Jump to main content
Jump to site search


The influence of antenna and anchoring moieties on the improvement of photoelectronic properties in Zn(II)–porphyrin–TiO2 as potential dye-sensitized solar cells

Author affiliations

Abstract

A systematic study for the rational design of porphyrins (P4 spider-shaped derivatives) with potential application in dye-sensitized solar cells is presented. Using density functional theory (DFT) (B3LYP/6-31G*) and time-dependent DFT (M06/6-31G*) we show that the UV-vis absorption properties of a spider-shaped Zn(II) porphyrin, previously synthesized by Stangel et al., may be greatly improved by applying some push–pull strategies in meso positions. We found that the selected triphenylamine push group induces a remarkable improvement in the absorption bands of P4 spider-shaped derivatives. The pull effect reached through the π-electron-rich phenyl group and the benzodithiazole (BTD) group allowed the Q bands to be red-shifted up to 689 nm, much longer than the 593 nm reported experimentally for the original spider-shaped porphyrin. The adsorption results of the P4 spider-shaped derivatives onto a TiO2-anatase surface model [Ti16O34H4] through the carboxylic acid group showed that the adsorptions energies were favourable and very similar in all cases. Natural bond orbitals (NBO) indicated a two-center bond (BD) O(carboxyl)–Ti(TiO2) for the porphyrin with the highest adsorption energy (8.27 kcal mol−1), and donor acceptor interactions from LP O(carboxyl) to Ti(TiO2) for the other porphyrins. The natural transition orbitals (NTO) for P4-derivatives-TiO2 confirm the nature of the excited states associated with Q and Soret bands. Finally, the frontier molecular orbitals revealed charge-separated states between those occupied and unoccupied, indicating a favourable charge-transfer process between the dyes and the surface conduction bands. In conclusion, this work showed a systematic study based on the push–pull strategy that improves the performance of porphyrins with the purpose to be used in dye-sensitized solar cells.

Graphical abstract: The influence of antenna and anchoring moieties on the improvement of photoelectronic properties in Zn(ii)–porphyrin–TiO2 as potential dye-sensitized solar cells

Back to tab navigation

Supplementary files

Publication details

The article was received on 11 Nov 2018, accepted on 25 Jan 2019 and first published on 25 Jan 2019


Article type: Paper
DOI: 10.1039/C8CP06988C
Citation: Phys. Chem. Chem. Phys., 2019, Advance Article

  •   Request permissions

    The influence of antenna and anchoring moieties on the improvement of photoelectronic properties in Zn(II)–porphyrin–TiO2 as potential dye-sensitized solar cells

    R. Urzúa-Leiva, R. Pino-Rios and G. Cárdenas-Jirón, Phys. Chem. Chem. Phys., 2019, Advance Article , DOI: 10.1039/C8CP06988C

Search articles by author

Spotlight

Advertisements