NDLI: Interfacial electron transfer in photoanodes based on phosphorus(v) porphyrin sensitizers co-deposited on SnO<sub>2</sub> with the Ir(III)Cp* water oxidation precatalyst

Content Provider	Royal Society of Chemistry (RSC)
Author	Milot, Rebecca L. Brudvig, Gary W. der Est, Art van Batista, Victor S. Garapati, Venkata K. R. Sheehan, Stafford W. Poddutoori, Prashanth K. Negre, Christian F. A. Schmuttenmaer, Charles A. Thomsen, Julianne M.
Copyright Year	2015
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.
Starting Page	3868
Ending Page	3879
Page Count	12
File Format	HTM / HTML PDF
ISSN	20507488
Volume Number	3
Issue Number	7
Journal	Journal of Materials Chemistry A
DOI	10.1039/c4ta07018f
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	EPR Phosphorus Electron paramagnetic resonance Fluorescence Terahertz radiation Spectroscopy Quantum tunnelling Covalent bond Chloride Ligand Valence and conduction bands Carrier generation and recombination Redox
Content Type	Text
Resource Type	Article
Subject	Chemistry Renewable Energy, Sustainability and the Environment Materials Science

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

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