High-Porosity Metal-Organic Framework Glasses

Wentao Xu; Nikita Hanikel; Kirill A Lomachenko; Cesare Atzori; Alicia Lund; Hao Lyu; Zihui Zhou; C Austen Angell; Omar M Yaghi

doi:10.1002/anie.202300003

High-Porosity Metal-Organic Framework Glasses

Angew Chem Int Ed Engl. 2023 Apr 11;62(16):e202300003. doi: 10.1002/anie.202300003. Epub 2023 Mar 6.

Authors

Wentao Xu¹, Nikita Hanikel¹, Kirill A Lomachenko², Cesare Atzori², Alicia Lund³, Hao Lyu¹, Zihui Zhou¹, C Austen Angell⁴, Omar M Yaghi^{5

6}

Affiliations

¹ Department of Chemistry and Kavli Energy Nanoscience Institute, University of California, Berkeley, Berkeley, CA 94720, USA.
² European Synchrotron Radiation Facility, 71 Avenue des Martyrs, CS 40220, 38043, Grenoble Cedex 9, France.
³ Department of Chemistry, University of California, Berkeley, Berkeley, CA 94720, USA.
⁴ School of Molecular Sciences, Arizona State University, Tempe, AZ 85287, USA.
⁵ Department of Chemistry, Kavli Energy Nanoscience Institute, and Bakar Institute of Digital Materials for the Planet, Division of Computing, Data Science, and Society, University of California, Berkeley, Berkeley, CA 94720, USA.
⁶ KACST-UC Berkeley Center of Excellence for Nanomaterials for Clean Energy Applications, King Abdulaziz City for Science and Technology, Riyadh, 11442, Saudi Arabia.

Abstract

We report a synthetic strategy to link titanium-oxo (Ti-oxo) clusters into metal-organic framework (MOF) glasses with high porosity though the carboxylate linkage. A new series of MOF glasses was synthesized by evaporation of solution containing Ti-oxo clusters Ti₁₆ O₁₆ (OEt)₃₂ , linkers, and m-cresol. The formation of carboxylate linkages between the Ti-oxo clusters and the carboxylate linkers was confirmed by Fourier-transform infrared (FT-IR) spectroscopy. The structural integrity of the Ti-oxo clusters within the glasses was evidenced by both X-ray absorption near edge structure (XANES) and ¹⁷ O magic-angle spinning (MAS) NMR. After ligand exchange and activation, the fumarate-linked MOF glass, termed Ti-Fum, showed a N₂ Brunauer-Emmett-Teller (BET) surface areas of 923 m² g^-1 , nearly three times as high as the phenolate-linked MOF glass with the highest BET surface area prior to this report.

Keywords: Glasses; Metal-Organic Frameworks; Porosity; Titanium-Oxo Clusters; XANES.

Grants and funding

S10 OD024998/OD/NIH HHS/United States