High-Potential Porphyrins Supported on SnO 2 and TiO 2 Surfaces for Photoelectrochemical Applications

Jiang, Jianbing; Swierk, John R.; Materna, Kelly L.; Hedström, Svante; Lee, Shin Hee; Crabtree, Robert H.; Schmuttenmaer, Charles A.; Batista, Victor S.; Brudvig, Gary W.

doi:10.1021/acs.jpcc.6b10350

High-Potential Porphyrins Supported on SnO ₂ and TiO ₂ Surfaces for Photoelectrochemical Applications

Journal Article · Sat Dec 03 00:00:00 EST 2016 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.6b10350· OSTI ID:1334233

Jiang, Jianbing ^[1]; Swierk, John R. ^[2]; Materna, Kelly L. ^[2]; ^[2]; Lee, Shin Hee ^[2]; Crabtree, Robert H. ^[2]; Schmuttenmaer, Charles A. ^[2]; Batista, Victor S. ^[2]; ^[2]

Yale Univ., New Haven, CT (United States). Dept. of Chemistry and Energy Sciences Inst.; Yale University
Yale Univ., New Haven, CT (United States). Dept. of Chemistry and Energy Sciences Inst.

Here, we report CF₃-substituted porphyrins and evaluate their use as photosensitizers in water-splitting dye-sensitized photoelectrochemical cells (WS-DSPECs) by characterizing interfacial electron transfer on metal oxide surfaces. Furthermore, by using (CF₃)₂C₆H₃ instead of C₆F₅ substituents at the meso positions, we obtain the desired high potentials while avoiding the sensitivity of C₆F₅ substituents to nucleophilic substitution, a process that limits the types of synthetic reactions that can be used. Both the number of CF₃ groups and the central metal tune the ground and excited-state potentials. A pair of porphyrins bearing carboxylic acids as anchoring groups were deposited on SnO₂ and TiO₂ surfaces and the interfacial charge-injection and charge-recombination kinetics were characterized by using a combination of computational modeling, terahertz measurements, and transient absorption spectroscopy. We also found that both free-base and metallated porphyrins inject into SnO₂, and that recombination is slower for the latter case. Our findings demonstrate that (CF₃)₂C₆H₃-substituted porphyrins are promising photosensitizers for use in WS-DSPECs.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Argonne-Northwestern Solar Energy Research Center (ANSER); Yale Univ., New Haven, CT (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: FG02-07ER15909; SC0001059

OSTI ID:: 1334233

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 51 Vol. 120; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Related Subjects

14 SOLAR ENERGY
density functional theory
interfacial electron transfer
photosensitizers
terahertz spectroscopy
transient absorption
trifluoromethylphenyl