Probing Acidic and Defective Sites in Sulfated UiO-66 and ZrO<sub>2</sub> via Adsorptive FTIR Spectroscopy
Sulfation is a common strategy to enhance the acidity and modify the adsorption properties of metal–organic frameworks (MOFs), yet its impact on the coordination and accessibility of active sites remains unclear. In this study, we investigate two structurally related systems—sulfated UiO-66 (UiO-66-...
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2025-05-01
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| author | Vera V. Butova Olga A. Burachevskaia Nikola L. Drenchev Andrei A. Tereshchenko Konstantin I. Hadjiivanov |
| author_facet | Vera V. Butova Olga A. Burachevskaia Nikola L. Drenchev Andrei A. Tereshchenko Konstantin I. Hadjiivanov |
| author_sort | Vera V. Butova |
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| description | Sulfation is a common strategy to enhance the acidity and modify the adsorption properties of metal–organic frameworks (MOFs), yet its impact on the coordination and accessibility of active sites remains unclear. In this study, we investigate two structurally related systems—sulfated UiO-66 (UiO-66-SO<sub>4</sub>) and sulfated tetragonal zirconia (S-ZrO<sub>2</sub>)—by FTIR spectroscopy with probe molecules. Isotope exchange experiments on S-ZrO<sub>2</sub> reveal that dehydration above 250 °C induces tridentate SO<sub>4</sub> coordination, while hydration leads to a reversible transition to a bidentate coordination mode. In UiO-66-SO<sub>4</sub>, sulfates are coordinated in a bidentate fashion to Zr<sub>6</sub>O<sub>6</sub> clusters, significantly affecting the accessibility of Zr sites in defective pores. This coordination prevents CO adsorption but allows acetonitrile adsorption even after room temperature activation. Unlike S-ZrO<sub>2</sub>, due to its lower thermal stability, UiO-66-SO<sub>4</sub> cannot be evacuated at high temperatures and dehydration at 250 °C does not induce tridentate coordination. The presence of H-bonded hydroxyls in UiO-66-SO<sub>4</sub> after activation at 250 °C supports this coordination model, indicating the formation of OH-coordinated Zr sites that are inaccessible to CO but interact with stronger bases like acetonitrile. Overall, this study provides new insights into the coordination chemistry of sulfated UiO-66 and highlights that sulfation can tune acidity and adsorption in MOFs for potential catalytic and adsorption applications. |
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| language | English |
| publishDate | 2025-05-01 |
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| series | Nanomaterials |
| spelling | doaj-art-650f86be151e4992ab018c58bcc7585b2025-08-20T02:23:44ZengMDPI AGNanomaterials2079-49912025-05-01151177910.3390/nano15110779Probing Acidic and Defective Sites in Sulfated UiO-66 and ZrO<sub>2</sub> via Adsorptive FTIR SpectroscopyVera V. Butova0Olga A. Burachevskaia1Nikola L. Drenchev2Andrei A. Tereshchenko3Konstantin I. Hadjiivanov4Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, 1113 Sofia, BulgariaThe Smart Materials Research Institute, Southern Federal University, 344090 Rostov-on-Don, RussiaInstitute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, 1113 Sofia, BulgariaThe Smart Materials Research Institute, Southern Federal University, 344090 Rostov-on-Don, RussiaInstitute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, 1113 Sofia, BulgariaSulfation is a common strategy to enhance the acidity and modify the adsorption properties of metal–organic frameworks (MOFs), yet its impact on the coordination and accessibility of active sites remains unclear. In this study, we investigate two structurally related systems—sulfated UiO-66 (UiO-66-SO<sub>4</sub>) and sulfated tetragonal zirconia (S-ZrO<sub>2</sub>)—by FTIR spectroscopy with probe molecules. Isotope exchange experiments on S-ZrO<sub>2</sub> reveal that dehydration above 250 °C induces tridentate SO<sub>4</sub> coordination, while hydration leads to a reversible transition to a bidentate coordination mode. In UiO-66-SO<sub>4</sub>, sulfates are coordinated in a bidentate fashion to Zr<sub>6</sub>O<sub>6</sub> clusters, significantly affecting the accessibility of Zr sites in defective pores. This coordination prevents CO adsorption but allows acetonitrile adsorption even after room temperature activation. Unlike S-ZrO<sub>2</sub>, due to its lower thermal stability, UiO-66-SO<sub>4</sub> cannot be evacuated at high temperatures and dehydration at 250 °C does not induce tridentate coordination. The presence of H-bonded hydroxyls in UiO-66-SO<sub>4</sub> after activation at 250 °C supports this coordination model, indicating the formation of OH-coordinated Zr sites that are inaccessible to CO but interact with stronger bases like acetonitrile. Overall, this study provides new insights into the coordination chemistry of sulfated UiO-66 and highlights that sulfation can tune acidity and adsorption in MOFs for potential catalytic and adsorption applications.https://www.mdpi.com/2079-4991/15/11/779MOFfunctionalizationsulfationUiO-66-SO<sub>4</sub>ZrO<sub>2</sub>-SO<sub>4</sub>S-ZrO<sub>2</sub> |
| spellingShingle | Vera V. Butova Olga A. Burachevskaia Nikola L. Drenchev Andrei A. Tereshchenko Konstantin I. Hadjiivanov Probing Acidic and Defective Sites in Sulfated UiO-66 and ZrO<sub>2</sub> via Adsorptive FTIR Spectroscopy Nanomaterials MOF functionalization sulfation UiO-66-SO<sub>4</sub> ZrO<sub>2</sub>-SO<sub>4</sub> S-ZrO<sub>2</sub> |
| title | Probing Acidic and Defective Sites in Sulfated UiO-66 and ZrO<sub>2</sub> via Adsorptive FTIR Spectroscopy |
| title_full | Probing Acidic and Defective Sites in Sulfated UiO-66 and ZrO<sub>2</sub> via Adsorptive FTIR Spectroscopy |
| title_fullStr | Probing Acidic and Defective Sites in Sulfated UiO-66 and ZrO<sub>2</sub> via Adsorptive FTIR Spectroscopy |
| title_full_unstemmed | Probing Acidic and Defective Sites in Sulfated UiO-66 and ZrO<sub>2</sub> via Adsorptive FTIR Spectroscopy |
| title_short | Probing Acidic and Defective Sites in Sulfated UiO-66 and ZrO<sub>2</sub> via Adsorptive FTIR Spectroscopy |
| title_sort | probing acidic and defective sites in sulfated uio 66 and zro sub 2 sub via adsorptive ftir spectroscopy |
| topic | MOF functionalization sulfation UiO-66-SO<sub>4</sub> ZrO<sub>2</sub>-SO<sub>4</sub> S-ZrO<sub>2</sub> |
| url | https://www.mdpi.com/2079-4991/15/11/779 |
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