(305f) Computational Study of the Adsorption Properties of M(bdc)(ted)0.5 (M = Ni, Zn)

Metal-organic frameworks (MOFs) have emerged as potential alternatives for the capture and storage of CO₂ from flue gas emissions.^1,2  Of particular interest is M(bdc)(ted)_0.5 (M = Ni or Zn; bdc = 1,4-benzenedicarboxylate; ted = triethylenediamine), as experimental and theoretical studies have shown that the Zn variant exhibits higher affinity towards CO₂ than other small molecules, such as CH₄, O₂ and N₂ when the bdc linkers are functionalized.³  While Zn(bdc)(ted)_0.5 has been extensively studied^4–8, neither experimental nor theoretical studies of the adsorption capacities of the Ni variant of this MOF have been reported in the literature.  In this work, a computational approach was used to shed light on the adsorption dynamics of CO₂ on the M(bdc)(ted)_0.5 (M = Ni, Zn) isostructures.  Adsorption isotherms were simulated with the grand canonical Monte Carlo technique.  The partial charges of the framework atoms were obtained from charge-assignment schemes based on DFT calculations^9,10and the computationally-inexpensive charge equilibration method.^11,12  The simulated isotherms of Zn(bdc)(ted)_0.5 were compared with experimental data available in the literature.  On the basis of agreement with the experimental isotherms, it was possible to examine the suitability of the different theoretical methods for rendering the charge distribution on the M(bdc)(ted)_0.5 frameworks.

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