Visible photoelectrochemical water splitting into H2 and O2 in a dye-sensitized photoelectrosynthesis cell.

A hybrid strategy for solar water splitting is exploited here based on a dye-sensitized photoelectrosynthesis cell (DSPEC) with a mesoporous SnO2/TiO2 core/shell nanostructured electrode derivatized with a surface-bound Ru(II) polypyridyl-based chromophore-catalyst assembly. The assembly, [(4,4'-(PO3H2)2bpy)2Ru(4-Mebpy-4'-bimpy)Ru(tpy)(OH2)](4+) ([Ru(a) (II)-Ru(b) (II)-OH2](4+), combines both a light absorber and a water oxidation catalyst in a single molecule. It was attached to the TiO2 shell by phosphonate-surface oxide binding. The oxide-bound assembly was further stabilized on the surface by atomic layer deposition (ALD) of either Al2O3 or TiO2 overlayers. Illumination of the resulting fluorine-doped tin oxide (FTO)|SnO2/TiO2|-[Ru(a) (II)-Ru(b) (II)-OH2](4+)(Al2O3 or TiO2) photoanodes in photoelectrochemical cells with a Pt cathode and a small applied bias resulted in visible-light water splitting as shown by direct measurements of both evolved H2 and O2. The performance of the resulting DSPECs varies with shell thickness and the nature and extent of the oxide overlayer. Use of the SnO2/TiO2 core/shell compared with nanoITO/TiO2 with the same assembly results in photocurrent enhancements of ∼ 5. Systematic variations in shell thickness and ALD overlayer lead to photocurrent densities as high as 1.97 mA/cm(2) with 445-nm, ∼ 90-mW/cm(2) illumination in a phosphate buffer at pH 7.

A Dye-Sensitized Photoelectrochemical Tandem Cell for Light Driven Hydrogen Production from Water.

Tandem junction photoelectrochemical water-splitting devices, whereby two light absorbing electrodes targeting separate portions of the solar spectrum generate the voltage required to convert water to oxygen and hydrogen, enable much higher possible efficiencies than single absorber systems. We report here on the development of a tandem system consisting of a dye-sensitized photoelectrochemical cell (DSPEC) wired in series with a dye-sensitized solar cell (DSC). The DSPEC photoanode incorporates a tris(bipyridine)ruthenium(II)-type chromophore and molecular ruthenium based water oxidation catalyst. The DSPEC was tested with two more-red absorbing DSC variations, one utilizing N719 dye with an I3-/I- redox mediator solution and the other D35 dye with a tris(bipyridine)cobalt ([Co(bpy)3]3+/2+) based mediator. The tandem configuration consisting of the DSPEC and D35/[Co(bpy)3]3+/2+ based DSC gave the best overall performance and demonstrated the production of H2 from H2O with the only energy input from simulated solar illumination.

Disentangling the Physical Processes Responsible for the Kinetic Complexity in Interfacial Electron Transfer of Excited Ru(II) Polypyridyl Dyes on TiO2.

Interfacial electron transfer at titanium dioxide (TiO2) is investigated for a series of surface bound ruthenium-polypyridyl dyes whose metal-to-ligand charge-transfer state (MLCT) energetics are tuned through chemical modification. The 12 complexes are of the form Ru(II)(bpy-A)(L)2(2+), where bpy-A is a bipyridine ligand functionalized with phosphonate groups for surface attachment to TiO2. Functionalization of ancillary bipyridine ligands (L) enables the potential of the excited state Ru(III/)* couple, E(+/)*, in 0.1 M perchloric acid (HClO4(aq)) to be tuned from -0.69 to -1.03 V vs NHE. Each dye is excited by a 200 fs pulse of light in the visible region of the spectrum and probed with a time-delayed supercontiuum pulse (350-800 nm). Decay of the MLCT excited-state absorption at 376 nm is observed without loss of the ground-state bleach, which is a clear signature of electron injection and formation of the oxidized dye. The dye-dependent decays are biphasic with time constants in the 3-30 and 30-500 ps range. The slower injection rate constant for each dye is exponentially distributed relative to E(+/)*. The correlation between the exponentially diminishing density of TiO2 sub-band acceptor levels and injection rate is well described using Marcus-Gerischer theory, with the slower decay components being assigned to injection from the thermally equilibrated state and the faster components corresponding to injection from higher energy states within the (3)MLCT manifold. These results and detailed analyses incorporating molecular photophysics and semiconductor density of states measurements indicate that the multiexponential behavior that is often observed in interfacial injection studies is not due to sample heterogeneity. Rather, this work shows that the kinetic heterogeneity results from competition between excited-state relaxation and injection as the photoexcited dye relaxes through the (3)MLCT manifold to the thermally equilibrated state, underscoring the potential for a simple kinetic model to reproduce the complex kinetic behavior often observed at the interface of mesoporous metal oxide materials.

