W. Justin Youngblood

Improving the efficiency of water splitting in dye-sensitized solar cells by using a biomimetic electron transfer mediator

Photoelectrochemical water splitting directly converts solar energy to chemical energy stored in hydrogen, a high energy density fuel. Although water splitting using semiconductor photoelectrodes has been studied for more than 40 years, it has only recently been demonstrated using dye-sensitized electrodes. The quantum yield for water splitting in these dye-based systems has, so far, been very low because the charge recombination reaction is faster than the catalytic four-electron oxidation of water to oxygen. We show here that the quantum yield is more than doubled by incorporating an electron transfer mediator that is mimetic of the tyrosine-histidine mediator in Photosystem II. The mediator molecule is covalently bound to the water oxidation catalyst, a colloidal iridium oxide particle, and is coadsorbed onto a porous titanium dioxide electrode with a Ruthenium polypyridyl sensitizer. As in the natural photosynthetic system, this molecule mediates electron transfer between a relatively slow metal oxide catalyst that oxidizes water on the millisecond timescale and a dye molecule that is oxidized in a fast light-induced electron transfer reaction. The presence of the mediator molecule in the system results in photoelectrochemical water splitting with an internal quantum efficiency of approximately 2.3% using blue light.

Photoluminescence of perovskite nanosheets prepared by exfoliation of layered oxides, K2Ln2Ti3O10, KLnNb2O7, and RbLnTa2O7 (Ln: lanthanide ion).

Luminescent perovskite nanosheets were prepared by exfoliation of single- or double-layered perovskite oxides, K2Ln2Ti3O10, KLnNb2O7, and RbLnTa2O7 (Ln: lanthanide ion). The thickness of the individual nanosheets corresponded to those of the perovskite block in the parent layered compounds. Intense red and green emissions were observed in aqueous solutions with Gd1.4Eu0.6Ti3O10- and La0.7Tb0.3Ta2O7-nanosheets, respectively, under UV illumination with energies greater than the corresponding host oxide band gap. The coincidence of the excitation spectrum and the band gap absorbance indicates that the visible emission results from energy transfer within the nanosheet. The red emission intensity of the Gd1.4Eu0.6Ti3O10-nanosheets was much stronger than that of the La0.90Eu0.05Nb2O7-nanosheets reported previously. The strong emission intensity is a result of a two-step energy transfer cascade within the nanosheet from the Ti-O network to Gd(3+) and then to Eu(3+). The emission intensities of the Gd1.4Eu0.6Ti3O10- and La0.7Tb0.3Ta2O7-nanosheets can be modulated by applying a magnetic field (1.3-1.4 T), which brings about a change in orientation of the nanosheets in solution. The emission intensities increased when the excitation light and the magnetic field directions were perpendicular to each other, and they decreased when the excitation and magnetic field were collinear and mutually perpendicular to the direction of detection of the emitted light.

Direct Deposition of Trivalent Rhodium Hydroxide Nanoparticles onto a Semiconducting Layered Calcium Niobate for Photocatalytic Hydrogen Evolution

Well-dispersed Rh(OH)3 nanoparticles were deposited in the interlayer galleries of a Dion-Jacobson type layered perovskite (ACa2Nb3O10: A=H or K). X-ray photoelectron spectra and zeta potential measurements suggest covalent bonding (Rh-O-Nb) between the nanoparticles and the niobate sheets. After calcination of Rh(OH)3/KCa2Nb3O10 at 350 degrees C in air, interlayer Rh(OH)3 nanoparticles were transformed to Rh2O3 and showed higher photocatalytic activity for hydrogen evolution using methanol as a sacrificial electron donor.

