Donor-Substituted β-functionalized porphyrin dyes on hierarchically structured mesoporous TiO2 spheres. Highly efficient dye-sensitized solar cells

Masatoshi Ishida, Sun Woo Park, Daesub Hwang, Young Bean Koo, Jonathan L. Sessler, Dong Young Kim, Dongho Kim

Research output: Contribution to journalArticle

112 Citations (Scopus)

Abstract

Novel zinc porphyrin dyes for use in dye-sensitized solar cells (DSSCs) have been synthesized. These dyes are based on a molecular design that relies on donorπ-acceptor interactions, a concept implemented by introducing a bis(4-tert-butylphenyl)amino group at the meso position of the porphyrin opposite to what are 2-propenoic or 2,4-pentadienoic acid anchoring groups at the β-pyrrolic positions. Incorporating an electron-donating group (i.e., the diarylamine) on the porphyrin core serves as the considerable electronic coupling between the donor site and porphyrin core, and hence, the HOMO-LUMO energy gap is decreased. This change is reflected in the remarkable red shift and broadening of the absorption spectra relative to an unfunctionalized parent system. This substitution, in conjunction with functionalization with carboxylic acid moieties on the β-pyrrolic positions, also provides what is an effectively aligned donorπ-acceptor dipolar architecture. This, in turn, gives rise to advantageous charge-transfer properties, including what are significant improvements of the electron injection efficiency on titanium oxide (TiO2) compared to our previous models without a donor substituent. The DSSCs of this study were composed of zero-dimensional hierarchical structured TiO2 spheres with a diameter of 600-800 nm prepared from P-25 and anatase TiO2 nanoparticles, which functioned as the photoelectrodes. With the anatase TiO2-based DSSCs, the power conversion efficiencies (η) as well as the photocurrent action spectra were relatively enhanced, an effect ascribed to the characteristic mesoporous effect and associated electrophysical properties of the anatase TiO2 spheres. Among the dyes prepared in the context of the present study, the doubly functionalized carboxylic acid derivative, tda-2b-bd-Zn, gave rise to the highest power conversion. The η value was 7.47%, and the maximum incident photon-to-current efficiency was 77.3% at the Soret band. The overall η value of tda-2b-bd-Zn is comparable to the performance of typical ruthenium-based dyes, such as N3 (η = 7.68%), under the same conditions.

Original languageEnglish
Pages (from-to)19343-19354
Number of pages12
JournalJournal of Physical Chemistry C
Volume115
Issue number39
DOIs
Publication statusPublished - Oct 6 2011
Externally publishedYes

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Porphyrins
porphyrins
Coloring Agents
Dyes
solar cells
dyes
Titanium dioxide
Carboxylic Acids
Carboxylic acids
anatase
Electron injection
Ruthenium
Titanium oxides
carboxylic acids
Photocurrents
Conversion efficiency
Charge transfer
Absorption spectra
Energy gap
Zinc

All Science Journal Classification (ASJC) codes

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

Cite this

Donor-Substituted β-functionalized porphyrin dyes on hierarchically structured mesoporous TiO2 spheres. Highly efficient dye-sensitized solar cells. / Ishida, Masatoshi; Park, Sun Woo; Hwang, Daesub; Koo, Young Bean; Sessler, Jonathan L.; Kim, Dong Young; Kim, Dongho.

In: Journal of Physical Chemistry C, Vol. 115, No. 39, 06.10.2011, p. 19343-19354.

