Studies of Gas Adsorption in Flexible Metal-organic Frameworks

Open Access
Sircar, Sarmishtha
Graduate Program:
Energy and Mineral Engineering
Doctor of Philosophy
Document Type:
Date of Defense:
December 19, 2013
Committee Members:
  • Angela Lueking, Dissertation Advisor
  • Angela Lueking, Committee Chair
  • Derek Elsworth, Committee Member
  • Jonathan P Mathews, Committee Member
  • Adri van Duin, Committee Member
  • Adsorption
  • Gate-Opening
  • Metal-Organic Frameworks
Flexible Metal-Organic frameworks that exhibit a gate-opening (GO) adsorption mechanism have potential for gas separations and gas storage. The GO phenomenon occurs when molecular gates in the structure expand/contract in response to the activation/de-activation of a system variable e.g. temperature, pressure or gas. Sharp discontinuities in the isotherm leading to S-shapes and large adsorption-desorption hysteresis are typical of this phenomenon. This study investigates the kinetics and thermodynamics of the GO behavior by combining adsorption measurements and analytical modeling of adsorption kinetics and capacity as a function of adsorbate, GO pressure, and temperature. Basic understanding of GO mechanism will help harness GO-MOF‘s as adsorbents for gas separations and storage. Experiments were performed on two precharacterized MOFs with verified GO behavior. These are (1) Zn2(bpdc)2(bpee), which expands from a relative amorphous to crystalline structure and (2) Cu[(dhbc)2(4,4‘-bpy)]H2O, a mutually interdigitated 2-D structure (bpdc = biphenyldicarboxylate, bpee = 1,2‐bipyridylethene; DMF = N,N-dimethyl formamide, dhbc= 2,5-dihydroxybenzoic acid, bpy=bipyridine). Both sub- and super-critical adsorption data were collected using three adsorption units: a standard low-pressure volumetric adsorption unit, a commercial high-pressure gravimetric analyzer and a custom-built high-pressure differential volumetric unit. Collected laboratory data were combined with published adsorption rate and isotherm data for analysis to broaden the range of data collection. The accuracy of the high-pressure differential unit was improved by over 300-fold by changing analytical methods of processing data to establish a reliable null correction. A pronounced effect of the allowed experimental time was found at cryogenic temperatures on (1). Tightening the stability criteria used by the adsorption equipment to determine equilibration increased the experimental time from the order of minutes to >60 hours, and this in turn, led to a ~300 fold increase in capacity, convergence of capacities at similar reduced temperatures (critical temperature being the reducing parameter), discontinuities in the isotherms, lowering of gate-opening pressures, changes in the isotherm shapes as well as width of hysteresis loops. Although an experimental time effect was also seen for H2 adsorption at 77K, H2 showed no discontinuity in the adsorption isotherm, adsorption-desorption hysteresis was much less pronounced, and equilibration required significantly less time. The significant difference in rates of adsorption by different gases was attributed to an activated configurational diffusion regime in which the diffusing species moves through a corrugated surface potential when the diameter of the adsorbate approaches that of the pore. A concentration-dependent diffusion model coupled with insufficient equilibration time provides an alternate explanation to describe the stepwise adsorption behavior in GO-MOFs and the changes in capacities. A sigmoid shape of adsorption rate data at cryogenic temperatures is atypical of simple Fickian diffusion, suggesting a more complex mechanistic explanation is required to explain adsorption kinetics to GO-MOFs. Extending the unreacted shrinking core model from the field of catalyst deactivation suggests that relaxation will be much faster relative to diffusion when temperature is increased even by just 10K. From a thermodynamic perspective, adsorption isotherms on (2) demonstrate universality when pressure and temperature are scaled/reduced according to those at critical conditions. At similar reduced conditions, isotherms of gases on (2) converged and both capacity and pressure points of discontinuities showed a predictive behavior. Discrete levels of capacities were found which decrease in temperature. Existence of a universal parameter of heat of gate-opening is calculated and the heats of adsorption and structural expansion are shown to be separable. This adsorption universality suggests a means to predict adsorption capacity and GO pressure at a particular temperature-pressure for a given adsorbent to other adsorbates at other temperatures and pressures. Such predictive analysis is useful for setting up mass balance and heat balance equations during adsorptive bed design and saves a lot of experimental and computational time. It helps identify key parameters for an effective separation or storage e.g. temperature, pressure, time, gas.