Cristin-resultat-ID: 1894875
Sist endret: 2. mars 2021, 11:58

Rational Design of MOFs for CO2 Capture

  • Robert Brevik



Kjemisk Institutt, Universitetet i Oslo

Om resultatet

Publiseringsår: 2020
Antall sider: 65


Fagfelt (NPI)

Fagfelt: Kjemi
- Fagområde: Realfag og teknologi

Beskrivelse Beskrivelse


Rational Design of MOFs for CO2 Capture


In this thesis, the structure and reactivity of functionalized UiO MOFs were studied using density functional theory. Specifically, UiO-66 and UiO-67 were the target materials for the metalation with MgMe2reagents. To model the material, both periodic and cluster models were used. The UiO MOFs has the possibility to take different configurations with regards to the μ3−OHgroups within the tetrahedral (Th) pores. These configurations were defined as (4,0) to indicate that Th pores have either 4 OMgMe groups or none; (3,1) to indicate that the Th pores have 3 or 1 MgMe groups; and (2,2) to indicate that all Th pores have 2 MgMe. Periodic gas phase calculations on UiO-66 and UiO-67 show that the (4,0) configuration is the most stable for the functionalized μ3−OHsites with MX groups being M=Mg or Zn, and X=Me and Cl. In contrast, (2,2) was found to be the most stable configuration with MX=MgMe using cluster calculation with implicit THF solvent. Periodic computations showed a compression of the unit cell volume for UiO-67 after the pristine SBUs are metalated due to the bending of the linkers, which is consistent with unpublished experimental results. The geometrical analysis of the metalated structures showed that Mg is three-fold coordinated with oxygen at the bridging site, while Zn is only one-fold coordinated.Calculations on the metalation energy using nodes involving a defect site showed that it is more favorable to metalate a defect site containing a –OH and coordinated H2O than the μ3−OHsite. For both bridging and defect site, the insertion of CO2into the Mg-Me and ZnMe bonds was calculated, and was found to be exergonic with the Mg-Me and Zn-Me located in the defect sites, while endergonic with the Zn-Me located in the bridging site. Lastly the mechanism for the catalytic conversion of pentenylamine to pyrrolidine on the bridging site of the [Zr node]-MgMe model was computed with implicit benzene solvent at room temperature. The computed transition state energy barriers is consisted with experimental results.


Robert Brevik

  • Tilknyttet:
    ved Kjemisk institutt ved Universitetet i Oslo

Ainara Nova

  • Tilknyttet:
    ved Senter for materialvitenskap og nanoteknologi ved Universitetet i Oslo
  • Tilknyttet:
    ved Kjemisk institutt ved Universitetet i Oslo
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