Finding the Way to Solar Fuels with Dye-Sensitized Photoelectrosynthesis Cells.

The dye-sensitized photoelectrosynthesis cell (DSPEC) integrates high bandgap, nanoparticle oxide semiconductors with the light-absorbing and catalytic properties of designed chromophore-catalyst assemblies. The goals are photoelectrochemical water splitting into hydrogen and oxygen and reduction of CO2 by water to give oxygen and carbon-based fuels. Solar-driven water oxidation occurs at a photoanode and water or CO2 reduction at a cathode or photocathode initiated by molecular-level light absorption. Light absorption is followed by electron or hole injection, catalyst activation, and catalytic water oxidation or water/CO2 reduction. The DSPEC is of recent origin but significant progress has been made. It has the potential to play an important role in our energy future.

Solar water splitting in a molecular photoelectrochemical cell.

Artificial photosynthesis and the production of solar fuels could be a key element in a future renewable energy economy providing a solution to the energy storage problem in solar energy conversion. We describe a hybrid strategy for solar water splitting based on a dye sensitized photoelectrosynthesis cell. It uses a derivatized, core-shell nanostructured photoanode with the core a high surface area conductive metal oxide film--indium tin oxide or antimony tin oxide--coated with a thin outer shell of TiO2 formed by atomic layer deposition. A "chromophore-catalyst assembly" 1, [(PO3H2)2bpy)2Ru(4-Mebpy-4-bimpy)Rub(tpy)(OH2)](4+), which combines both light absorber and water oxidation catalyst in a single molecule, was attached to the TiO2 shell. Visible photolysis of the resulting core-shell assembly structure with a Pt cathode resulted in water splitting into hydrogen and oxygen with an absorbed photon conversion efficiency of 4.4% at peak photocurrent.

Crossing the divide between homogeneous and heterogeneous catalysis in water oxidation.

Enhancing the surface binding stability of chromophores, catalysts, and chromophore-catalyst assemblies attached to metal oxide surfaces is an important element in furthering the development of dye sensitized solar cells, photoelectrosynthesis cells, and interfacial molecular catalysis. Phosphonate-derivatized catalysts and molecular assemblies provide a basis for sustained water oxidation on these surfaces in acidic solution but are unstable toward hydrolysis and loss from surfaces as the pH is increased. Here, we report enhanced surface binding stability of a phosphonate-derivatized water oxidation catalyst over a wide pH range (1-12) by atomic layer deposition of an overlayer of TiO2. Increased stability of surface binding, and the reactivity of the bound catalyst, provides a hybrid approach to heterogeneous catalysis combining the advantages of systematic modifications possible by chemical synthesis with heterogeneous reactivity. For the surface-stabilized catalyst, greatly enhanced rates of water oxidation are observed upon addition of buffer bases -H2PO(-)(4)/HPO(2-)(4), B(OH)3/B(OH)2 O-, HPO(2-)4 /PO(3-)(4) - and with a pathway identified in which O-atom transfer to OH(-) occurs with a rate constant increase of 10(6) compared to water oxidation in acid.

Atomic layer deposition of TiO2 on mesoporous nanoITO: conductive core-shell photoanodes for dye-sensitized solar cells.

Core-shell structures consisting of thin shells of conformal TiO2 deposited on high surface area, conductive Sn-doped In2O3 nanoparticle. Mesoscopic films were synthesized by atomic layer deposition and studied for application in dye-sensitized solar cells. Results obtained with the N719 dye show that short-circuit current densities, open-circuit voltages, and back electron transfer lifetimes all increased with increasing TiO2 shell thickness up to 1.8-2.4 nm and then decline as the thickness was increased further. At higher shell thicknesses, back electron transfer to -Ru(III) is increasingly competitive with transport to the nanoITO core resulting in decreased device efficiencies.

