Interfacial electron transfer in photoanodes based on phosphorus(v) porphyrin sensitizers co-deposited on SnO2 with the Ir(III)Cp∗ water oxidation precatalyst

Prashanth K. Poddutoori, Julianne M. Thomsen, Rebecca L. Milot, Stafford W. Sheehan, Christian F A Negre, Venkata K R Garapati, Charles A. Schmuttenmaer, Victor S. Batista, Gary W Brudvig, Art Van Der Est

Research output: Contribution to journalArticle

20 Citations (Scopus)

Abstract

We introduce phosphorus(v) porphyrins (PPors) as sensitizers of high-potential photoanodes with potentials in the 1.62-1.65 V (vs. NHE) range when codeposited with Ir(III)Cp∗ on SnO2. The ability of PPors to advance the oxidation state of the Ir(III)Cp∗ to Ir(IV)Cp∗, as required for catalytic water oxidation, is demonstrated by combining electron paramagnetic resonance (EPR), steady-state fluorescence and time-resolved terahertz spectroscopy (TRTS) measurements, in conjunction with quantum dynamics simulations based on DFT structural models. Contrary to most other types of porphyrins previously analyzed in solar cells, our PPors bind to metal-oxide surfaces through axial coordination, a binding mode that makes them less prone to aggregation. The comparison of covalent binding via anchoring groups, such as m-hydroxidebenzoate (-OPh-COO-) and 3-(3-phenoxy)-acetylacetonate (-OPh-AcAc) as well as by direct deposition upon exchange of a chloride (Cl-) ligand provides insight on the effect of the anchoring group on forward and reverse light-induced interfacial electron transfer (IET). TRTS and quantum dynamics simulations reveal efficient photoinduced electron injection, from the PPor to the conduction band of SnO2, with faster and more efficient IET from directly bound PPor than from anchor-bound PPors. The photocurrents of solar cells, however, are higher for PPor-OPh-COO- and PPor-OPh-AcAc than for the directly bound PPor-O- for which charge recombination is faster. The high-potentials and the ability to induce redox state transitions of Ir(III)Cp∗ suggest that PPor/SnO2 assemblies are promising photoanode components for direct solar water-oxidation devices.

Original languageEnglish
Pages (from-to)3868-3879
Number of pages12
JournalJournal of Materials Chemistry A
Volume3
Issue number7
DOIs
Publication statusPublished - Feb 21 2015

Fingerprint

Porphyrins
Terahertz spectroscopy
Phosphorus
Oxidation
Electrons
Water
Solar cells
Electron injection
Computer simulation
Conduction bands
Anchors
Photocurrents
Discrete Fourier transforms
Oxides
Paramagnetic resonance
Chlorides
Agglomeration
Metals
Fluorescence
Ligands

ASJC Scopus subject areas

  • Chemistry(all)
  • Renewable Energy, Sustainability and the Environment
  • Materials Science(all)

Cite this

Poddutoori, P. K., Thomsen, J. M., Milot, R. L., Sheehan, S. W., Negre, C. F. A., Garapati, V. K. R., ... Van Der Est, A. (2015). Interfacial electron transfer in photoanodes based on phosphorus(v) porphyrin sensitizers co-deposited on SnO2 with the Ir(III)Cp∗ water oxidation precatalyst. Journal of Materials Chemistry A, 3(7), 3868-3879. https://doi.org/10.1039/c4ta07018f

Interfacial electron transfer in photoanodes based on phosphorus(v) porphyrin sensitizers co-deposited on SnO2 with the Ir(III)Cp∗ water oxidation precatalyst. / Poddutoori, Prashanth K.; Thomsen, Julianne M.; Milot, Rebecca L.; Sheehan, Stafford W.; Negre, Christian F A; Garapati, Venkata K R; Schmuttenmaer, Charles A.; Batista, Victor S.; Brudvig, Gary W; Van Der Est, Art.

In: Journal of Materials Chemistry A, Vol. 3, No. 7, 21.02.2015, p. 3868-3879.

