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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| Format: | Article |
| Language: | English |
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Nature Portfolio
2021-04-01
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| Series: | Scientific Reports |
| Online Access: | https://doi.org/10.1038/s41598-021-86880-1 |
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| 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 |
| collection | DOAJ |
| 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. |
| first_indexed | 2024-12-19T08:54:11Z |
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| id | doaj.art-252c924e7912494a9ba7cd5bc6b89ee8 |
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| language | English |
| last_indexed | 2024-12-19T08:54:11Z |
| publishDate | 2021-04-01 |
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| spelling | doaj.art-252c924e7912494a9ba7cd5bc6b89ee82022-12-21T20:28:39ZengNature PortfolioScientific Reports2045-23222021-04-0111111410.1038/s41598-021-86880-1Lerf–Klinowski-type models of graphene oxide and reduced graphene oxide are robust in analyzing non-covalent functionalization with porphyrinsAlexandra Siklitskaya0Ewelina Gacka1Daria Larowska2Marta Mazurkiewicz-Pawlicka3Artur Malolepszy4Leszek Stobiński5Bronisław Marciniak6Anna Lewandowska-Andrałojć7Adam Kubas8Institute of Physical Chemistry, Polish Academy of SciencesFaculty of Chemistry, Adam Mickiewicz UniversityFaculty of Chemistry, Adam Mickiewicz UniversityFaculty of Chemical and Process Engineering, Warsaw University of TechnologyFaculty of Chemical and Process Engineering, Warsaw University of TechnologyFaculty of Chemical and Process Engineering, Warsaw University of TechnologyFaculty of Chemistry, Adam Mickiewicz UniversityFaculty of Chemistry, Adam Mickiewicz UniversityInstitute of Physical Chemistry, Polish Academy of SciencesAbstract 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.https://doi.org/10.1038/s41598-021-86880-1 |
| spellingShingle | 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 Scientific Reports |
| title | 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_short | 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 |
| url | https://doi.org/10.1038/s41598-021-86880-1 |
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