Photoelectrochemical Cells Utilizing Tunable Corroles

Bradley J. Brennan, Yick Chong Lam, Paul M. Kim, Xing Zhang, Gary W Brudvig

Research output: Contribution to journalArticle

19 Citations (Scopus)

Abstract

Organic dyes with their wide range of molecular structures and spectroscopic features show great promise for solar energy applications. Corroles, structural analogues to porphyrins, are highly fluorescent molecules with tunable properties. We have synthesized a series of structurally similar corroles chelating gallium and phosphorus, along with a β-chlorinated phosphorus corrole, and determined their photophysical and electrochemical properties. The electrochemical potentials to oxidize the corroles range from 0.78 V vs NHE for the gallium corrole to 1.42 V for the β-octachlorinated phosphorus corrole. We are interested in developing photosensitizers for water oxidation on a metal oxide-based photoanode, so the corroles were modified to contain a meso-phenyl-COOH substituent for binding to metal oxide surfaces. The ability of these corrole dyes to act as photosensitizers was assessed by comparing the corroles in a model dye sensitized solar cell design. Transient absorption spectroscopy was utilized to analyze recombination dynamics and determine the kinetics of iodide oxidation. The most efficient photoelectrochemical cell was achieved for the phosphorus corrole P-2 with electrochemical properties and kinetics suitable for both photoinduced electron injection into TiO2 and oxidation of iodide. This structure-function study highlights the wide window for tuning corrole electrochemical potentials while still maintaining desirable photophysical properties, important variables when designing dyes for applications in photoelectrochemical water-oxidation cells. (Chemical Equation Presented).

Original languageEnglish
Pages (from-to)16124-16130
Number of pages7
JournalACS Applied Materials and Interfaces
Volume7
Issue number29
DOIs
Publication statusPublished - Jul 29 2015

Fingerprint

Photoelectrochemical cells
Phosphorus
Oxidation
Photosensitizers
Dyes
Gallium
Electrochemical properties
Electron injection
Kinetics
Oxides
Porphyrins
Chelation
Metals
Absorption spectroscopy
Solar energy
Molecular structure
Photosensitizing Agents
Coloring Agents
Water
Iodides

Keywords

  • corroles
  • electrochemistry
  • molecular design
  • nanosecond transient absorption spectroscopy
  • photoelectrochemical cells

ASJC Scopus subject areas

  • Materials Science(all)

Cite this

Photoelectrochemical Cells Utilizing Tunable Corroles. / Brennan, Bradley J.; Lam, Yick Chong; Kim, Paul M.; Zhang, Xing; Brudvig, Gary W.

In: ACS Applied Materials and Interfaces, Vol. 7, No. 29, 29.07.2015, p. 16124-16130.

Research output: Contribution to journalArticle

Brennan, Bradley J. ; Lam, Yick Chong ; Kim, Paul M. ; Zhang, Xing ; Brudvig, Gary W. / Photoelectrochemical Cells Utilizing Tunable Corroles. In: ACS Applied Materials and Interfaces. 2015 ; Vol. 7, No. 29. pp. 16124-16130.
@article{a737504b235b4c8bbd64e609a2ef6204,
title = "Photoelectrochemical Cells Utilizing Tunable Corroles",
abstract = "Organic dyes with their wide range of molecular structures and spectroscopic features show great promise for solar energy applications. Corroles, structural analogues to porphyrins, are highly fluorescent molecules with tunable properties. We have synthesized a series of structurally similar corroles chelating gallium and phosphorus, along with a β-chlorinated phosphorus corrole, and determined their photophysical and electrochemical properties. The electrochemical potentials to oxidize the corroles range from 0.78 V vs NHE for the gallium corrole to 1.42 V for the β-octachlorinated phosphorus corrole. We are interested in developing photosensitizers for water oxidation on a metal oxide-based photoanode, so the corroles were modified to contain a meso-phenyl-COOH substituent for binding to metal oxide surfaces. The ability of these corrole dyes to act as photosensitizers was assessed by comparing the corroles in a model dye sensitized solar cell design. Transient absorption spectroscopy was utilized to analyze recombination dynamics and determine the kinetics of iodide oxidation. The most efficient photoelectrochemical cell was achieved for the phosphorus corrole P-2 with electrochemical properties and kinetics suitable for both photoinduced electron injection into TiO2 and oxidation of iodide. This structure-function study highlights the wide window for tuning corrole electrochemical potentials while still maintaining desirable photophysical properties, important variables when designing dyes for applications in photoelectrochemical water-oxidation cells. (Chemical Equation Presented).",
keywords = "corroles, electrochemistry, molecular design, nanosecond transient absorption spectroscopy, photoelectrochemical cells",
author = "Brennan, {Bradley J.} and Lam, {Yick Chong} and Kim, {Paul M.} and Xing Zhang and Brudvig, {Gary W}",
year = "2015",
month = "7",
day = "29",
doi = "10.1021/acsami.5b05050",
language = "English",
volume = "7",
pages = "16124--16130",
journal = "ACS applied materials & interfaces",
issn = "1944-8244",
publisher = "American Chemical Society",
number = "29",

