Welcoming gallium- and indium-fumarate MOFs to the family: synthesis, comprehensive characterization, observation of porous hydrophobicity, and CO2 dynamics

Yue Zhang, Bryan E. G. Lucier, Sarah M. Mckenzie, Mihails Arhangelskis, Andrew J. Morris, Tomislav Friščić, Joel W. Reid, Victor V. Terskikh, Mansheng Chen, Yining Huang*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

9 Citations (Scopus)
310 Downloads (Pure)

Abstract

The properties and applications of metal-organic frameworks (MOFs) are strongly dependent on the nature of the metals and linkers employed, along with the specific conditions employed during synthesis. Al-fumarate, trademarked as Basolite A520, is a porous MOF that incorporates aluminum centers along with fumarate linkers, and is a promising material for applications involving adsorption of gases such as CO2. In this work, the solvothermal synthesis and detailed characterization of the gallium and indium fumarate MOFs (Ga-fumarate, In-fumarate) are described. Using a combination of powder X-ray diffraction, Rietveld refinements, solid-state NMR spectroscopy, infrared spectroscopy, and thermogravimetric analysis, the topologies of Ga-fumarate and In-fumarate are revealed to be analogous to Al-fumarate. Ultra-wideline 69Ga, 71Ga and 115In NMR experiments at 21.1 T strongly support our refined structure. Adsorption isotherms show that the Al-, Ga-, and In-fumarate MOFs all exhibit an affinity for CO2, with Al-fumarate the superior adsorbent at 1 bar and 273 K. Static direct excitation and cross-polarized 13C NMR experiments permit investigation of CO2 adsorption locations, binding strengths, motional rates, and motional angles that are critical to increasing adsorption capacity and selectivity in these materials. Conducting the synthesis of the indium-based framework in methanol demonstrates a simple route to introduce porous hydrophobicity into a MIL-53-type framework, by incorporation of metal-bridging -OCH3 groups in the MOF pores.

Original languageEnglish
Pages (from-to)28582-28596
Number of pages15
JournalACS Applied Materials & Interfaces
Volume10
Issue number34
Early online date2 Aug 2018
DOIs
Publication statusPublished - 29 Aug 2018

Keywords

  • carbon dioxide
  • gas adsorption
  • guest dynamics
  • metal-organic frameworks
  • porous hydrophobicity
  • solid-state NMR
  • X-ray diffraction

ASJC Scopus subject areas

  • Materials Science(all)

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