Anodic TiO2 nanotube arrays decorated with Ni, Cu, and NiCu alloy thin films were investigated for the first time for the photocatalytic degradation of paracetamol in water solution under UV irradiation. Metallic co-catalysts were deposited on TiO2 nanotubes using magnetron sputtering. The influence of the metal layer composition and thickness on the photocatalytic activity was systematically studied. Photocatalytic experiments showed that only Cu-rich co-catalysts provide enhanced paracetamol degradation rates, whereas Ni-modified photocatalysts exhibit no improvement compared with unmodified TiO2. The best-performing material was obtained by sputtering a 20 nm thick film of 1:1 atomic ratio NiCu alloy: this material exhibits a reaction rate more than doubled compared with pristine TiO2, enabling the complete degradation of 10 mg L-1 of paracetamol in 8 h. The superior performance of NiCu-modified systems over pure Cu-based ones is ascribed to a Ni and Cu synergistic effect. Kinetic tests using selective holes and radical scavengers unveiled, unlike prior findings in the literature, that paracetamol undergoes direct oxidation at the photocatalyst surface via valence band holes. Finally, Chemical Oxygen Demand (COD) tests and High-Resolution Mass Spectrometry (HR-MS) analysis were conducted to assess the degree of mineralization and identify intermediates. In contrast with the existing literature, we demonstrated that the mechanistic pathway involves direct oxidation by valence band holes.

Department of Chemical Engineering MESA Institute for Nanotechnology University of Twente P O Box 217 7500 AE Enschede The Netherlands

Department of Human Sciences and Innovation for the Territory University of Insubria via Sant'Abbondio 12 22100 Como Italy

Department of Materials Science WW4 LKO Friedrich Alexander University of Erlangen Nuremberg Martensstrasse 7 91058 Erlangen Germany

Department of Science and High Technology University of Insubria Via Valleggio 11 22100 Como Italy

Dipartimento di Chimica Università Degli Studi di Milano Via Golgi 19 20133 Milan Italy

Regional Center of Advanced Technologies and Materials Šlechtitelů 27 78371 Olomouc Czech Republic

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