NH3 and O2 interaction with tetrahedral Ti3+ ions isomorphously substituted in the framework of TiAlPO-5. A combined pulse EPR, pulse ENDOR, UV-Vis and FT-IR study |
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Authors: | Maurelli Sara Vishnuvarthan Muthusamy Berlier Gloria Chiesa Mario |
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Institution: | Dipartimento di Chimica IFM, Università di Torino and NIS, Nanostructured Interfaces and Surfaces Centre of Excellence, Torino, Italy. |
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Abstract: | Continuous Wave (CW), pulse Electron Paramagnetic Resonance (EPR) and pulse Electron Nuclear Double Resonance (ENDOR) spectroscopies, in conjunction with UV-Vis and Infrared (IR) spectroscopies, are used to investigate the chemical reactivity of tetrahedrally coordinated Ti(3+) ions isomorphously substituted in the framework of AlPO-5 towards NH(3) and O(2). The coordination of ammonia to Ti(3+) centres is followed in detail by complementary vibrational and electron magnetic resonance techniques. In particular HYSCORE spectra allow identifying the coordination of two ammonia molecules to Ti(3+) centres resolving the full hyperfine and quadrupole (14)N coupling tensors. The reactivity of the reduced TiAlPO sample towards molecular oxygen is detailed by means of CW-EPR and pulse ENDOR spectroscopy. (17)O(2) is employed, allowing to establish the formation of a "side-on" η(2) O(2)(-)-Ti(4+) electrostatic complex. Pulse ENDOR spectra provide detailed information on the local environment of the formed superoxide radical anion which acts as a paramagnetic probe, providing evidence for Ti-O-Ti oligomeric species. |
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