on the Hysteretic Adsorption-Desorption of H-2, Ar, and N-2 in the Metal-Organic Framework Zn-2(bpdc)(2)(bpee)
The intriguing hysteretic adsorption-desorption behavior of certain microporous metal-organic frameworks (MMOFs) has received considerable attention and is often associated with a gate-opening (GO) effect. Here, the hysteretic adsorption of N-2 and Ar to Zn-2(bpdc)(2)(bpee) (bpdc = 4,4'-biplienyldicarboxylate; bpee = 1,2-bipyridylethene) shows a pronounced effect of allowed experimental time at 77 and 87 K. When the time allowed is on the order of minutes for N-2 at 77 K, no adsorption is observed, whereas times in excess of 60 h is required to achieve appreciable adsorption up to a limiting total coverage. Given sufficient time, the total uptake for N-2 and Ar converged at similar reduced temperatures, but the adsorption of Ar was significantly more rapid than that of N-2, an observation that can be described by activated configurational diffusion. N-2 and Ar both exhibited discontinuous stepped adsorption isotherms with significant hysteresis, features that were dependent upon the allowed time. The uptake of H-2 at 77 K was greater than for both N-2 and Ar but showed no discontinuity in the isotherm, and hysteretic effects were much less pronounced. N-2 and Ar adsorption data can be described by an activated diffusion process, with characteristic times leading to activation energies of 6.7 and 12 kJ/mot. Fits of H-2 adsorption data led to activation energies in the range 2-7 kJ/mot at low coverage and nonactivated diffusion at higher coverage. An alternate concentration-dependent diffusion model is presented to describe the stepwise adsorption behavior, which is observed for N-2 and Ar but not for H-2. Equilibrium is approached very slowly for adsorption to molecularly sized pores at low temperature, and structural change (gate opening), although it may occur, is not required to explain the observations.