A molecular tandem cell for efficient solar water splitting.

Artificial photosynthesis provides a way to store solar energy in chemical bonds. Achieving water splitting without an applied external potential bias provides the key to artificial photosynthetic devices. We describe here a tandem photoelectrochemical cell design that combines a dye-sensitized photoelectrosynthesis cell (DSPEC) and an organic solar cell (OSC) in a photoanode for water oxidation. When combined with a Pt electrode for H2 evolution, the electrode becomes part of a combined electrochemical cell for water splitting, 2H2O → O2 + 2H2, by increasing the voltage of the photoanode sufficiently to drive bias-free reduction of H+ to H2 The combined electrode gave a 1.5% solar conversion efficiency for water splitting with no external applied bias, providing a mimic for the tandem cell configuration of PSII in natural photosynthesis. The electrode provided sustained water splitting in the molecular photoelectrode with sustained photocurrent densities of 1.24 mA/cm2 for 1 h under 1-sun illumination with no applied bias.

A stable dye-sensitized photoelectrosynthesis cell mediated by a NiO overlayer for water oxidation.

In the development of photoelectrochemical cells for water splitting or CO2 reduction, a major challenge is O2 evolution at photoelectrodes that, in behavior, mimic photosystem II. At an appropriate semiconductor electrode, a water oxidation catalyst must be integrated with a visible light absorber in a stable half-cell configuration. Here, we describe an electrode consisting of a light absorber, an intermediate electron donor layer, and a water oxidation catalyst for sustained light driven water oxidation catalysis. In assembling the electrode on nanoparticle SnO2/TiO2 electrodes, a Ru(II) polypyridyl complex was used as the light absorber, NiO was deposited as an overlayer, and a Ru(II) 2,2'-bipyridine-6,6'-dicarboxylate complex as the water oxidation catalyst. In the final electrode, addition of the NiO overlayer enhanced performance toward water oxidation with the final electrode operating with a 1.1 mA/cm2 photocurrent density for 2 h without decomposition under one sun illumination in a pH 4.65 solution. We attribute the enhanced performance to the role of NiO as an electron transfer mediator between the light absorber and the catalyst.

CO2 reduction to acetate in mixtures of ultrasmall (Cu) n ,(Ag) m bimetallic nanoparticles.

Monodispersed mixtures of 6-nm Cu and Ag nanoparticles were prepared by electrochemical reduction on electrochemically polymerized poly-Fe(vbpy)3(PF6)2 film electrodes on glassy carbon. Conversion of the complex to poly-Fe(vbpy)2(CN)2 followed by surface binding of salts of the cations and electrochemical reduction gave a mixture of chemically distinct clusters on the surface, (Cu) m ,(Ag) n |polymer|glassy carbon electrode (GCE), as shown by X-ray photoelectron spectroscopy (XPS) measurements. A (Cu)2,(Ag)3|(80-monolayer-poly-Fe(vbpy)32+|GCE electrode at -1.33 V vs. reversible hydrogen electrode (RHE) in 0.5 M KHCO3, with 8 ppm added benzotriazole (BTA) at 0 °C, gave acetate with a faradaic efficiency of 21.2%.

Stabilized photoanodes for water oxidation by integration of organic dyes, water oxidation catalysts, and electron-transfer mediators.

Stabilized photoanodes for light-driven water oxidation have been prepared on nanoparticle core/shell electrodes with surface-stabilized donor-acceptor chromophores, a water oxidation catalyst, and an electron-transfer mediator. For the electrode, fluorine-doped tin oxide FTO|SnO2/TiO2|-Org1-|1.1 nm Al2O3|-RuP2+-WOC (water oxidation catalyst) with Org1 (1-cyano-2-(4-(diphenylamino)phenyl)vinyl)phosphonic acid), the mediator RuP2+ ([Ru(4,4-(PO3H2)2-2,2-bipyridine)(2,2-bipyridine)2]2+), and the WOC, Ru(bda)(py(CH2)(3or10)P(O3H)2)2 (bda is 2,2-bipyridine-6,6-dicarboxylate with x = 3 or 10), solar excitation resulted in photocurrents of ∼500 µA/cm2 and quantitative O2 evolution at pH 4.65. Related results were obtained for other Ru(II) polypyridyl mediators. For the organic dye PP (5-(4-(dihydroxyphosphoryl)phenyl)-10,15,20-Tris(mesityl)porphyrin), solar water oxidation occurred with a driving force near 0 V.

Chemical approaches to artificial photosynthesis: A molecular, dye-sensitized photoanode for O2 production prepared by layer-by-layer self-assembly.