Stabilization of ruthenium(II) polypyridyl chromophores on nanoparticle metal-oxide electrodes in water by hydrophobic PMMA overlayers.

We describe a poly(methyl methacrylate) (PMMA) dip-coating procedure, which results in surface stabilization of phosphonate and carboxylate derivatives of Ru(II)-polypyridyl complexes surface-bound to mesoporous nanoparticle TiO2 and nanoITO films in aqueous solutions. As shown by contact angle and transmission electron microscopy (TEM) measurements, PMMA oligomers conformally coat the metal-oxide nanoparticles changing the mesoporous films from hydrophilic to hydrophobic. The thickness of the PMMA overlayer on TiO2-Ru(II) can be controlled by changing the wt % of PMMA in the dipcoating solution. There are insignificant perturbations in electrochemical or spectral properties at thicknesses of up to 2.1 nm with the Ru(III/II) couple remaining electrochemically reversible and E1/2 values and current densities nearly unaffected. Surface binding by PMMA overlayers results in stable surface binding even at pH 12 with up to a ∼100-fold enhancement in photostability. As shown by transient absorption measurements, the MLCT excited state(s) of phosphonate derivatized [Ru(bpy)2((4,4'-(OH)2PO)2bpy)](2+) undergo efficient injection and back electron transfer with pH independent kinetics characteristic of the local pH in the initial loading solution.

Visible light driven benzyl alcohol dehydrogenation in a dye-sensitized photoelectrosynthesis cell.

Light-driven dehydrogenation of benzyl alcohol (BnOH) to benzaldehyde and hydrogen has been shown to occur in a dye-sensitized photoelectrosynthesis cell (DSPEC). In the DSPEC, the photoanode consists of mesoporous films of TiO2 nanoparticles or of core/shell nanoparticles with tin-doped In2O3 nanoparticle (nanoITO) cores and thin layers of TiO2 deposited by atomic layer deposition (nanoITO/TiO2). Metal oxide surfaces were coderivatized with both a ruthenium polypyridyl chromophore in excess and an oxidation catalyst. Chromophore excitation and electron injection were followed by cross-surface electron-transfer activation of the catalyst to -Ru(IV)═O(2+), which then oxidizes benzyl alcohol to benzaldehyde. The injected electrons are transferred to a Pt electrode for H2 production. The nanoITO/TiO2 core/shell structure causes a decrease of up to 2 orders of magnitude in back electron-transfer rate compared to TiO2. At the optimized shell thickness, sustained absorbed photon to current efficiency of 3.7% was achieved for BnOH dehydrogenation, an enhancement of ~10 compared to TiO2.

Synthesis and electrocatalytic water oxidation by electrode-bound helical peptide chromophore-catalyst assemblies.

Artificial photosynthesis based on dye-sensitized photoelectrosynthesis cells requires the assembly of a chromophore and catalyst in close proximity on the surface of a transparent, high band gap oxide semiconductor for integrated light absorption and catalysis. While there are a number of approaches to assemble mixtures of chromophores and catalysts on a surface for use in artificial photosynthesis based on dye-sensitized photoelectrosynthesis cells, the synthesis of discrete surface-bound chromophore-catalyst conjugates is a challenging task with few examples to date. Herein, a versatile synthetic approach and electrochemical characterization of a series of oligoproline-based light-harvesting chromophore-water-oxidation catalyst assemblies is described. This approach combines solid-phase peptide synthesis for systematic variation of the backbone, copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) as an orthogonal approach to install the chromophore, and assembly of the water-oxidation catalyst in the final step. Importantly, the catalyst was found to be incompatible with the conditions both for amide bond formation and for the CuAAC reaction. The modular nature of the synthesis with late-stage assembly of the catalyst allows for systematic variation in the spatial arrangement of light-harvesting chromophore and water-oxidation catalyst and the role of intrastrand distance on chromophore-catalyst assembly properties. Controlled potential electrolysis experiments verified that the surface-bound assemblies function as water-oxidation electrocatalysts, and electrochemical kinetics data demonstrate that the assemblies exhibit greater than 10-fold rate enhancements compared to the homogeneous catalyst alone.

