Lerf–Klinowski-type models of graphene oxide and reduced graphene oxide are robust in analyzing non-covalent functionalization with porphyrins

Abstract Graphene-based nanohybrids are good candidates for various applications. However, graphene exhibits some unwanted features such as low solubility in an aqueous solution or tendency to aggregate, limiting its potential applications. On the contrary, its derivatives, such as graphene oxide (G...

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Autores principales:	Alexandra Siklitskaya, Ewelina Gacka, Daria Larowska, Marta Mazurkiewicz-Pawlicka, Artur Malolepszy, Leszek Stobiński, Bronisław Marciniak, Anna Lewandowska-Andrałojć, Adam Kubas
Formato:	article
Lenguaje:	EN
Publicado:	Nature Portfolio 2021
Materias:	Medicine R Science Q
Acceso en línea:	https://doaj.org/article/252c924e7912494a9ba7cd5bc6b89ee8
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spelling	oai:doaj.org-article:252c924e7912494a9ba7cd5bc6b89ee82021-12-02T14:27:59ZLerf–Klinowski-type models of graphene oxide and reduced graphene oxide are robust in analyzing non-covalent functionalization with porphyrins10.1038/s41598-021-86880-12045-2322https://doaj.org/article/252c924e7912494a9ba7cd5bc6b89ee82021-04-01T00:00:00Zhttps://doi.org/10.1038/s41598-021-86880-1https://doaj.org/toc/2045-2322Abstract Graphene-based nanohybrids are good candidates for various applications. However, graphene exhibits some unwanted features such as low solubility in an aqueous solution or tendency to aggregate, limiting its potential applications. On the contrary, its derivatives, such as graphene oxide (GO) and reduced graphene oxide (RGO), have excellent properties and can be easily produced in large quantities. GO/RGO nanohybrids with porphyrins were shown to possess great potential in the field of photocatalytic hydrogen production, pollutant photodegradation, optical sensing, or drug delivery. Despite the rapid progress in experimental research on the porphyrin-graphene hybrids some fundamental questions about the structures and the interaction between components in these systems still remain open. In this work, we combine detailed experimental and theoretical studies to investigate the nature of the interaction between the GO/RGO and two metal-free porphyrins 5,10,15,20-tetrakis(4-aminophenyl) porphyrin (TAPP) and 5,10,15,20-tetrakis(4-hydroxyphenyl) porphyrin (TPPH)]. The two porphyrins form stable nanohybrids with GO/RGO support, although both porphyrins exhibited a slightly higher affinity to RGO. We validated finite, Lerf–Klinowski-type (Lerf et al. in J Phys Chem B 102:4477, 1998) structural models of GO ( $$\hbox {C}_{59}\hbox {O}_{26}\hbox {H}_{26}$$ C 59 O 26 H 26 ) and RGO ( $$\hbox {C}_{59}\hbox {O}_{17}\hbox {H}_{26}$$ C 59 O 17 H 26 ) and successfully used them in ab initio absorption spectra simulations to track back the origin of experimentally observed spectral features. We also investigated the nature of low-lying excited states with high-level wavefunction-based methods and shown that states’ density becomes denser upon nanohybrid formation. The studied nanohybrids are non-emissive, and our study suggests that this is due to excited states that gain significant charge-transfer character. The presented efficient simulation protocol may ease the properties screening of new GO/RGO-nanohybrids.Alexandra SiklitskayaEwelina GackaDaria LarowskaMarta Mazurkiewicz-PawlickaArtur MalolepszyLeszek StobińskiBronisław MarciniakAnna Lewandowska-AndrałojćAdam KubasNature PortfolioarticleMedicineRScienceQENScientific Reports, Vol 11, Iss 1, Pp 1-14 (2021)
institution	DOAJ
collection	DOAJ
language	EN
topic	Medicine R Science Q
spellingShingle	Medicine R Science Q Alexandra Siklitskaya Ewelina Gacka Daria Larowska Marta Mazurkiewicz-Pawlicka Artur Malolepszy Leszek Stobiński Bronisław Marciniak Anna Lewandowska-Andrałojć Adam Kubas Lerf–Klinowski-type models of graphene oxide and reduced graphene oxide are robust in analyzing non-covalent functionalization with porphyrins