We describe here the preparation of a family of photoanodes for water oxidation that incorporate an electron acceptor-chromophore-catalyst in single molecular assemblies on nano-indium tin oxide (nanoITO) electrodes on fluorine-doped tin oxide (FTO). The assemblies were prepared by using a layer-by-layer, Atomic Layer Deposition (ALD), self-assembly approach. In the procedure, addition of an electron acceptor viologen derivative followed by a RuII(bpy) chromophore and a pyridyl derivative of the water oxidation catalyst [Ru(bda) (L)2] (bda = 2,2'-bipyridine-6,6'-dicarboxylate)2, were linked by ALD by addition of the bridge precursors TiO2, ZrO2, and Al2O3 as the bridging groups giving the assemblies, FTO|nanoITO|-MV2+-ALD MO2-RuP2 2+-ALD M'O2-WOC. In a series of devices, the most efficient gave water oxidation with an incident photon to current efficiency of 2.2% at 440 nm. Transient nanosecond absorption measurements on the assemblies demonstrated that the slow step in the intra-assembly electron transfer is the electron transfer from the chromophore through the viologen bridge to the nanoITO electrode.

Plasmon-enhanced light-driven water oxidation by a dye-sensitized photoanode.

Dye-sensitized photoelectrosynthesis cells (DSPECs) provide a flexible approach for solar water splitting based on the integration of molecular light absorption and catalysis on oxide electrodes. Recent advances in this area, including the use of core/shell oxide interfacial structures and surface stabilization by atomic layer deposition, have led to improved charge-separation lifetimes and the ability to obtain substantially improved photocurrent densities. Here, we investigate the introduction of Ag nanoparticles into the core/shell structure and report that they greatly enhance light-driven water oxidation at a DSPEC photoanode. Under 1-sun illumination, Ag nanoparticle electrodes achieved high photocurrent densities, surpassing 2 mA cm-2 with an incident photon-to-current efficiency of 31.8% under 450-nm illumination.

Molecular Photoelectrode for Water Oxidation Inspired by Photosystem II.

In artificial photosynthesis, the sun drives water splitting into H2 and O2 or converts CO2 into a useful form of carbon. In most schemes, water oxidation is typically the limiting half-reaction. Here, we introduce a molecular approach to the design of a photoanode that incorporates an electron acceptor, a sensitizer, an electron donor, and a water oxidation catalyst in a single molecular assembly. The strategy mimics the key elements in Photosystem II by initiating light-driven water oxidation with integration of a light absorber, an electron acceptor, an electron donor, and a catalyst in a controlled molecular environment on the surface of a conducting oxide electrode. Visible excitation of the assembly results in the appearance of reductive equivalents at the electrode and oxidative equivalents at a catalyst that persist for seconds in aqueous solutions. Steady-state illumination of the assembly with 440 nm light with an applied bias results in photoelectrochemical water oxidation with a per-photon absorbed efficiency of 2.3%. The results are notable in demonstrating that light-driven water oxidation can be carried out at a conductive electrode in a structure with the functional elements of Photosystem II including charge separation and water oxidation.

Effect of Ionizing Radiation on the Redox Chemistry of Penta- and Hexavalent Americium.

The recent development of facile methods to oxidize trivalent americium to its higher valence states holds promise for the discovery of new chemistries and critical insight into the behavior of the 5f electrons. However, progress in understanding high-valent americium chemistry has been hampered by americium's inherent ionizing radiation field and its concomitant effects on americium redox chemistry. Any attempt to understand high-valent americium reduction and/or disproportionation must account for the effects of these radiolytic processes. Therefore, we present a complete, quantitative, mechanistic description of the radiation-induced redox chemistry of the americyl oxidation states in aerated, aqueous nitric acid, as a function of radiation quality (type and energy) and solution composition using multiscale modeling calculations supported by experiment. The reduction of Am(VI) to Am(V) was found to be most sensitive to the effects of ionizing radiation, undergoing rapid reductions with the steady-state products of aqueous HNO3 radiolysis, i.e., HNO2, H2O2, and HO2•, which dictated its practical lifetime under acidic conditions. In contrast, Am(V) is only susceptible to radiolytic oxidation, mainly through its reactions with NO3•, and is notably radiation-resistant with respect to direct one-electron reduction to produce Am(IV). Our multiscale modeling calculations predict that the lifetime of Am(V) is dictated by its rate of disproportionation, 2AmO2+ + 4Haq+ → AmO22+ + Am4+ + 2H2O, with a fourth-order dependence on [Haq+] in agreement with previous experimental findings, giving an optimized rate coefficient of k = 2.27 × 10-6 M-5 s-1. This disproportionation initially produces Am(IV) and Am(VI) species, but the lack of any spectroscopic evidence in our study for Am(IV) suggests that solvent reduction of this cation occurs rapidly. The ultimate product of all the Am(VI)/Am(V) irradiations is Am(III), which shows great stability in an irradiation field.