Synthesis of perylene–porphyrin building blocks and rod-like oligomers for light-harvesting applications

We present the synthesis of four perylene–porphyrin building blocks for use in Glaser, Sonogashira, or Suzuki polymerizations. The building blocks bear synthetic handles (4-ethynylphenyl, 4-iodophenyl, bromo) at the trans (5,15) meso-positions of a zinc porphyrin and contain two or four perylene-monoimide dyes attached at the 3,5-positions of the non-linking meso-aryl rings of the porphyrin. Each perylene-monoimide bears three 4-tert-butylphenoxy substituents (at the 1-, 6-, and 9-positions) and two isopropyl groups (on the N-aryl unit) for increased solubility. In each case the intervening linker is a diarylethyne unit that bridges the N-imide position of the perylene and the meso-position of the porphyrin. The perylene–porphyrin building blocks were prepared by (1) reaction of a diperylene-dipyrromethane with an aldehyde yielding a trans-A2B2-porphyrin, (2) reaction of a diperylene-aldehyde with a dipyrromethane yielding a trans-A2B2-porphyrin, and (3) reaction of a diperylene-dipyrromethane with a dipyrromethane-dicarbinol yielding a trans-AB2C-porphyrin or ABCD-porphyrin. The building blocks were subjected to Glaser, Sonogashira, or Suzuki coupling conditions in an effort to prepare oligomers containing porphyrins joined via 4,4′-diphenylbutadiyne (dpb), 4,4′-diphenylethyne (dpe), or 1,4-phenylene linkers (p), respectively. Each porphyrin in the backbone bears two or four pendant perylene-monoimide dyes. The Glaser and Sonogashira reactions afforded a distribution of oligomers, whereas the Suzuki reaction was unsuccessful. The oligomers were soluble in solvents such as toluene, THF, or CHCl3 enabling routine handling. The use of perylenes results in (1) increased light-harvesting efficiency particularly in the green spectral region where porphyrins are relatively transparent and (2) greater solubility than is achieved with the use of porphyrins alone. The soluble perylene–porphyrin oligomers are attractive for use as light-harvesting materials in molecular-based solar cells.

Electron transfer kinetics in water splitting dye-sensitized solar cells based on core–shell oxide electrodes

Photoelectrochemical water splitting occurs in a dye-sensitized solar cell when a [Ru(bpy)3]2+-based dye covalently links a porous TiO2 anode film to IrO2 x nH2O nanoparticles. The quantum yield for oxygen evolution is low because of rapid back electron transfer between TiO2 and the oxidized dye, which occurs on a timescale of hundreds of microseconds, When iodide is added as an electron donor, the photocurrent increases, confirming that the initial charge injection efficiency is high. When the porous TiO2 film is coated with a 1-2 nm thick layer of ZrO2 or Nb2O5, both the charge injection rate and back electron transfer rate decrease. The efficiency of the cell increases and then decreases with increasing film thickness, consistent with the trends in charge injection and recombination rates. The current efficiency for oxygen evolution, measured electrochemically in a generator-collector geometry, is close to 100%. The factors that lead to polarization of the photoanode and possible ways to re-design the system for higher efficiency are discussed.

Influence of Seeding and Bath Conditions in Hydrothermal Growth of Very Thin (∼20 nm) Single-Crystalline Rutile TiO2 Nanorod Films

New seeding conditions have been examined for the hydrothermal growth of single-crystalline rutile TiO₂ nanorods. Rutile nanorods of ∼20 nm diameter are grown from seed layers consisting of either (A) TiO₂ or MnOOH nanocrystals deposited from suspension, or (B) a continuous sheet of TiO₂. These seed layers are more effective for seeding the growth of rutile nanorods compared to the use of bare F-SnO₂ substrates. The TiO₂ sheet seeding allows lower concentration of titanium alkoxide precursor relative to previously reported procedures, but fusion of the resulting TiO₂ nanorods into bundles occurs at higher precursor concentration and/or longer growth duration. Performance of polymer-oxide solar cells prepared using these nanorods shows a dependence on the extent of bundling as well as rod height.

