From Homogeneous to Heterogenized Solar Fuels Assemblies: Observation of Electron Transfer Events in Systems Containing Dye-Sensitized Semiconductors and Molecular Catalysts

The conversion of solar energy into chemical energy by simultaneously oxidizing water and reducing protons to hydrogen could provide a much-needed fuel source within a more sustainable energy economy. Dye-sensitized photoelectrochemical cells (DSPECs) are capable of forming fuels using sunlight if photoexcited chromophores transfer charges to semiconductor electrodes and catalysts, and catalysis occurs, at rates exceeding those of charge recombination. The rational design of efficient DSPECs will require an understanding of the catalytic mechanisms and rate-limiting steps of the oxidative and reductive reactions. Here, we focus on how molecular and electrode design can be used to favor the desired charge transfer events from photoexcited perylene-3,4-dicarboximide (PMI) chromophores into semiconductor films and to molecular catalysts.;Previous efforts with related chromophores have focused on charge transfer between dyes and catalysts in homogeneous covalent systems without the presence of a supporting electrode. In this work, femtosecond to millisecond transient absorption spectroscopies are utilized to identify a PMI derivative capable of injecting electrons into nanostructured semiconductor films with favorable rates and yields. The identified derivative is further used to oxidize covalently attached homogeneous water oxidation catalyst (WOC) precursor Cp*Ir III(ppy)Cl, where ppy = 2-phenylpyridine, on TiO2 and then incorporated into several photoelectrodes for photodriven water oxidation and hydrogen production. Atomic layer deposition of Al2O3 following chromophore adsorption is employed to improve the chemical stability of the chromophores and to prevent rapid electron-hole recombination. The TiO2-based photoanodes contain a coadsorbed WOC [(Ir IV(pyalc)(H2O)R)2(micro-O)] +2, where pyalc = 2-(2'pyridyl)-2-propanolate, or its mononuclear precursor functionalized with a siloxane binding group. NiO-based photocathodes include molecular cobaloxime- or [Ni(P2N2) 2]2+-based proton reduction catalysts in solution. Photoelectrochemical experiments and ultrafast optical spectroscopies are used to probe the photocatalytic activities and photodriven electron transfer events with respect to electrode design and cell working conditions. After prolonged irradiation, O2 and H2 are observed by electrochemical techniques and by gas chromatography, respectively, supporting the broad applicability of this electrode architecture in DSPECs and the relevance of the time-resolved information gained. Future work should emphasize the analysis of subsequent charge accumulation steps and the design of more efficient photocatalytic systems.