4.1 Article

Thermodynamics of adsorption of aromatic compounds from non-aqueous solutions by MIL-53(Al) metal-organic framework

Journal

RUSSIAN CHEMICAL BULLETIN
Volume 66, Issue 1, Pages 16-22

Publisher

SPRINGER
DOI: 10.1007/s11172-017-1693-z

Keywords

metal-organic frameworks; MIL-53(Al); thermodynamics; liquid-phase adsorption; entropy-driven separations

Funding

  1. Russian Foundation for Basic Research [14-03-31979-mol_a, 14-03-97077-r_povolzhye_a]
  2. Ministry of Education and Science of the Russian Federation [1288]
  3. Council for Grants of the President of the Russian Federation [SP-134.2015.1]
  4. Russian Science Foundation [14-50-00126]

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The thermodynamics of adsorption of mono-, di-, and tricyclic aromatic compounds by MIL-53(Al) metal-organic framework from their solutions in MeCN, MeOH and n-C6H14-(PrOH)-O-i was studied for the first time. It was found that the adsorption of the test substances from solutions in MeCN and MeOH is characterized by positive values of enthalpy and entropy changes, and the adsorption from n-C6H14-(PrOH)-O-i medium is characterized by negative enthalpy and entropy changes. Upon adsorption by MIL-53(Al) framework from polar media, aromatic compounds were proposed to transfer from the liquid phase with a higher degree of association into the solvent medium with a lower degree of association, molecules of which are disordered due to the strong interaction with the hydrophobic walls of the framework pores. It was concluded that the driving force of adsorption by MIL-53(Al) from MeCN and MeOH is increase in entropy of the system, while the factor of adsorption from n-C6H14-(PrOH)-O-i medium is decrease in enthalpy of the adsorption system. The compensation effect in liquid-phase adsorption of aromatic compounds by MIL-53(Al) framework was discovered. The effect of the liquid phase nature on selectivity of adsorption from solutions onto investigated metal-organic framework was demonstrated.

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