Stabilizing chromophore binding on TiO2 for long-term stability of dye-sensitized solar cells using multicomponent atomic layer deposition.

Ambient humidity and high temperature are known to degrade dye-sensitized solar cells (DSSCs) via chromophore desorption. Recently, enhanced dye-attachment to TiO2 surfaces has been realized by coating molecularly functionalized surfaces with inorganic atomic layer deposition (ALD) coatings. Here, we apply this ALD approach to DSSCs and demonstrate that high energy conversion efficiencies can be maintained while significantly extending device lifetimes. While single component ALD layers show improved high-temperature stability, it significantly degraded up to 45% of initial DSSC performance right after ALD. We, however, find that mixed component ALD layers provide initial efficiencies within 90% of their untreated counterparts while still extending device lifetimes. Optimized ALD protection schemes maintain 80% of their initial efficiency after 500 h of thermal aging at 80 °C whereas efficiency of DSSCs with no ALD protection drop below 60% of their initial efficiencies. IR spectroscopy conducted in situ during ALD reveals that carboxylate linker groups transition from unbound or weakly-bound states, respectively, to more strongly bound bidentate structures. This strategy to improve dye-attachment by ALD while maintaining high performance is novel and promising for extending the functional lifetime for DSSCs and other related devices.

Solution-processed, antimony-doped tin oxide colloid films enable high-performance TiO2 photoanodes for water splitting.

Photoelectrochemical (PEC) water splitting and solar fuels hold great promise for harvesting solar energy. TiO2-based photoelectrodes for water splitting have been intensively investigated since 1972. However, solar-to-fuel conversion efficiencies of TiO2 photoelectrodes are still far lower than theoretical values. This is partially due to the dilemma of a short minority carrier diffusion length, and long optical penetration depth, as well as inefficient electron collection. We report here the synthesis of TiO2 PEC electrodes by coating solution-processed antimony-doped tin oxide nanoparticle films (nanoATO) on FTO glass with TiO2 through atomic layer deposition. The conductive, porous nanoATO film-supported TiO2 electrodes, yielded a highest photocurrent density of 0.58 mA/cm(2) under AM 1.5G simulated sunlight of 100 mW/cm(2). This is approximately 3× the maximum photocurrent density of planar TiO2 PEC electrodes on FTO glass. The enhancement is ascribed to the conductive interconnected porous nanoATO film, which decouples the dimensions for light absorption and charge carrier diffusion while maintaining efficient electron collection. Transient photocurrent measurements showed that nanoATO films reduce charge recombination by accelerating transport of photoelectrons through the less defined conductive porous nanoATO network. Owing to the large band gap, scalable solution processed porous nanoATO films are promising as a framework to replace other conductive scaffolds for PEC electrodes.

Controlled electropolymerization of ruthenium(II) vinylbipyridyl complexes in mesoporous nanoparticle films of TiO(2).

Surface-initiated, oligomeric assemblies of ruthenium(II) vinylpolypyridyl complexes have been grown within the cavities of mesoporous nanoparticle films of TiO2 by electrochemically controlled radical polymerization. Surface growth was monitored by cyclic voltammetry as well as UV/Vis and X-ray photoelectron spectroscopy. Polymerization occurs by a radical chain mechanism following cyclic voltammetry scans to negative potentials where reduction occurs at the π* levels of the polypyridyl ligands. Oligomeric growth within the cavities of the TiO2 films occurs until an average of six repeat units are added to the surface-bound initiator site, which is in agreement with estimates of the internal volumes of the pores in the nanoparticle films.

Interfacial energy conversion in Ru(II) polypyridyl-derivatized oligoproline assemblies on TiO2.