Research output: Contribution to journalArticle

Ishida, Masatoshi ; Park, Sun Woo ; Hwang, Daesub ; Koo, Young Bean ; Sessler, Jonathan L. ; Kim, Dong Young ; Kim, Dongho. / Donor-Substituted β-functionalized porphyrin dyes on hierarchically structured mesoporous TiO2 spheres. Highly efficient dye-sensitized solar cells. In: Journal of Physical Chemistry C. 2011 ; Vol. 115, No. 39. pp. 19343-19354.
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abstract = "Novel zinc porphyrin dyes for use in dye-sensitized solar cells (DSSCs) have been synthesized. These dyes are based on a molecular design that relies on donorπ-acceptor interactions, a concept implemented by introducing a bis(4-tert-butylphenyl)amino group at the meso position of the porphyrin opposite to what are 2-propenoic or 2,4-pentadienoic acid anchoring groups at the β-pyrrolic positions. Incorporating an electron-donating group (i.e., the diarylamine) on the porphyrin core serves as the considerable electronic coupling between the donor site and porphyrin core, and hence, the HOMO-LUMO energy gap is decreased. This change is reflected in the remarkable red shift and broadening of the absorption spectra relative to an unfunctionalized parent system. This substitution, in conjunction with functionalization with carboxylic acid moieties on the β-pyrrolic positions, also provides what is an effectively aligned donorπ-acceptor dipolar architecture. This, in turn, gives rise to advantageous charge-transfer properties, including what are significant improvements of the electron injection efficiency on titanium oxide (TiO2) compared to our previous models without a donor substituent. The DSSCs of this study were composed of zero-dimensional hierarchical structured TiO2 spheres with a diameter of 600-800 nm prepared from P-25 and anatase TiO2 nanoparticles, which functioned as the photoelectrodes. With the anatase TiO2-based DSSCs, the power conversion efficiencies (η) as well as the photocurrent action spectra were relatively enhanced, an effect ascribed to the characteristic mesoporous effect and associated electrophysical properties of the anatase TiO2 spheres. Among the dyes prepared in the context of the present study, the doubly functionalized carboxylic acid derivative, tda-2b-bd-Zn, gave rise to the highest power conversion. The η value was 7.47{\%}, and the maximum incident photon-to-current efficiency was 77.3{\%} at the Soret band. The overall η value of tda-2b-bd-Zn is comparable to the performance of typical ruthenium-based dyes, such as N3 (η = 7.68{\%}), under the same conditions.",
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N2 - Novel zinc porphyrin dyes for use in dye-sensitized solar cells (DSSCs) have been synthesized. These dyes are based on a molecular design that relies on donorπ-acceptor interactions, a concept implemented by introducing a bis(4-tert-butylphenyl)amino group at the meso position of the porphyrin opposite to what are 2-propenoic or 2,4-pentadienoic acid anchoring groups at the β-pyrrolic positions. Incorporating an electron-donating group (i.e., the diarylamine) on the porphyrin core serves as the considerable electronic coupling between the donor site and porphyrin core, and hence, the HOMO-LUMO energy gap is decreased. This change is reflected in the remarkable red shift and broadening of the absorption spectra relative to an unfunctionalized parent system. This substitution, in conjunction with functionalization with carboxylic acid moieties on the β-pyrrolic positions, also provides what is an effectively aligned donorπ-acceptor dipolar architecture. This, in turn, gives rise to advantageous charge-transfer properties, including what are significant improvements of the electron injection efficiency on titanium oxide (TiO2) compared to our previous models without a donor substituent. The DSSCs of this study were composed of zero-dimensional hierarchical structured TiO2 spheres with a diameter of 600-800 nm prepared from P-25 and anatase TiO2 nanoparticles, which functioned as the photoelectrodes. With the anatase TiO2-based DSSCs, the power conversion efficiencies (η) as well as the photocurrent action spectra were relatively enhanced, an effect ascribed to the characteristic mesoporous effect and associated electrophysical properties of the anatase TiO2 spheres. Among the dyes prepared in the context of the present study, the doubly functionalized carboxylic acid derivative, tda-2b-bd-Zn, gave rise to the highest power conversion. The η value was 7.47%, and the maximum incident photon-to-current efficiency was 77.3% at the Soret band. The overall η value of tda-2b-bd-Zn is comparable to the performance of typical ruthenium-based dyes, such as N3 (η = 7.68%), under the same conditions.

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