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Electronic Properties of Electron-Deficient Zn(II) Porphyrins for HBr Splitting
oleh: Serena Berardi, Stefano Caramori, Elisabetta Benazzi, Nico Zabini, Alessandro Niorettini, Alessio Orbelli Biroli, Maddalena Pizzotti, Francesca Tessore, Gabriele Di Carlo
Format: | Article |
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Diterbitkan: | MDPI AG 2019-07-01 |
Deskripsi
Two different high potential Zn(II) porphyrin designs carrying either 4 or 5 <i>meso</i> pentafluorophenyl moieties as electron acceptor groups and a further electron withdrawing branch inserted in either the β (<b>1</b>) or <i>meso</i> (<b>2</b>) position were tested in photoelectrosynthetic cells for HBr splitting. Photoaction spectra in the presence of HBr showed that red photons up to 700 nm could be harvested and converted and that <b>2</b> performed better than <b>1</b>, thanks to better electronic properties of the excited state, favored by the insertion of the benzothiadiazole electron withdrawing group. Photoanodic performances in the presence of HBr, however, remained low, due to inefficient regeneration of the oxidized sensitizer as a result of an insufficient driving force for Br<sup>−</sup> oxidation.