Guest-Host Interactions in Symmetrical Carboxy Heptamethine Cyanine Dyes-Titanium Dioxide Systems: Synthesis, Theoretical Calculations, Aggregation Properties, and Application in Dye-Sensitized Solar Cells
In this work, the role of deoxycholic acid (DCA) as a coadsorbent was investigated in the sensitization of mesoporous TiO2 layers (host) with symmetrical carboxy heptamethine cyanine dyes (guest). Different approaches have been tested, aimed at reducing the H-aggregation and minimizing the competiti...
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| Format: | Article |
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Wiley
2021-01-01
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| Series: | International Journal of Photoenergy |
| Online Access: | http://dx.doi.org/10.1155/2021/8852979 |
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| author | Rodrigo da Costa Duarte Matheus Costa de Oliveira Josene Maria Toldo Paulo Fernando Bruno Gonçalves Marcos José Leite Santos Fabiano Severo Rodembusch |
| author_facet | Rodrigo da Costa Duarte Matheus Costa de Oliveira Josene Maria Toldo Paulo Fernando Bruno Gonçalves Marcos José Leite Santos Fabiano Severo Rodembusch |
| author_sort | Rodrigo da Costa Duarte |
| collection | DOAJ |
| description | In this work, the role of deoxycholic acid (DCA) as a coadsorbent was investigated in the sensitization of mesoporous TiO2 layers (host) with symmetrical carboxy heptamethine cyanine dyes (guest). Different approaches have been tested, aimed at reducing the H-aggregation and minimizing the competition between cyanine molecules and DCA for active sites of the host, thus improving solar cell efficiency. Heptamethine cyanines containing carboxylic anchoring groups were obtained with good yields. The cyanines present UV-Vis absorption in methanol and dimethylformamide solutions ascribed to fully allowed electronic transitions (1ππ∗), as well as fluorescence emission in the NIR region, with any evidence of aggregations in both ground and excited states. TD-DFT calculations were also performed in order to study the geometry and charge distribution of these compounds in their ground and excited electronic states. Solid-state photophysics indicates that the cyanines showed excellent adsorption on TiO2, which can be justified by the presence of the -COOH moieties in the structure. Photophysical measurements have revealed the best concentrations of dye and DCA, which resulted in efficient inhibition of cyanine H-aggregates on the TiO2 surface in addition to allow large dye loading. HOMO and LUMO energy levels of the dyes were identified by cyclic voltammetry, showing oxidation and reduction potentials within acceptable limits for application as a photosensitizer in dye-sensitized solar cells (DSSCs) based on a TiO2 mesoporous photoanode. Assembled DSSCs have shown a large improvement of the electrical parameters and efficiency when a balance between dye aggregation and the competition to the host active sites was reached. |
| format | Article |
| id | doaj-art-315fa0c4f0c5408cb62fffc122db5ced |
| institution | Kabale University |
| issn | 1110-662X 1687-529X |
| language | English |
| publishDate | 2021-01-01 |
| publisher | Wiley |
| record_format | Article |
| series | International Journal of Photoenergy |
| spelling | doaj-art-315fa0c4f0c5408cb62fffc122db5ced2025-02-03T01:05:28ZengWileyInternational Journal of Photoenergy1110-662X1687-529X2021-01-01202110.1155/2021/88529798852979Guest-Host Interactions in Symmetrical Carboxy Heptamethine Cyanine Dyes-Titanium Dioxide Systems: Synthesis, Theoretical Calculations, Aggregation Properties, and Application in Dye-Sensitized Solar CellsRodrigo da Costa Duarte0Matheus Costa de Oliveira1Josene Maria Toldo2Paulo Fernando Bruno Gonçalves3Marcos José Leite Santos4Fabiano Severo Rodembusch5Grupo de Pesquisa em Fotoquímica Orgânica Aplicada (GPFOA), Instituto de Química, Universidade Federal do Rio Grande do Sul, Av. Bento Gonçalves 9500 CEP 91501-970 Porto Alegre RS, BrazilLaboratório de Materiais Aplicados e Interfaces (LAMAI), Instituto de Química, Universidade Federal do Rio Grande do Sul, Av. Bento Gonçalves 9500 CEP 91501-970 Porto Alegre RS, BrazilGrupo de Química Teórica e Computacional, Universidade Federal do Rio Grande