Research output: Contribution to journalArticle

Poddutoori, PK, Thomsen, JM, Milot, RL, Sheehan, SW, Negre, CFA, Garapati, VKR, Schmuttenmaer, CA, Batista, VS, Brudvig, GW & Van Der Est, A 2015, 'Interfacial electron transfer in photoanodes based on phosphorus(v) porphyrin sensitizers co-deposited on SnO2 with the Ir(III)Cp∗ water oxidation precatalyst', Journal of Materials Chemistry A, vol. 3, no. 7, pp. 3868-3879. https://doi.org/10.1039/c4ta07018f
Poddutoori, Prashanth K. ; Thomsen, Julianne M. ; Milot, Rebecca L. ; Sheehan, Stafford W. ; Negre, Christian F A ; Garapati, Venkata K R ; Schmuttenmaer, Charles A. ; Batista, Victor S. ; Brudvig, Gary W ; Van Der Est, Art. / Interfacial electron transfer in photoanodes based on phosphorus(v) porphyrin sensitizers co-deposited on SnO2 with the Ir(III)Cp∗ water oxidation precatalyst. In: Journal of Materials Chemistry A. 2015 ; Vol. 3, No. 7. pp. 3868-3879.
@article{f36403f309a24857a537bfd9261422fa,
title = "Interfacial electron transfer in photoanodes based on phosphorus(v) porphyrin sensitizers co-deposited on SnO2 with the Ir(III)Cp∗ water oxidation precatalyst",
abstract = "We introduce phosphorus(v) porphyrins (PPors) as sensitizers of high-potential photoanodes with potentials in the 1.62-1.65 V (vs. NHE) range when codeposited with Ir(III)Cp∗ on SnO2. The ability of PPors to advance the oxidation state of the Ir(III)Cp∗ to Ir(IV)Cp∗, as required for catalytic water oxidation, is demonstrated by combining electron paramagnetic resonance (EPR), steady-state fluorescence and time-resolved terahertz spectroscopy (TRTS) measurements, in conjunction with quantum dynamics simulations based on DFT structural models. Contrary to most other types of porphyrins previously analyzed in solar cells, our PPors bind to metal-oxide surfaces through axial coordination, a binding mode that makes them less prone to aggregation. The comparison of covalent binding via anchoring groups, such as m-hydroxidebenzoate (-OPh-COO-) and 3-(3-phenoxy)-acetylacetonate (-OPh-AcAc) as well as by direct deposition upon exchange of a chloride (Cl-) ligand provides insight on the effect of the anchoring group on forward and reverse light-induced interfacial electron transfer (IET). TRTS and quantum dynamics simulations reveal efficient photoinduced electron injection, from the PPor to the conduction band of SnO2, with faster and more efficient IET from directly bound PPor than from anchor-bound PPors. The photocurrents of solar cells, however, are higher for PPor-OPh-COO- and PPor-OPh-AcAc than for the directly bound PPor-O- for which charge recombination is faster. The high-potentials and the ability to induce redox state transitions of Ir(III)Cp∗ suggest that PPor/SnO2 assemblies are promising photoanode components for direct solar water-oxidation devices.",
author = "Poddutoori, {Prashanth K.} and Thomsen, {Julianne M.} and Milot, {Rebecca L.} and Sheehan, {Stafford W.} and Negre, {Christian F A} and Garapati, {Venkata K R} and Schmuttenmaer, {Charles A.} and Batista, {Victor S.} and Brudvig, {Gary W} and {Van Der Est}, Art",
year = "2015",
month = "2",
day = "21",
doi = "10.1039/c4ta07018f",
language = "English",
volume = "3",
pages = "3868--3879",
journal = "Journal of Materials Chemistry A",
issn = "2050-7488",
publisher = "Royal Society of Chemistry",
number = "7",

}

TY - JOUR

T1 - Interfacial electron transfer in photoanodes based on phosphorus(v) porphyrin sensitizers co-deposited on SnO2 with the Ir(III)Cp∗ water oxidation precatalyst

AU - Poddutoori, Prashanth K.

AU - Thomsen, Julianne M.

AU - Milot, Rebecca L.