Synthesis and characterization of the multi-photon absorption and excited-state properties of a neat liquid 4-propyl 4'-butyl diphenyl acetylene

The synthesis, characterization, and quantitative electronic structure modeling of multi-photon absorption properties of a neat liquid L34 (4-propyl 4′-butyl diphenyl acetylene) are reported. The liquid is (linearly) transparent in the visible spectrum, but possesses large two-photon absorption (2PA) and 2PA-induced singlet and triplet excited-state absorption as measured by the Z-scan technique and non-linear transmission measurements using both picosecond and nanosecond pulses. The most dominant contributions to the intensity-dependent non-linear absorption come from the 2PA-induced triplet excited states in the nanosecond time regime. We also present transient absorption spectra of the liquid obtained by nanosecond laser-flash photolysis and compare these results with electronic structure calculations. The energy of the absorption bands, both singlet and triplet are in reasonable agreement with calculations performed with Gaussian 03. The experimentally measured spectra and theoretical electronic structure modeling provide information about the energy levels of the excited states of this liquid, including 2PA and 2PA-induced process that is responsible for its non-linear optical properties.

Templated Electrodeposition and Photocatalytic Activity of Cuprous Oxide Nanorod Arrays

Cuprous oxide (Cu2O) nanorod arrays have been prepared via a novel templated electrodeposition process and were characterized for their photocatalytic behavior in nonaqueous photoelectrochemical cells. Zinc oxide (ZnO) nanorod films serve as sacrificial templates for the in situ formation of polymer nanopore membranes on transparent conductive oxide substrates. Nitrocellulose and poly(lactic acid) are effective membrane-forming polymers that exhibit different modes of template formation, with nitrocellulose forming conformal coatings on the ZnO surface while poly(lactic acid) acts as an amorphous pore-filling material. Robust template formation is sensitive to the seeding method used to prepare the precursor ZnO nanorod films. Photoelectrochemical cells prepared from electrodeposited Cu2O films using methyl viologen as a redox shuttle in acetonitrile electrolyte exhibit significant charge recombination that can be partially suppressed by a combination of surface passivation methods. Surface-passivated nanostructured Cu2O films show enhanced photocurrent relative to planar electrodeposited Cu2O films of similar thickness. We have obtained the highest photocurrent ever reported for electrodeposited Cu2O in a nonaqueous photoelectrochemical cell.

Electron Transport in Acceptor-Sensitized Polymer–Oxide Solar Cells: The Importance of Surface Dipoles and Electron Cascade Effects

Fullerene and acenequinone compounds have been examined as electron mediators between a p-type semiconductive polymer and two n-type oxide semiconductors. Composite interlayer materials and photovoltaic test cells were assembled and studied for their fluorescence quenching, current-voltage, and quantum efficiency behavior to characterize the efficacy of the acceptor-sensitizers as electron-selective interlayers. The sensitizers are generally more effective with titanium dioxide than with zinc oxide, due to the difference in magnitude of dipole-induced vacuum level shifts at the respective oxide interfaces. In titanium dioxide-based solar cells, where dipole effects are weak, photovoltage and fill factor increase in a trend that matches the increase in the first reduction potential of the acceptor-sensitizers. Photosensitization of the oxide semiconductor by the acceptor-sensitizers is observed to operate either in parallel with the polymer as an alternate photosensitizer or in series with the polymer in a two-photon process, according to an acceptor-sensitizers first reduction potential. In zinc oxide-based solar cells, where dipole effects are stronger, the acceptor-sensitizers impaired most devices, which is attributed to an upward shift of the oxides conduction band edge caused by dipole-induced vacuum level shifts. These results have broad implications for designing electron-selective interlayers and solid-state photocells using sensitized oxide semiconductors.

Optoelectronic Tuning of Organoborylazadipyrromethenes via Effective Electronegativity at the Metalloid Center

Organoborylazadipyrromethenes were synthesized from free base and fluoroborylazadipyrromethenes and characterized with regard to their structural and electronic properties. B-N bond lengths, along with photophysical and redox behavior, appear dependent on the effective electronegativity at the boron atom as tuned by its substituents, with stronger electronegativity correlating to a shorter B-N bond length, red-shifted absorbance, enhanced fluorescence lifetime and yield, and positively shifted redox potentials.