Long-wavelength sensitization of TiO2 by ruthenium diimine compounds with low-lying π* orbitals.
Langmuir
; 27(23): 14522-31, 2011 Dec 06.
Article
em En
| MEDLINE
| ID: mdl-21913708
ABSTRACT
The role of low-lying π* orbitals in dye-sensitized solar cells based on mesoporous thin films of anatase TiO(2) nanocrystallites remains unknown. Herein we report three ruthenium compounds, cis-Ru(dcbq)(2)(NCS)(2), cis-Ru(dcbq)(bpy)(NCS)(2), and cis-Ru(dcb)(bq)(NCS)(2), where bpy is 2,2'-bipyridine, dcb is 4,4'-(CO(2)H)(2)-2,2'-bipyridine, bq is 2,2'-biquinoline, and dcbq is 4,4'-(CO(2)H)(2)-2,2'-biquinoline, that were synthesized, characterized, and contrasted with the well-known N3 compound (i.e., cis-Ru(dcb)(2)(NCS)(2)) in dye-sensitized solar cells. These compounds maintain the same cis-Ru(NCS)(2) core with a systematic variation in the energy of the π* orbitals of the diimine ligand bpy > dcb > bq > dcbq. The lowered π* orbitals resulted in enhanced red absorption relative to N3. With HCl pretreated TiO(2) in regenerative solar cells, sensitization from 400 to 900 nm was realized with cis-Ru(dcb)(bq)(NCS)(2) and global power conversion efficiencies as high as 6.5% were achieved under 1 sun of AM 1.5 irradiation. The energy conversion efficiency was found to be acutely sensitive to the presence of p-tert-butylpyridine (TBP) in a 0.5 M LiI/0.05 M I(2) acetonitrile electrolyte. Nanosecond transient absorption studies revealed that the addition of TBP decreased the excited-state injection yield for the compounds with biquinoline ligands. Spectro-electrochemical studies showed that the HCl pretreatment lowered the effective density of TiO(2) acceptor states and confirmed that the presence of TBP raised them toward the vacuum level. There was no spectroscopic data to support the hypothesis that the π* levels of the diimine ligand mediate back-electron transfer to the oxidized dye or the redox mediator was found.
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Coleções:
01-internacional
Base de dados:
MEDLINE
Assunto principal:
Compostos Organometálicos
/
Teoria Quântica
/
Rutênio
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Titânio
/
Iminas
Idioma:
En
Revista:
Langmuir
Assunto da revista:
QUIMICA
Ano de publicação:
2011
Tipo de documento:
Article
País de afiliação:
Estados Unidos