Cationic porphyrin‐graphene oxide hybrid: Donor‐acceptor composite for efficient photoinduced electron transfer

Daria Larowska , Aleksandra Wójcik , Marta Mazurkiewicz-Pawlicka , Artur Małolepszy , Leszek Stobiński , Bronisław Marciniak , Anna Lewandowska-Andrałojć


Non‐covalent nanohybrids composed of cationic 5,10,15,20‐tetra(4‐trimethylammoniophenyl)porphyrin tetra(p‐toluenesulfonate) (TMAP) and the graphene oxide sheets were prepared under two pH values (6.2 vs. 1.8). The TMAP molecule was positively charged, regardless of the pH value during preparation. However, protonation of the imino nitrogens increased the overall charge of the porphyrin molecule from +4 to +6 (TMAP4+ and TMAP6+). It was found that at acidic pH, interaction of TMAP6+ with GO was largely suppressed. On the other hand, results of FTIR, Raman spectroscopy, thermogravimetric analysis, atomic force microscopy (AFM) and elemental analysis confirmed effective non‐covalent functionalization of graphene oxide with cationic porphyrin at pH 6.2. The TMAP4+‐GO hybrids exhibited well defined structure with a monolayer of TMAP4+ on the GO sheets as confirmed by AFM. Formation of the ground‐state TMAP4+‐GO complex in solution was monitored by the red‐shift of the porphyrin Soret absorption band. This ground‐state interaction between TMAP4+ and GO is responsible for the static quenching of the porphyrin emission. Fluorescence was not detected for the nanohybrid which indicated that a very fast deactivation process had to take place. Ultrafast time‐resolved transient absorption spectroscopy clearly demonstrated the occurrence of electron transfer from the photoexcited TMAP4+ singlet state to GO sheets, as proven by the formation of a porphyrin radical cation.
Author Daria Larowska
Daria Larowska,,
, Aleksandra Wójcik
Aleksandra Wójcik,,
, Marta Mazurkiewicz-Pawlicka (FCPE / DSP)
Marta Mazurkiewicz-Pawlicka,,
- Department of Separation Processes
, Artur Małolepszy (FCPE / DSP)
Artur Małolepszy,,
- Department of Separation Processes
, Leszek Stobiński (FCPE / GL)
Leszek Stobiński,,
- WUT Grafen Laboratory
, Bronisław Marciniak - Adam Mickiewicz University (UAM)
Bronisław Marciniak,,
, Anna Lewandowska-Andrałojć - Adam Mickiewicz University (UAM)
Anna Lewandowska-Andrałojć,,
Journal seriesChemphyschem, ISSN 1439-4235, (A 35 pkt)
Issue year2019
Publication size in sheets0.6
Keywords in Englishelectron transfer, femtosecond spectroscopy, graphene oxide, nanohybrid, porphyrin
ASJC Classification1606 Physical and Theoretical Chemistry; 3107 Atomic and Molecular Physics, and Optics
Languageen angielski
Larowska D. (i in.) - Cationic porphyrin‐graphene...pdf 2.75 MB
Score (nominal)35
ScoreMinisterial score = 35.0, 05-06-2019, ArticleFromJournal
Publication indicators WoS Citations = 0; Scopus SNIP (Source Normalised Impact per Paper): 2016 = 0.771; WoS Impact Factor: 2017 = 2.947 (2) - 2017=2.95 (5)
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