Probing Reactive Platinum Sites in UiO-67 Zirconium Metal–Organic Frameworks
| Autor: | Lorenzo Mino, Giovanni Agostini, Unni Olsbye, Karl Petter Lillerud, Kirill A. Lomachenko, Sigurd Øien, Carlo Lamberti, Elisa Borfecchia, Stian Svelle, Erik Gallo, Silvia Bordiga |
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| Rok vydání: | 2015 |
| Předmět: |
Zirconium
Ligand Chemistry General Chemical Engineering Inorganic chemistry Pt Infrared spectroscopy chemistry.chemical_element General Chemistry Metallorganic Framework Photochemistry Oxidative addition XANES Einstein solid EXAFS Bipyridine chemistry.chemical_compound Oxidation state Materials Chemistry Metal-organic framework Metallorganic Framework MOF functionalized MOF EXAFS XANES Einstein solid Pt Platinum functionalized MOF MOF |
| Zdroj: | Chemistry of Materials. 27:1042-1056 |
| ISSN: | 1520-5002 0897-4756 |
| DOI: | 10.1021/cm504362j |
| Popis: | We present three methods of the synthesis of zirconium metal–organic framework UiO-67 functionalized with platinum bipyridine coordination complexes (bpydcPtIICl2 and bpydcPtIVCl4) acting as linkers in the MOF framework. These Pt complexes can be reduced to bpydcPt0 under flow of H2 gas in the 600–700 K range, as probed by a sophisticated parametric refinement of in situ EXAFS data. IR spectroscopy testifies the high coordinative unsaturation of the reduced centers, able to form bpydcPt0(CO)2 dicarbonyl complexes upon CO adsorption. The large pore size of UiO-67 allows for ligand exchange between 2 Cl– and even bulky ligands such as toluene-3,4-dithiol. Framework bpydcPtIICl2 complexes can also be oxidized at room temperature to bpydcPtIVBr4 through oxidative addition of liquid Br2. XANES spectroscopy was used to monitor the changes in the Pt oxidation state along the observed reactions. Platinum bipyridine-functionalized UiO-67-Pt displays the same exceptional stability as the parent material as testifie... |
| Databáze: | OpenAIRE |
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