We synthesized UiO-67 Metal Organic Frameworks (MOFs) functionalized with bpydcPt(II)Cl-2 and bpydcPt(IV)Cl-4 complexes (bpydc = bipyridine-dicarboxylate), as attractive candidates for the heterogenization of homogeneous catalytic reactions. Pt L-3-edge XAFS experiments allowed us to thoroughly characterize these materials, in the local environment of the Pt centers. XAFS studies evidenced the rich reactivity of UiO-67-Pt(II) MOFs, including reduction to bpydcPt(0) under H-2 flow in the 600-700 K range, room-temperature oxidation to bpydcPt(IV)Br-4 through oxidative addition of liquid Br-2 and ligand exchange between 2 Cl- and even bulky ligands such as toluene-3,4-dithiol. Preliminary XANES simulations with ADF code provide additional information on the oxidation state of Pt sites.

A XAFS study of the local environment and reactivity of Pt- sites in functionalized UiO-67 MOFs

BORFECCHIA, ELISA;MINO, LORENZO;BRAGLIA, LUCA;AGOSTINI, Giovanni;Gallo, Erik;LOMACHENKO, KIRILL;BORDIGA, Silvia;LAMBERTI, Carlo
2016-01-01

Abstract

We synthesized UiO-67 Metal Organic Frameworks (MOFs) functionalized with bpydcPt(II)Cl-2 and bpydcPt(IV)Cl-4 complexes (bpydc = bipyridine-dicarboxylate), as attractive candidates for the heterogenization of homogeneous catalytic reactions. Pt L-3-edge XAFS experiments allowed us to thoroughly characterize these materials, in the local environment of the Pt centers. XAFS studies evidenced the rich reactivity of UiO-67-Pt(II) MOFs, including reduction to bpydcPt(0) under H-2 flow in the 600-700 K range, room-temperature oxidation to bpydcPt(IV)Br-4 through oxidative addition of liquid Br-2 and ligand exchange between 2 Cl- and even bulky ligands such as toluene-3,4-dithiol. Preliminary XANES simulations with ADF code provide additional information on the oxidation state of Pt sites.
2016
16th International Conference on X‐ray Absorption Fine Structure (XAFS16)
Karlsruhe Germany
23-28/08/2015
712
1
012125
012125
http://www.iop.org/EJ/journal/conf
http://iopscience.iop.org/article/10.1088/1742-6596/712/1/012125/meta
MOF, metal-organic frameworks, functionalization, Pt, EXAFS, XANES, XANES simulation, ligand exchange
Borfecchia, Elisa; Øien, S.; Svelle, S.; Mino, Lorenzo; Braglia, Luca; Agostini, Giovanni; Gallo, Erik; Lomachenko, Kirill; Bordiga, Silvia; Guda, A. ...espandi
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2318/1633126
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