Iridium oxide nanoparticles stabilized by a heteroleptic ruthenium tris(bipyridyl) dye were used as sensitizers in photoelectrochemical cells consisting of a nanocrystalline anatase anode and a Pt cathode. The dye coordinated the IrO(2) x nH(2)O nanoparticles through a malonate group and the porous TiO(2) electrode through phosphonate groups. Under visible illumination (lambda > 410 nm) in pH 5.75 aqueous buffer, oxygen was generated at anode potentials positive of -325 mV vs Ag/AgCl and hydrogen was generated at the cathode. The internal quantum yield for photocurrent generation was ca. 0.9%. Steady-state luminescence and time-resolved flash photolysis/transient absorbance experiments were done to measure the rates of forward and back electron transfer. The low quantum yield for overall water splitting in this system can be attributed to slow electron transfer (approximately 2.2 ms) from IrO(2) x nH(2)O to the oxidized dye. Forward electron transfer does not compete effectively with the back electron transfer reaction from TiO(2) to the oxidized dye, which occurred on a time scale of 0.37 ms.

R esearchers are intensively investigating photochemical water splitting as a means of converting solar to chemical energy in the form of fuels. Hydrogen is a key solar fuel because it can be used directly in combustion engines or fuel cells, or combined catalytically with CO 2 to make carbon containing fuels. Different approaches to solar water splitting include semiconductor particles as photocatalysts and photoelectrodes, molecular donor-acceptor systems linked to catalysts for hydrogen and oxygen evolution, and photovoltaic cells coupled directly or indirectly to electrocatalysts.Despite several decades of research, solar hydrogen generation is efficient only in systems that use expensive photovoltaic cells to power water electrolysis. Direct photocatalytic water splitting is a challenging problem because the reaction is thermodynamically uphill. Light absorption results in the formation of energetic charge-separated states in both molecular donor-acceptor systems and semiconductor particles. Unfortunately, energetically favorable charge recombination reactions tend to be much faster than the slow multielectron processes of water oxidation and reduction. Consequently, visible light water splitting has only recently been achieved in semiconductor-based photocatalytic systems and remains an inefficient process.This Account describes our approach to two problems in solar water splitting: the organization of molecules into assemblies that promote long-lived charge separation, and catalysis of the electrolysis reactions, in particular the four-electron oxidation of water. The building blocks of our artificial photosynthetic systems are wide band gap semiconductor particles, photosensitizer and electron relay molecules, and nanoparticle catalysts. We intercalate layered metal oxide semiconductors with metal nanoparticles. These intercalation compounds, when sensitized with [Ru(bpy) 3 ] 2+ derivatives, catalyze the photoproduction of hydrogen from sacrificial electron donors (EDTA 2-) or non-sacrificial donors (I -). Through exfoliation of layered metal oxide semiconductors, we construct multilayer electron donor-acceptor thin films or sensitized colloids in which individual nanosheets mediate light-driven electron transfer reactions. When sensitizer molecules are "wired" to IrO 2 · nH 2 O nanoparticles, a dye-sensitized TiO 2 electrode becomes the photoanode of a water-splitting photoelectrochemical cell.Although this system is an interesting proof-of-concept, the performance of these cells is still poor (∼1% quantum yield) and the dye photodegrades rapidly. We can understand the quantum efficiency and degradation in terms of competing kinetic pathways for water oxidation, back electron transfer, and decomposition of the oxidized dye molecules. Laser flash photolysis experiments allow us to measure these competing rates and, in principle, to improve the performance of the cell by changing the architecture of the electron transfer chain.

We report a quantitative comparison of the photoaction spectra, short circuit current densities, and power conversion efficiencies of dye-sensitized solar cells (DSSCs) that contain bilayers of nanocrystalline TiO2 (nc-TiO2) and titania inverse opal photonic crystals (PCs). Cells were fabricated with PC/nc-TiO2 and nc-TiO2/PC bilayer films on glass/tin oxide anode of the cell, as well as in a split configuration in which the nc-TiO2 and PC layers were deposited on the anode and cathode sides of the cell, respectively. Incident photon current efficiencies at single wavelengths and current-voltage curves in white light were obtained with both cathode and anode side illumination. The results obtained support a model proposed by Miguez and co-workers, in which coupling of the low refractive index PC layer to the higher index nc-TiO2 layer creates a standing wave in the nc-TiO2 layer, enhancing the response of the DSSC in the red region of the spectrum. This enhancement is very sensitive to the degree of physical contact between the two layers. A gap on the order of 200 nm thick, created by a polymer templating technique, is sufficient to decouple the two layers optically. The coupling of the nc-TiO2 and PC layers across the gap could be improved slightly by treatment with TiCl4 vapor. In the bilayer configuration, there is an enhancement in the IPCE across the visible spectrum, which is primarily caused by defect scattering in the PC layer. There is also an increase of 20-50 mV in the open circuit photovoltage of the cell. With anode side illumination, the addition of a PC layer to the nc-TiO2 layer increased the efficiency of DSSCs from 6.5 to 8.3% at a constant N719 dye loading of 155-160 nmol/cm2.

The measurements were performed with a Brookhaven Instruments Zeta PALS at 298 K. R-HCa 2 Nb 3 O 10 and NS-H 4 Nb 6 O 17 powders were dispersed in pure water with concentrations of ca. 0.1 and 0.01 g•L -1 , respectively. In order to measure the pH dependence of the zeta-potential, the pH was adjusted by addition of aqueous HCl or sodium hydroxide (NaOH) solutions.