Interfacial Deposition of Ru(II) Bipyridine-Dicarboxylate Complexes by Ligand Substitution for Applications in Water Oxidation Catalysis.

Water oxidation is a critical step in artificial photosynthesis and provides the protons and electrons used in reduction reactions to make solar fuels. Significant advances have been made in the area of molecular water oxidation catalysts with a notable breakthrough in the development of Ru(II) complexes that use a planar "bda" ligand (bda is 2,2'-bipyridine-6,6'-dicarboxylate). These Ru(II)(bda) complexes show lower overpotentials for driving water oxidation making them ideal for light-driven applications with a suitable chromophore. Nevertheless, synthesis of heterogeneous Ru(II)(bda) complexes remains challenging. We discuss here a new "bottom-up" synthetic method for immobilizing these catalysts at the surface of a photoanode for use in a dye-sensitized photoelectrosynthesis cell (DSPEC). The procedure provides a basis for rapidly screening the role of ligand variations at the catalyst in order to understand the impact on device performance. The best results of a water-oxidation DSPEC photoanode based on this procedure reached 1.4 mA/cm2 at pH 7 in 0.1 M [PO4H2]-/[PO4H]2-solution with minimal loss in catalytic behavior over 30 min, and produced an incident photon to current efficiency (IPCE) of 24.8% at 440 nm.

Polymer-supported CuPd nanoalloy as a synergistic catalyst for electrocatalytic reduction of carbon dioxide to methane.

Developing sustainable energy strategies based on CO2 reduction is an increasingly important issue given the world's continued reliance on hydrocarbon fuels and the rise in CO2 concentrations in the atmosphere. An important option is electrochemical or photoelectrochemical CO2 reduction to carbon fuels. We describe here an electrodeposition strategy for preparing highly dispersed, ultrafine metal nanoparticle catalysts on an electroactive polymeric film including nanoalloys of Cu and Pd. Compared with nanoCu catalysts, which are state-of-the-art catalysts for CO2 reduction to hydrocarbons, the bimetallic CuPd nanoalloy catalyst exhibits a greater than twofold enhancement in Faradaic efficiency for CO2 reduction to methane. The origin of the enhancement is suggested to arise from a synergistic reactivity interplay between Pd-H sites and Cu-CO sites during electrochemical CO2 reduction. The polymer substrate also appears to provide a basis for the local concentration of CO2 resulting in the enhancement of catalytic current densities by threefold. The procedure for preparation of the nanoalloy catalyst is straightforward and appears to be generally applicable to the preparation of catalytic electrodes for incorporation into electrolysis devices.

Base-enhanced catalytic water oxidation by a carboxylate-bipyridine Ru(II) complex.

In aqueous solution above pH 2.4 with 4% (vol/vol) CH3CN, the complex [Ru(II)(bda)(isoq)2] (bda is 2,2'-bipyridine-6,6'-dicarboxylate; isoq is isoquinoline) exists as the open-arm chelate, [Ru(II)(CO2-bpy-CO2(-))(isoq)2(NCCH3)], as shown by (1)H and (13)C-NMR, X-ray crystallography, and pH titrations. Rates of water oxidation with the open-arm chelate are remarkably enhanced by added proton acceptor bases, as measured by cyclic voltammetry (CV). In 1.0 M PO4(3-), the calculated half-time for water oxidation is ∼7 µs. The key to the rate accelerations with added bases is direct involvement of the buffer base in either atom-proton transfer (APT) or concerted electron-proton transfer (EPT) pathways.

Light-Driven Water Splitting Mediated by Photogenerated Bromine.

Light-driven water splitting was achieved using a dye-sensitized mesoporous oxide film and the oxidation of bromide (Br- ) to bromine (Br2 ) or tribromide (Br3- ). The chemical oxidant (Br2 or Br3- ) is formed during illumination at the photoanode and used as a sacrificial oxidant to drive a water oxidation catalyst (WOC), here demonstrated using [Ru(bda)(pic)2 ], (1; pic=picoline, bda=2,2'-bipyridine-6,6'-dicarboxylate). The photochemical oxidation of bromide produces a chemical oxidant with a potential of 1.09 V vs. NHE for the Br2 /Br- couple or 1.05 V vs. NHE for the Br3- /Br- couple, which is sufficient to drive water oxidation at 1 (RuV/IV ≈1.0 V vs. NHE at pH 5.6). At pH 5.6, using a 0.2 m acetate buffer containing 40 mm LiBr and the [Ru(4,4'-PO3 H2 -bpy)(bpy)2 ]2+ (RuP2+ , bpy=2,2'-bipyridine) chromophore dye on a SnO2 /TiO2 core-shell electrode resulted in a photocurrent density of around 1.2 mA cm-2 under approximately 1 Sun illumination and a Faradaic efficiency upon addition of 1 of 77 % for oxygen evolution.

