title: New V(IV)-based metal-organic framework having framework flexibility and high CO2 adsorption capacity.
abstract: A vanadium based metal-organic framework (MOF), VO(BPDC) (BPDC(2-) = biphenyl-4,4'-dicarboxylate), adopting an expanded MIL-47 structure type, has been synthesized via solvothermal and microwave methods. Its structural and gas/vapor sorption properties have been studied. This compound displays a distinct breathing effect toward certain adsorptives at workable temperatures. The sorption isotherms of CO(2) and CH(4) indicate a different sorption behavior at specific temperatures. In situ synchrotron X-ray powder diffraction measurements and molecular simulations have been utilized to characterize the structural transition. The experimental measurements clearly suggest the existence of both narrow pore and large pore forms. A free energy profile along the pore angle was computationally determined for the empty host framework. Apart from a regular large pore and a regular narrow pore form, an overstretched narrow pore form has also been found. Additionally, a variety of spectroscopic techniques combined with N(2) adsorption/desorption isotherms measured at 77 K demonstrate that the existence of the mixed oxidation states V(III)/V(IV) in the titled MOF structure compared to pure V(IV) increases the difficulty in triggering the flexibility of the framework.
authors.affiliation: COMOC-Center for Ordered Materials, Organometallics and Catalysis, Department of Inorganic and Physical Chemistry, Ghent University, Krijgslaan 281-S3, 9000 Ghent, Belgium.
authors.forename: Ying-Ya
authors.initials: YY
authors.lastname: Liu
authors.forename: Sarah
authors.initials: S
authors.lastname: Couck
authors.forename: Matthias
authors.initials: M
authors.lastname: Vandichel
authors.forename: Maciej
authors.initials: M
authors.lastname: Grzywa
authors.forename: Karen
authors.initials: K
authors.lastname: Leus
authors.forename: Shyam
authors.initials: S
authors.lastname: Biswas
authors.forename: Dirk
authors.initials: D
authors.lastname: Volkmer
authors.forename: Jorge
authors.initials: J
authors.lastname: Gascon
authors.forename: Freek
authors.initials: F
authors.lastname: Kapteijn
authors.forename: Joeri F M
authors.initials: JF
authors.lastname: Denayer
authors.forename: Michel
authors.initials: M
authors.lastname: Waroquier
authors.forename: Veronique
authors.initials: V
authors.lastname: Van Speybroeck
authors.forename: Pascal
authors.initials: P
authors.lastname: Van Der Voort
mesh_terms: D000327:Adsorption; D002245:Carbon Dioxide / Q000737:chemistry*; D008697:Methane / Q000737:chemistry; D008872:Microwaves; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D033362:Powder Diffraction; D013499:Surface Properties; D017356:Synchrotrons; D014639:Vanadium / Q000737:chemistry*
chemical_list: D009942:Organometallic Compounds; D014639:Vanadium; D002245:Carbon Dioxide; D008697:Methane