Rare-Earth MOFs for Applications of Acid-gas Binding and Sensing

April 8, 2022
Rare-Earth MOFs for Applications of Acid-gas Binding and Sensing
(a) Monodentate (MD) binding of both carboxylate oxygens to one Eu cation (right) vs the bidentate (BD) binding of each carboxylate oxygen to individual Eu cations (left). C-brown, O-red, and Eu-pink. (b) Comparison of pure BD bond Eu-DOBDC (right) against the three-dimensional supramolecular structure of mixed MD & BD bond Eu-DOBDC (left). The unit cell has been highlighted by the black square. As viewed down the c-axis.

Scientific Achievement

It is shown that the structure of a series of rare-earth (RE) containing metal organic frameworks (MOFs) can be controlled through the selected RE (affecting the pore size) and synthesis conditions (affecting the ligand binding) and this can influence the acid gas selectivity and sorption at the metal cluster.

Significance and Impact

This study demonstrates a potential kinetic route to develop highly stable and selective MOFs for the adsorption of caustic acid gas species.

Research Details

  • Optimized hydrothermal synthesis procedures developed to produce new family of MOFs.
  • Single crystal and powder X-ray diffraction determined the crystal structure.
  • High resolution neutron powder diffraction data was used to gain details of the ligand structure and disorder.
  • Density-functional theory (DFT) calculations were used to investigate the binding energies of the acid gas molecules.

“Kinetically Controlled Linker Binding in Rare Earth-2,5-Dihydroxyterepthalic Acid Metal−Organic Frameworks and Its Predicted Effects on Acid Gas Adsorption”

Susan E. Henkelis, Dayton J. Vogel, Peter C. Metz, Nichole R. Valdez, Mark A. Rodriguez, David X. Rademacher, Stephen Purdy, Stephen J. Percival, Jessica M. Rimsza, Katharine Page, and Tina M. Nenoff,

ACS Applied Materials Interfaces 13, 56337−56347 (2021). DOI: https://doi.org/10.1021/acsami.1c17670