Synthesis and Application of New Ruthenium Complexes Containing β-Diketonato Ligands as Sensitizers for Nanocrystalline TiO2 Solar Cells
Five heteroleptic ruthenium complexes having different β-diketonato ligands, [Ru(tctpy)(dppd)(NCS)] (1), [Ru(tctpy)(pd)(NCS)] (2), [Ru(tctpy)(tdd)(NCS)] (3), [Ru(tctpy)(mepd)(NCS)] (4), and [Ru(tctpy)(tmhd)(NCS)] (5), where tctpy = 4,4′,4′′-tricarboxy-2,2′:6′,2′′-terpyridine,...
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| Format: | Article |
| Language: | English |
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Wiley
2011-01-01
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| Series: | International Journal of Photoenergy |
| Online Access: | http://dx.doi.org/10.1155/2011/204639 |
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| _version_ | 1832561868256837632 |
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| author | Ashraful Islam Surya Prakash Singh Liyuan Han |
| author_facet | Ashraful Islam Surya Prakash Singh Liyuan Han |
| author_sort | Ashraful Islam |
| collection | DOAJ |
| description | Five heteroleptic
ruthenium complexes having different β-diketonato ligands, [Ru(tctpy)(dppd)(NCS)]
(1), [Ru(tctpy)(pd)(NCS)] (2),
[Ru(tctpy)(tdd)(NCS)] (3), [Ru(tctpy)(mepd)(NCS)]
(4), and [Ru(tctpy)(tmhd)(NCS)] (5),
where tctpy = 4,4′,4′′-tricarboxy-2,2′:6′,2′′-terpyridine, pd = pentane-2,4-dione, mepd = 3-methylpentane-2,4-dione, tmhd = 2,2,6,6-tetramethylheptane-3,5-dione, tdd = tridecane-6,8-dione, and dppd = 1,3-diphenylpropane-1,3-dione, were synthesized and characterized. These heteroleptic complexes exhibit a broad metal-to-ligand charge transfer absorption band over the whole visible range extending up to 950 nm. The low-energy absorption bands and the E (Ru3+/2+) oxidation potentials in these complexes could be tuned to about 15 nm and 110 mV, respectively, by choosing appropriate β-diketonate ligands. Molecular orbital calculation of complex 1 shows that the HOMO is localized on the NCS ligand and the LUMO is localized on the tctpy ligand, which is anchored to the TiO2 nanoparticles. The β-diketonato-ruthenium(II)-polypyridyl sensitizers, when anchored to nanocrystalline TiO2 films for light to electrical energy conversion in regenerative photoelectrochemical cells, achieve efficient sensitization to TiO2 electrodes with increasing activity in the order
5 < 4 < 3 ≈ 2 < 1. Under standard AM 1.5 sunlight, the complex 1 yielded a short-circuit photocurrent density of 16.7 mA/cm2, an open-circuit voltage of 0.58 V, and a fill factor of 0.64, corresponding to an overall conversion efficiency of 6.2%. A systematic tuning of HOMO energy level shows that an efficient sensitizer should possess a ground-state redox potential value of >+.53 V versus SCE. |
| format | Article |
| id | doaj-art-b06d48e46b124b73a4acc18e8ebd1ff4 |
| institution | Kabale University |
| issn | 1110-662X 1687-529X |
| language | English |
| publishDate | 2011-01-01 |
| publisher | Wiley |
| record_format | Article |
| series | International Journal of Photoenergy |