do Sul-Instituto de Química, Avenida Bento Gonçalves, 9500, CP 15003, CEP 91501-970 Porto Alegre RS, BrazilGrupo de Química Teórica e Computacional, Universidade Federal do Rio Grande do Sul-Instituto de Química, Avenida Bento Gonçalves, 9500, CP 15003, CEP 91501-970 Porto Alegre RS, BrazilLaboratório de Materiais Aplicados e Interfaces (LAMAI), Instituto de Química, Universidade Federal do Rio Grande do Sul, Av. Bento Gonçalves 9500 CEP 91501-970 Porto Alegre RS, BrazilGrupo de Pesquisa em Fotoquímica Orgânica Aplicada (GPFOA), Instituto de Química, Universidade Federal do Rio Grande do Sul, Av. Bento Gonçalves 9500 CEP 91501-970 Porto Alegre RS, BrazilIn this work, the role of deoxycholic acid (DCA) as a coadsorbent was investigated in the sensitization of mesoporous TiO2 layers (host) with symmetrical carboxy heptamethine cyanine dyes (guest). Different approaches have been tested, aimed at reducing the H-aggregation and minimizing the competition between cyanine molecules and DCA for active sites of the host, thus improving solar cell efficiency. Heptamethine cyanines containing carboxylic anchoring groups were obtained with good yields. The cyanines present UV-Vis absorption in methanol and dimethylformamide solutions ascribed to fully allowed electronic transitions (1ππ∗), as well as fluorescence emission in the NIR region, with any evidence of aggregations in both ground and excited states. TD-DFT calculations were also performed in order to study the geometry and charge distribution of these compounds in their ground and excited electronic states. Solid-state photophysics indicates that the cyanines showed excellent adsorption on TiO2, which can be justified by the presence of the -COOH moieties in the structure. Photophysical measurements have revealed the best concentrations of dye and DCA, which resulted in efficient inhibition of cyanine H-aggregates on the TiO2 surface in addition to allow large dye loading. HOMO and LUMO energy levels of the dyes were identified by cyclic voltammetry, showing oxidation and reduction potentials within acceptable limits for application as a photosensitizer in dye-sensitized solar cells (DSSCs) based on a TiO2 mesoporous photoanode. Assembled DSSCs have shown a large improvement of the electrical parameters and efficiency when a balance between dye aggregation and the competition to the host active sites was reached.http://dx.doi.org/10.1155/2021/8852979 |
| spellingShingle | Rodrigo da Costa Duarte Matheus Costa de Oliveira Josene Maria Toldo Paulo Fernando Bruno Gonçalves Marcos José Leite Santos Fabiano Severo Rodembusch Guest-Host Interactions in Symmetrical Carboxy Heptamethine Cyanine Dyes-Titanium Dioxide Systems: Synthesis, Theoretical Calculations, Aggregation Properties, and Application in Dye-Sensitized Solar Cells International Journal of Photoenergy |
| title | Guest-Host Interactions in Symmetrical Carboxy Heptamethine Cyanine Dyes-Titanium Dioxide Systems: Synthesis, Theoretical Calculations, Aggregation Properties, and Application in Dye-Sensitized Solar Cells |
| title_full | Guest-Host Interactions in Symmetrical Carboxy Heptamethine Cyanine Dyes-Titanium Dioxide Systems: Synthesis, Theoretical Calculations, Aggregation Properties, and Application in Dye-Sensitized Solar Cells |
| title_fullStr | Guest-Host Interactions in Symmetrical Carboxy Heptamethine Cyanine Dyes-Titanium Dioxide Systems: Synthesis, Theoretical Calculations, Aggregation Properties, and Application in Dye-Sensitized Solar Cells |
| title_full_unstemmed | Guest-Host Interactions in Symmetrical Carboxy Heptamethine Cyanine Dyes-Titanium Dioxide Systems: Synthesis, Theoretical Calculations, Aggregation Properties, and Application in Dye-Sensitized Solar Cells |
| title_short | Guest-Host Interactions in Symmetrical Carboxy Heptamethine Cyanine Dyes-Titanium Dioxide Systems: Synthesis, Theoretical Calculations, Aggregation Properties, and Application in Dye-Sensitized Solar Cells |
| title_sort | guest host interactions in symmetrical carboxy heptamethine cyanine dyes titanium dioxide systems synthesis theoretical calculations aggregation properties and application in dye sensitized solar cells |
| url | http://dx.doi.org/10.1155/2021/8852979 |
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