AU - Sheehan, Stafford W.

AU - Negre, Christian F A

AU - Garapati, Venkata K R

AU - Schmuttenmaer, Charles A.

AU - Batista, Victor S.

AU - Brudvig, Gary W

AU - Van Der Est, Art

PY - 2015/2/21

Y1 - 2015/2/21

N2 - We introduce phosphorus(v) porphyrins (PPors) as sensitizers of high-potential photoanodes with potentials in the 1.62-1.65 V (vs. NHE) range when codeposited with Ir(III)Cp∗ on SnO2. The ability of PPors to advance the oxidation state of the Ir(III)Cp∗ to Ir(IV)Cp∗, as required for catalytic water oxidation, is demonstrated by combining electron paramagnetic resonance (EPR), steady-state fluorescence and time-resolved terahertz spectroscopy (TRTS) measurements, in conjunction with quantum dynamics simulations based on DFT structural models. Contrary to most other types of porphyrins previously analyzed in solar cells, our PPors bind to metal-oxide surfaces through axial coordination, a binding mode that makes them less prone to aggregation. The comparison of covalent binding via anchoring groups, such as m-hydroxidebenzoate (-OPh-COO-) and 3-(3-phenoxy)-acetylacetonate (-OPh-AcAc) as well as by direct deposition upon exchange of a chloride (Cl-) ligand provides insight on the effect of the anchoring group on forward and reverse light-induced interfacial electron transfer (IET). TRTS and quantum dynamics simulations reveal efficient photoinduced electron injection, from the PPor to the conduction band of SnO2, with faster and more efficient IET from directly bound PPor than from anchor-bound PPors. The photocurrents of solar cells, however, are higher for PPor-OPh-COO- and PPor-OPh-AcAc than for the directly bound PPor-O- for which charge recombination is faster. The high-potentials and the ability to induce redox state transitions of Ir(III)Cp∗ suggest that PPor/SnO2 assemblies are promising photoanode components for direct solar water-oxidation devices.

AB - We introduce phosphorus(v) porphyrins (PPors) as sensitizers of high-potential photoanodes with potentials in the 1.62-1.65 V (vs. NHE) range when codeposited with Ir(III)Cp∗ on SnO2. The ability of PPors to advance the oxidation state of the Ir(III)Cp∗ to Ir(IV)Cp∗, as required for catalytic water oxidation, is demonstrated by combining electron paramagnetic resonance (EPR), steady-state fluorescence and time-resolved terahertz spectroscopy (TRTS) measurements, in conjunction with quantum dynamics simulations based on DFT structural models. Contrary to most other types of porphyrins previously analyzed in solar cells, our PPors bind to metal-oxide surfaces through axial coordination, a binding mode that makes them less prone to aggregation. The comparison of covalent binding via anchoring groups, such as m-hydroxidebenzoate (-OPh-COO-) and 3-(3-phenoxy)-acetylacetonate (-OPh-AcAc) as well as by direct deposition upon exchange of a chloride (Cl-) ligand provides insight on the effect of the anchoring group on forward and reverse light-induced interfacial electron transfer (IET). TRTS and quantum dynamics simulations reveal efficient photoinduced electron injection, from the PPor to the conduction band of SnO2, with faster and more efficient IET from directly bound PPor than from anchor-bound PPors. The photocurrents of solar cells, however, are higher for PPor-OPh-COO- and PPor-OPh-AcAc than for the directly bound PPor-O- for which charge recombination is faster. The high-potentials and the ability to induce redox state transitions of Ir(III)Cp∗ suggest that PPor/SnO2 assemblies are promising photoanode components for direct solar water-oxidation devices.

UR - http://www.scopus.com/inward/record.url?scp=84922698624&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84922698624&partnerID=8YFLogxK

U2 - 10.1039/c4ta07018f

DO - 10.1039/c4ta07018f

M3 - Article

AN - SCOPUS:84922698624

VL - 3

SP - 3868

EP - 3879

JO - Journal of Materials Chemistry A

JF - Journal of Materials Chemistry A

SN - 2050-7488

IS - 7

ER -