| spelling | doaj-art-b06d48e46b124b73a4acc18e8ebd1ff42025-02-03T01:24:05ZengWileyInternational Journal of Photoenergy1110-662X1687-529X2011-01-01201110.1155/2011/204639204639Synthesis and Application of New Ruthenium Complexes Containing β-Diketonato Ligands as Sensitizers for Nanocrystalline TiO2 Solar CellsAshraful Islam0Surya Prakash Singh1Liyuan Han2International Center for Materials Nanoarchitectonics (MANA), National Institute for Materials Science (NIMS), 1-2-1 Sengen, Tsukuba, Ibaraki 305-0047, JapanInternational Center for Materials Nanoarchitectonics (MANA), National Institute for Materials Science (NIMS), 1-2-1 Sengen, Tsukuba, Ibaraki 305-0047, JapanInternational Center for Materials Nanoarchitectonics (MANA), National Institute for Materials Science (NIMS), 1-2-1 Sengen, Tsukuba, Ibaraki 305-0047, JapanFive heteroleptic ruthenium complexes having different β-diketonato ligands, [Ru(tctpy)(dppd)(NCS)] (1), [Ru(tctpy)(pd)(NCS)] (2), [Ru(tctpy)(tdd)(NCS)] (3), [Ru(tctpy)(mepd)(NCS)] (4), and [Ru(tctpy)(tmhd)(NCS)] (5), where tctpy = 4,4′,4′′-tricarboxy-2,2′:6′,2′′-terpyridine, pd = pentane-2,4-dione, mepd = 3-methylpentane-2,4-dione, tmhd = 2,2,6,6-tetramethylheptane-3,5-dione, tdd = tridecane-6,8-dione, and dppd = 1,3-diphenylpropane-1,3-dione, were synthesized and characterized. These heteroleptic complexes exhibit a broad metal-to-ligand charge transfer absorption band over the whole visible range extending up to 950 nm. The low-energy absorption bands and the E (Ru3+/2+) oxidation potentials in these complexes could be tuned to about 15 nm and 110 mV, respectively, by choosing appropriate β-diketonate ligands. Molecular orbital calculation of complex 1 shows that the HOMO is localized on the NCS ligand and the LUMO is localized on the tctpy ligand, which is anchored to the TiO2 nanoparticles. The β-diketonato-ruthenium(II)-polypyridyl sensitizers, when anchored to nanocrystalline TiO2 films for light to electrical energy conversion in regenerative photoelectrochemical cells, achieve efficient sensitization to TiO2 electrodes with increasing activity in the order 5 < 4 < 3 ≈ 2 < 1. Under standard AM 1.5 sunlight, the complex 1 yielded a short-circuit photocurrent density of 16.7 mA/cm2, an open-circuit voltage of 0.58 V, and a fill factor of 0.64, corresponding to an overall conversion efficiency of 6.2%. A systematic tuning of HOMO energy level shows that an efficient sensitizer should possess a ground-state redox potential value of >+.53 V versus SCE.http://dx.doi.org/10.1155/2011/204639 |
| spellingShingle | Ashraful Islam Surya Prakash Singh Liyuan Han Synthesis and Application of New Ruthenium Complexes Containing β-Diketonato Ligands as Sensitizers for Nanocrystalline TiO2 Solar Cells International Journal of Photoenergy |
| title | Synthesis and Application of New Ruthenium Complexes Containing
β-Diketonato Ligands as Sensitizers for Nanocrystalline TiO2 Solar Cells |
| title_full | Synthesis and Application of New Ruthenium Complexes Containing
β-Diketonato Ligands as Sensitizers for Nanocrystalline TiO2 Solar Cells |
| title_fullStr | Synthesis and Application of New Ruthenium Complexes Containing
β-Diketonato Ligands as Sensitizers for Nanocrystalline TiO2 Solar Cells |
| title_full_unstemmed | Synthesis and Application of New Ruthenium Complexes Containing
β-Diketonato Ligands as Sensitizers for Nanocrystalline TiO2 Solar Cells |
| title_short | Synthesis and Application of New Ruthenium Complexes Containing
β-Diketonato Ligands as Sensitizers for Nanocrystalline TiO2 Solar Cells |
| title_sort | synthesis and application of new ruthenium complexes containing β diketonato ligands as sensitizers for nanocrystalline tio2 solar cells |
| url | http://dx.doi.org/10.1155/2011/204639 |
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