CNR ExploRA

Articolo in rivista, 2022, ENG, 10.1016/j.checat.2022.03.015

Defect engineering over anisotropic brookite toward substrate-specific photo-oxidation of alcohols

S. M. Hossein Hejazi, Mahdi Shahrezaei, Piotr Blonski, Mattia Allieta, Polina M. Sheverdyaeva, Paolo Moras, Zdenek Badura, Sergii Kalytchuk, Elmira Mohammadi, Radek Zboril, Stepán Kment, Michal Otyepka, Alberto Naldoni, Paolo Fornasiero

Czech Advanced Technology and Research Institute, Regional Centre of Advanced Technologies and Materials, Palacky University Olomouc, Krivzkovskeho 511/8, 77900 Olomouc, Czech Republic; Department of Physical Chemistry, Faculty of Science, Palacky University, 17. listopadu 1192/12, 779 00 Olomouc, Czech Republic; Ronin Institute Montclair, Montclair, NJ 07043, USA; Istituto di Struttura della Materia-CNR (ISM-CNR), SS 14, Km 163,5, 34149 Trieste, Italy; Nanotechnology Centre, Centre of Energy and Environmental Technologies, VSB-Technical University of Ostrava, 17. listopadu 2172/15, 70800 Ostrava-Poruba, Czech Republic; IT4Innovations, VSB - Technical University of Ostrava, 17. listopadu 2172/15, 708 00 Ostrava-Poruba, Czech Republic; Department of Chemical and Pharmaceutical Sciences, ICCOM-CNR Trieste Research Unit, INSTM-Trieste, University of Trieste, Via L. Giorgieri 1, 34127 Trieste, Italy; Center for Energy, Environment and Transport Giacomo Ciamician - University of Trieste, Trieste, Italy

Generally adopted strategies for enhancing the photocatalytic activity are aimed at tuning the visible light response, the exposed crystal facets, and the nanocrystal shape. Here, we present a different approach for designing efficient photocatalysts displaying a substrate-specific reactivity upon defect engineering. The platinized, defective anisotropic brookite TiO 2 photocatalysts are tested for alcohol photoreforming showing up to an 11-fold increase in methanol oxidation rate, compared with the pristine one, while presenting much lower ethanol or isopropanol specific oxidation rates. We demonstrate that the substrate-specific alcohol oxidation and hydrogen evolution reactions are tightly related, and when the former is increased, the latter is boosted. The reduced anisotropic brookite shows up to 18-fold higher specific photoactivity with respect to anatase and brookite with isotropic nanocrystals. Advanced in situ characterizations and theoretical investigations reveal that controlled engineering over oxygen vacancies and lattice strain produces large electron polarons hosting the substrate-specific active sites for alcohol photo-oxidation.

Chem catalysis (Online) 2 (5), pp. 1177–1190