Three perfluorinated Zn-II porphyrins were evaluated as n-type sensitizers in photoelectrosynthetic cells for HBr and water splitting. All the dyes are featured by the presence of pentafluorophenyl electron-withdrawing groups to increase the ground-state oxidation potential and differ for the nature and position of the pi-conjugate linker between the core and anchoring group tasked to bind the metal oxide, in order to assess the best way of coupling with the semiconductor. A phenyl-triazole moiety was used to link the carboxylic anchoring group onto the meso position, while an ethynyl-phenyl linker was chosen to bridge carboxylic and cyanoacrylic groups onto the beta-pyrrolic position. A combination of electrochemical, computational, and spectroscopic investigations confirmed the strong electron-withdrawing effect of the perfluorinated porphyrin core, which assures all the investigated dyes of the high oxidation potential required to the coupling with water oxidation catalysts (WOC). Such an electron-poor core, however, affects the charge separation character of the dyes, as demonstrated by the spatial distribution of the excited states, leading to a nonquantitative charge injection, although tilting of the molecules on the semiconductor surface could bring the porphyrin ring closer to the semiconductor, offering additional charge-transfer pathways. Indeed, all the dyes demonstrated successful in the splitting of both aqueous HBr and water, with the best results found for the SnO2/TiO2 photoanode sensitized with the beta-substituted porphyrin equipped with a cyanoacrylic terminal group, achieving 0.4 and 0.1 mA/cm(2) photoanodic currents in HBr and water under visible light, respectively. The faradaic yield for oxygen evolution in the presence of an Ir-IV catalyst was over 95%, and the photoanode operation was stable for more than 1000 s. Thus, the perfluorinated porphyrins with a cyanoacrylic anchoring group at the beta-position should be considered for further development to improve the charge-transfer character.

Fluorinated ZnII porphyrins for dye-sensitized aqueous photoelectrosynthetic cells / A. Orbelli Biroli, F. Tessore, G. Di Carlo, M. Pizzotti, E. Benazzi, F. Gentile, S. Berardi, C.A. Bignozzi, R. Argazzi, M. Natali, A. Sartorel, S. Caramori. - In: ACS APPLIED MATERIALS & INTERFACES. - ISSN 1944-8244. - 11:36(2019 Sep 11), pp. 32895-32908.

Fluorinated ZnII porphyrins for dye-sensitized aqueous photoelectrosynthetic cells

A. Orbelli Biroli;F. Tessore
;
G. Di Carlo;M. Pizzotti;
2019-09-11

Abstract

Three perfluorinated Zn-II porphyrins were evaluated as n-type sensitizers in photoelectrosynthetic cells for HBr and water splitting. All the dyes are featured by the presence of pentafluorophenyl electron-withdrawing groups to increase the ground-state oxidation potential and differ for the nature and position of the pi-conjugate linker between the core and anchoring group tasked to bind the metal oxide, in order to assess the best way of coupling with the semiconductor. A phenyl-triazole moiety was used to link the carboxylic anchoring group onto the meso position, while an ethynyl-phenyl linker was chosen to bridge carboxylic and cyanoacrylic groups onto the beta-pyrrolic position. A combination of electrochemical, computational, and spectroscopic investigations confirmed the strong electron-withdrawing effect of the perfluorinated porphyrin core, which assures all the investigated dyes of the high oxidation potential required to the coupling with water oxidation catalysts (WOC). Such an electron-poor core, however, affects the charge separation character of the dyes, as demonstrated by the spatial distribution of the excited states, leading to a nonquantitative charge injection, although tilting of the molecules on the semiconductor surface could bring the porphyrin ring closer to the semiconductor, offering additional charge-transfer pathways. Indeed, all the dyes demonstrated successful in the splitting of both aqueous HBr and water, with the best results found for the SnO2/TiO2 photoanode sensitized with the beta-substituted porphyrin equipped with a cyanoacrylic terminal group, achieving 0.4 and 0.1 mA/cm(2) photoanodic currents in HBr and water under visible light, respectively. The faradaic yield for oxygen evolution in the presence of an Ir-IV catalyst was over 95%, and the photoanode operation was stable for more than 1000 s. Thus, the perfluorinated porphyrins with a cyanoacrylic anchoring group at the beta-position should be considered for further development to improve the charge-transfer character.
porphyrins; perfluorination; dye-sensitized photoelectrosynthetic cell; hydrohalic acid splitting; water splitting
Settore CHIM/03 - Chimica Generale e Inorganica
Laboratorio multifunzionale e centro di formazione per la caratterizzazione e la sperimentazione preapplicativa di smart materials
PIANO DI SOSTEGNO ALLA RICERCA 2015-2017 - LINEA 2 "DOTAZIONE ANNUALE PER ATTIVITA' ISTITUZIONALE" (ANNO 2016)
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/2434/672331
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