Abstract
The metal-organic framework MOF-808 contains Zr6O8nodes with a high density of vacancy sites, which can incorporate carboxylate-containing functional groups to tune chemical reactivity. Although the postsynthetic methods to modify the chemistry of the Zr6O8nodes in MOFs are well known, tackling these alterations from a structural perspective is still a challenge. We have combined infrared spectroscopy experiments and first-principles calculations to identify the presence of node vacancies accessible for chemical modifications within the MOF-808. We demonstrate the potential of our approach to assess the decoration of MOF-808 nodes with different catechol-benzoate ligands. Furthermore, we have applied advanced synchrotron characterization tools, such as pair distribution function analyses and X-ray absorption spectroscopy, to resolve the atomic structure of single metal sites incorporated into the catechol groups postsynthetically. Finally, we demonstrate the catalytic activity of these MOF-808 materials decorated with single copper sites for 1,3-dipolar cycloadditions.
| Original language | English |
|---|---|
| Pages (from-to) | 27040-27047 |
| Number of pages | 8 |
| Journal | ACS Applied Materials and Interfaces |
| Volume | 14 |
| Issue number | 23 |
| DOIs | |
| Publication status | Published - 15 Jun 2022 |
Bibliographical note
Funding Information:A.E.P.-P. acknowledges the Spanish Ministry of Science and Innovation for a Ramón y Cajal fellowship (RYC2018-024328-I). I.R.-M. acknowledges FPI-UAM 2019 fellowship from UAM. C.R.-M. acknowledges funding from the Plan Andaluz de Investigación, Desarrollo e Innovación (PAIDI 2020) of Junta de Andalucía. I.d.C.-V. acknowledges FPI-UAM 2021 fellowship from UAM. The authors thank the Red Española de Supercomputación (RES) at the Marenostrum Supercomputer (BSC, Barcelona) for providing computational resources. The authors acknowledge DESY (Hamburg, Germany), a member of the Helmholtz Association HGF, for the provision of experimental facilities. Parts of this research were carried out at PETRA III, and the authors would like to thank Dr. Michael Wharmby and Dr. Alexander Schökel for assistance in using powder diffraction and total scattering beamline P02.1. Beamtime was allocated for proposal I-20190208-EC and I-20190239-EC. The authors also acknowledge the reimbursement of all travel expenses by DESY. The research leading to this result has been supported by the project CALIPSOplus under the Grant Agreement 730872 from the EU Framework Programme for Research and Innovation HORIZON 2020. Additional total scattering experiments were carried out at Diamond Light Source, Rutherford Appleton Laboratory, U.K., for the provision of synchrotron access to Beamline I15-1 (CY28223 proposal). XAS experiments were performed at BL22 CLAESS beamline at ALBA Synchrotron with the collaboration of Laura Simonelli (2021024939 proposal). The authors thank Dr. Andreas Mavrandonakis for his useful comments regarding the theoretical calculations.
Funding Information:
This work was supported by RTI2018-096138-A-I00 funded by MCIN/AEI/10.13039/501100011033 and EUR2020-112294 funded by MCIN/AEI/10.13039/501100011033 and by the European Union “NextGenerationEU”/PRTR. A.E.P.-P. and F.Z. acknowledge the financial support from the Spanish Ministry of Science and Innovation through the “María de Maeztu” Programme for Units of Excellence in R&D (CEX2018-000805-M).
Keywords
- 1,3-dipolar cycloaddition
- density functional theory calculations
- local structure
- vibrational spectroscopy
- zirconium metal-organic frameworks