Solid-phase peptide synthesis has been applied to the preparation of phosphonate-derivatized oligoproline assemblies containing two different Ru(II) polypyridyl chromophores coupled via "click" chemistry. In water or methanol the assembly adopts the polyproline II (PPII) helical structure, which brings the chromophores into close contact. Excitation of the assembly on ZrO2 at the outer Ru(II) in 0.1 M HClO4 at 25 °C is followed by rapid, efficient intra-assembly energy transfer to the inner Ru(II) (k(EnT) = 3.0 × 10(7) s(-1), implying 96% relative efficiency). The comparable energy transfer rate constants in solution and on nanocrystalline ZrO2 suggest that the PPII structure is retained when bound to ZrO2. On nanocrystalline films of TiO2, excitation at the inner Ru(II) is followed by rapid, efficient injection into TiO2. Excitation of the outer Ru(II) is followed by rapid intra-assembly energy transfer and then by electron injection. The oligoproline/click chemistry approach holds great promise for the preparation of interfacial assemblies for energy conversion based on a family of assemblies having controlled compositions and distances between key functional groups.

Application of the rotating ring-disc-electrode technique to water oxidation by surface-bound molecular catalysts.

We report here the application of a simple hydrodynamic technique, linear sweep voltammetry with a modified rotating-ring-disc electrode, for the study of water oxidation catalysis. With this technique, we have been able to reliably obtain turnover frequencies, overpotentials, Faradaic conversion efficiencies, and mechanistic information from single samples of surface-bound metal complex catalysts.

HPLC-DAD-ESI/MS identification of light harvesting and light screening pigments in the lake sediments at Edmonson Point.

The composition of sedimentary pigments in the Antarctic lake at Edmonson Point has been investigated and compared with the aim to provide a useful analytical method for pigments separation and identification, providing reference data for future assessment of possible changes in environmental conditions. Reversed phase high performance liquid chromatography (HPLC) with electrospray-mass spectrometry (ESI-MS) detection and diode array detection (DAD) has been used to identify light screening and light harvesting pigments. The results are discussed in terms of local environmental conditions.

Dye-Sensitized Nonstoichiometric Strontium Titanate Core-Shell Photocathodes for Photoelectrosynthesis Applications.

A core-shell approach that utilizes a high-surface-area conducting core and an outer semiconductor shell is exploited here to prepare p-type dye-sensitized solar energy cells that operate with a minimal applied bias. Photocathodes were prepared by coating thin films of nanocrystalline indium tin oxide with a 0.8 nm Al2O3 seeding layer, followed by the chemical growth of nonstoichiometric strontium titanate. Films were annealed and sensitized with either a porphyrin chromophore or a chromophore-catalyst molecular assembly consisting of the porphyrin covalently tethered to the ruthenium complex. The sensitized photoelectrodes produced cathodic photocurrents of up to -315 µA/cm2 under simulated sunlight (AM1.5G, 100 mW/cm2) in aqueous media, pH 5. The photocurrent was increased by the addition of regenerative hole donors to the system, consistent with slow interfacial recombination kinetics, an important property of p-type dye-sensitized electrodes.

Kinetic model for astaxanthin aggregation in water-methanol mixtures.

The aggregation of astaxanthin in hydrated methanol was kinetically studied in the temperature range from 10 degrees C to 50 degrees C, at different astaxanthin concentrations and solvent composition. A kinetic model for the formation and transformation of astaxanthin aggregated has been proposed. Spectrophotometric studies showed that monomeric astaxanthin decayed to H-aggregates that after-wards formed J-aggregates when water content was 50% and the temperature lower than 20 degrees C; at higher temperatures, very stable J-aggregates were formed directly. Monomer formed very stable H-aggregates when the water content was greater than 60%; in these conditions H-aggregates decayed into J-aggregates only when the temperature was at least 50 degrees C. Through these findings it was possible to establish that the aggregation reactions took place through a two steps consecutive reaction with first order kinetic constants and that the values of these depended on the solvent composition and temperature.

Structure investigations of binary azeotrope of diethyl amine-acetone by FT-IR and (1)H NMR spectroscopy.

The article shows results of FT-IR and (1)H NMR study for azeotrope diethyl amine-acetone. Changes in chemical shifts and vibrational frequencies for pure diethyl amine, pure acetone and their azeotrope were obtained. The unit-structure of cluster has been suggested on the basis of mole ratio, boiling point depression for azeotrope of diethyl amine and acetone, and comparison between the spectra obtained by FT-IR and (1)H NMR techniques.