Theoretical Studies on Performance of Transiton Metal-substituted Keggin-type Phosphotungstate Dyes for Dye-sensitized Solar Cells†

doi:10.7503/cjcu20150710

Abstract

Abstract:

A series of Keggin type phosphotungstate with different transition metal-substituted dyes was designed. The electronic properties, UV-Vis absorption spectra and performance parameters of transition metal-substituted Keggin-type phosphotungstate dyes were systematically investigated via density functional theory(DFT) and time-dependent DFT(TD-DFT) methods. The results reveal that the absorption spectra of systems [PW₁₁O₃₉MCH₂COOH]ⁿ^- [M=Ru^Ⅱ(2), Ir^Ⅲ(3), Os^Ⅱ(4), Co^Ⅲ(5)] are red-shifted compared to the experimental system [PW₁₁O₃₉RhCH₂COOH]^5-(1). Especially, the spectra of system 4(M=Os^Ⅱ) has wide and strong absorption in visible region. And it has high electron injection efficiency and light harvesting efficiency, which may have important application in dye-sensitized solar cells(DSSCs) field.

Key words: Transition metal-substituted Keggin-type phosphotungstate, Absorption spectrum, Incident photon-to-electron conversion efficient, Density functional theory

CLC Number:

O641

TrendMD:

SUN Linlin, ZHANG Ting, YAN Likai, SU Zhongmin. Theoretical Studies on Performance of Transiton Metal-substituted Keggin-type Phosphotungstate Dyes for Dye-sensitized Solar Cells^†[J]. Chem. J. Chinese Universities, 2016, 37(3): 529.

Figures/Tables 4

Fig.1 Molecular structures of systems[PW11O39·MCH2COOH]n-[M=RhⅢ(1), RuⅡ(2), IrⅢ(3), OsⅡ(4), CoⅢ(5)

Table 1 Calculated energies of HOMO, LUMO and H-L of systems 1—5

System	E_HOMO/eV	E_LUMO/eV	E_H-L/eV	System	E_HOMO/eV	E_LUMO/eV	E_H-L/eV
1	-5.65	-3.65	2.00	4	-3.78	-3.24	0.54
2	-4.03	-3.21	0.82	5	-5.88	-3.64	2.24
3	-5.19	-3.68	1.51

Fig.2 Simulated absorption spectrum of systems 1—5(a—e)

Table 2 Calculated transition energy(ΔE), the free enthalpy of electron injection(ΔG), oxidation potential(Edye, Edye*) and LHE of the systems 1—5

System	E^dye/eV	ΔE/eV	$E dy e *$ /eV	ΔG/eV	LHE
1	6.11	4.29	1.82	-2.18	0.06
2	4.49	3.11	1.38	-2.62	0.09
3	5.58	2.89	2.69	-1.31	0.05
4	4.10	2.74	1.36	-2.64	0.14
5	6.21	4.71	1.50	-2.50	0.08

Table 2 Calculated transition energy(ΔE), the free enthalpy of electron injection(ΔG), oxidation potential(Edye, Edye*) and LHE of the systems 1—5

System	E^dye/eV	ΔE/eV	$E dy e *$ /eV	ΔG/eV	LHE
1	6.11	4.29	1.82	-2.18	0.06
2	4.49	3.11	1.38	-2.62	0.09
3	5.58	2.89	2.69	-1.31	0.05
4	4.10	2.74	1.36	-2.64	0.14
5	6.21	4.71	1.50	-2.50	0.08

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