Interaction of Acid Gases SO2 and NO2 with Coordinatively Unsaturated Metal Organic Frameworks: M-MOF-74 (M = Zn, Mg, Ni, Co)

Tan, K.; Zuluaga, S.; Wang, H.; Canepa, P.; Soliman, K.; Cure, J.; Li, J.; Thonhauser, T.; Chabal, Y. J.

doi:10.1021/acs.chemmater.7b00005

Interaction of Acid Gases SO₂ and NO₂ with Coordinatively Unsaturated Metal Organic Frameworks: M-MOF-74 (M = Zn, Mg, Ni, Co)

K. Tan, S. Zuluaga, H. Wang, P. Canepa, K. Soliman, J. Cure, J. Li, T. Thonhauser, and Y. J. Chabal; Chem. Mater. 29, 4227–4235 (2017).

BibTeX

@article{Tan2017interaction,
  author  = {Tan, K. and Zuluaga, S. and Wang, H. and Canepa, P. and Soliman, K. and Cure, J. and Li, J. and Thonhauser, T. and Chabal, Y. J.},
  title   = {{Interaction of Acid Gases SO$_{2}$ and NO$_{2}$ with Coordinatively Unsaturated Metal Organic Frameworks: M-MOF-74 (M = Zn, Mg, Ni, Co)}},
  journal = {Chemistry of Materials},
  volume  = {29},
  pages   = {4227--4235},
  year    = {2017},
  doi     = {10.1021/acs.chemmater.7b00005}
}

Abstract

In situ infrared spectroscopy and ab initio density functional theory (DFT) calculations are combined to study the interaction of the corrosive gases SO₂ and NO₂ with metal organic frameworks M-MOF-74 (M = Zn, Mg, Ni, Co). We find that NO₂ dissociatively adsorbs into MOF-74 compounds, forming NO and NO₃⁻. The mechanism is unraveled by considering the Zn-MOF-74 system, for which DFT calculations show that a strong NO₂–Zn bonding interaction induces a significant weakening of the N–O bond, facilitating the decomposition of the NO₂ molecules. In contrast, SO₂ is only molecularly adsorbed into MOF-74 with high binding energy (>90 kJ/mol for Mg-MOF-74 and >70 for Zn-MOF-74). This work gives insight into poisoning issues by minor components of flue gases in metal organic frameworks materials.