description	Abstract Graphene-based nanohybrids are good candidates for various applications. However, graphene exhibits some unwanted features such as low solubility in an aqueous solution or tendency to aggregate, limiting its potential applications. On the contrary, its derivatives, such as graphene oxide (GO) and reduced graphene oxide (RGO), have excellent properties and can be easily produced in large quantities. GO/RGO nanohybrids with porphyrins were shown to possess great potential in the field of photocatalytic hydrogen production, pollutant photodegradation, optical sensing, or drug delivery. Despite the rapid progress in experimental research on the porphyrin-graphene hybrids some fundamental questions about the structures and the interaction between components in these systems still remain open. In this work, we combine detailed experimental and theoretical studies to investigate the nature of the interaction between the GO/RGO and two metal-free porphyrins 5,10,15,20-tetrakis(4-aminophenyl) porphyrin (TAPP) and 5,10,15,20-tetrakis(4-hydroxyphenyl) porphyrin (TPPH)]. The two porphyrins form stable nanohybrids with GO/RGO support, although both porphyrins exhibited a slightly higher affinity to RGO. We validated finite, Lerf–Klinowski-type (Lerf et al. in J Phys Chem B 102:4477, 1998) structural models of GO ( $$\hbox {C}_{59}\hbox {O}_{26}\hbox {H}_{26}$$ C 59 O 26 H 26 ) and RGO ( $$\hbox {C}_{59}\hbox {O}_{17}\hbox {H}_{26}$$ C 59 O 17 H 26 ) and successfully used them in ab initio absorption spectra simulations to track back the origin of experimentally observed spectral features. We also investigated the nature of low-lying excited states with high-level wavefunction-based methods and shown that states’ density becomes denser upon nanohybrid formation. The studied nanohybrids are non-emissive, and our study suggests that this is due to excited states that gain significant charge-transfer character. The presented efficient simulation protocol may ease the properties screening of new GO/RGO-nanohybrids.
format	article
author	Alexandra Siklitskaya Ewelina Gacka Daria Larowska Marta Mazurkiewicz-Pawlicka Artur Malolepszy Leszek Stobiński Bronisław Marciniak Anna Lewandowska-Andrałojć Adam Kubas
author_facet	Alexandra Siklitskaya Ewelina Gacka Daria Larowska Marta Mazurkiewicz-Pawlicka Artur Malolepszy Leszek Stobiński Bronisław Marciniak Anna Lewandowska-Andrałojć Adam Kubas
author_sort	Alexandra Siklitskaya
title	Lerf–Klinowski-type models of graphene oxide and reduced graphene oxide are robust in analyzing non-covalent functionalization with porphyrins
title_short	Lerf–Klinowski-type models of graphene oxide and reduced graphene oxide are robust in analyzing non-covalent functionalization with porphyrins
title_full	Lerf–Klinowski-type models of graphene oxide and reduced graphene oxide are robust in analyzing non-covalent functionalization with porphyrins
title_fullStr	Lerf–Klinowski-type models of graphene oxide and reduced graphene oxide are robust in analyzing non-covalent functionalization with porphyrins
title_full_unstemmed	Lerf–Klinowski-type models of graphene oxide and reduced graphene oxide are robust in analyzing non-covalent functionalization with porphyrins
title_sort	lerf–klinowski-type models of graphene oxide and reduced graphene oxide are robust in analyzing non-covalent functionalization with porphyrins
publisher	Nature Portfolio
publishDate	2021
url	https://doaj.org/article/252c924e7912494a9ba7cd5bc6b89ee8
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Lerf–Klinowski-type models of graphene oxide and reduced graphene oxide are robust in analyzing non-covalent functionalization with porphyrins

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