}

TY - JOUR

T1 - Photoelectrochemical Cells Utilizing Tunable Corroles

AU - Brennan, Bradley J.

AU - Lam, Yick Chong

AU - Kim, Paul M.

AU - Zhang, Xing

AU - Brudvig, Gary W

PY - 2015/7/29

Y1 - 2015/7/29

N2 - Organic dyes with their wide range of molecular structures and spectroscopic features show great promise for solar energy applications. Corroles, structural analogues to porphyrins, are highly fluorescent molecules with tunable properties. We have synthesized a series of structurally similar corroles chelating gallium and phosphorus, along with a β-chlorinated phosphorus corrole, and determined their photophysical and electrochemical properties. The electrochemical potentials to oxidize the corroles range from 0.78 V vs NHE for the gallium corrole to 1.42 V for the β-octachlorinated phosphorus corrole. We are interested in developing photosensitizers for water oxidation on a metal oxide-based photoanode, so the corroles were modified to contain a meso-phenyl-COOH substituent for binding to metal oxide surfaces. The ability of these corrole dyes to act as photosensitizers was assessed by comparing the corroles in a model dye sensitized solar cell design. Transient absorption spectroscopy was utilized to analyze recombination dynamics and determine the kinetics of iodide oxidation. The most efficient photoelectrochemical cell was achieved for the phosphorus corrole P-2 with electrochemical properties and kinetics suitable for both photoinduced electron injection into TiO2 and oxidation of iodide. This structure-function study highlights the wide window for tuning corrole electrochemical potentials while still maintaining desirable photophysical properties, important variables when designing dyes for applications in photoelectrochemical water-oxidation cells. (Chemical Equation Presented).

AB - Organic dyes with their wide range of molecular structures and spectroscopic features show great promise for solar energy applications. Corroles, structural analogues to porphyrins, are highly fluorescent molecules with tunable properties. We have synthesized a series of structurally similar corroles chelating gallium and phosphorus, along with a β-chlorinated phosphorus corrole, and determined their photophysical and electrochemical properties. The electrochemical potentials to oxidize the corroles range from 0.78 V vs NHE for the gallium corrole to 1.42 V for the β-octachlorinated phosphorus corrole. We are interested in developing photosensitizers for water oxidation on a metal oxide-based photoanode, so the corroles were modified to contain a meso-phenyl-COOH substituent for binding to metal oxide surfaces. The ability of these corrole dyes to act as photosensitizers was assessed by comparing the corroles in a model dye sensitized solar cell design. Transient absorption spectroscopy was utilized to analyze recombination dynamics and determine the kinetics of iodide oxidation. The most efficient photoelectrochemical cell was achieved for the phosphorus corrole P-2 with electrochemical properties and kinetics suitable for both photoinduced electron injection into TiO2 and oxidation of iodide. This structure-function study highlights the wide window for tuning corrole electrochemical potentials while still maintaining desirable photophysical properties, important variables when designing dyes for applications in photoelectrochemical water-oxidation cells. (Chemical Equation Presented).

KW - corroles

KW - electrochemistry

KW - molecular design

KW - nanosecond transient absorption spectroscopy

KW - photoelectrochemical cells

UR - http://www.scopus.com/inward/record.url?scp=84938313614&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84938313614&partnerID=8YFLogxK

U2 - 10.1021/acsami.5b05050

DO - 10.1021/acsami.5b05050

M3 - Article

VL - 7

SP - 16124

EP - 16130

JO - ACS applied materials & interfaces

JF - ACS applied materials & interfaces

SN - 1944-8244

IS - 29

ER -