Layer-by-Layer Molecular Assemblies for Dye-Sensitized Photoelectrosynthesis Cells Prepared by Atomic Layer Deposition.

In a dye sensitized photoelectrosynthesis cell (DSPEC), the relative orientation of the catalyst and chromophore plays an important role in determining the device efficiency. Here we introduce a new, robust atomic layer deposition (ALD) procedure for the preparation of molecular chromophore-catalyst assemblies on wide bandgap semiconductors. In this procedure, solution deposited, phosphonate derivatized metal complexes on metal oxide surfaces are treated with reactive metal reagents in the gas phase by ALD to form an outer metal ion bridging group, which can bind a second phosphonate containing species from solution to establish a R1-PO2-O-M-O-PO2-R2 type surface assembly. With the ALD procedure, assemblies bridged by Al(III), Sn(IV), Ti(IV), or Zr(IV) metal oxide units have been prepared. To evaluate the performance of this new type of surface assembly, intra-assembly electron transfer was investigated by transient absorption spectroscopy, and light-driven water splitting experiments under steady-state illumination were conducted. A SnO2 bridged assembly on SnO2/TiO2 core/shell electrodes undergoes light-driven water oxidation with an incident photon to current efficiency (IPCE) of 17.1% at 440 nm. Light-driven water reduction with a ruthenium trisbipyridine chromophore and molecular Ni(II) catalyst on NiO films was also used to produce H2. Compared to conventional solution-based procedures, the ALD approach offers significant advantages in scope and flexibility for the preparation of stable surface structures.

Kinetics of the Autoreduction of Hexavalent Americium in Aqueous Nitric Acid.

The rate of reduction of hexavalent 243Am due to self-radiolysis was measured across a range of total americium and nitric acid concentrations. These so-called autoreduction rates exhibited zero-order kinetics with respect to the concentration of hexavalent americium, and pseudo-first-order kinetics with respect to the total concentration of americium. However, the rate constants did vary with nitric acid concentration, resulting in values of 0.0048 ± 0.0003, 0.0075 ± 0.0005, and 0.0054 ± 0.0003 h-1 for 1.0, 3.0, and 6.5 M HNO3, respectively. This indicates that reduction is due to reaction of hexavalent americium with the radiolysis products of total americium decay. The concentration changes of Am(III), Am(V), and Am(VI) were determined by UV-vis spectroscopy. The Am(III) molar extinction coefficients are known; however, the unknown values for the Am(V) and Am(VI) absorbances across the studied range of nitric acid concentrations were determined by sensitivity analysis in which a mass balance with the known total americium concentration was obtained. The new extinction coefficients and reduction rate constants have been tabulated here. Multiscale radiation chemical modeling using a reaction set with both known and optimized rate coefficients was employed to achieve excellent agreement with the experimental results, and indicates that radiolytically produced nitrous acid from nitric acid radiolysis and hydrogen peroxide from water radiolysis are the important reducing agents. Since these species also react with each other, modeling indicated that the highest concentrations of these species available for Am(VI) reduction occurred at 3.0 M HNO3. This is in agreement with the empirical finding that the highest rate constant for autoreduction occurred at the intermediate acid concentration.

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.

Two Electrode Collector-Generator Method for the Detection of Electrochemically or Photoelectrochemically Produced O2.

A dual working electrode technique for the in situ production and quantification of electrochemically or photoelectrochemically produced O2 is described. This technique, termed a collector-generator cell, utilizes a transparent fluorine doped tin oxide electrode to sense O2. This setup is specifically designed for detecting O2 in dye sensitized photoelectrosynthesis cells.

Analysis of Homogeneous Water Oxidation Catalysis with Collector-Generator Cells.

A collector-generator (C-G) technique has been applied to determine the Faradaic efficiencies for electrocatalytic O2 production by the homogeneous water oxidation catalysts Ru(bda)(isoq)2 (1; bda = 2,2'-bipyridine and isoq = isoquinoline) and [Ru(tpy)(bpz)(OH2)](2+) (2; tpy = 2,2':6',2″-terpyridine and bpz = 2,2'-bipyrazine). This technique uses a custom-fabricated cell consisting of two fluorine-doped tin oxide (FTO) working electrodes separated by 1 mm with the conductive sides facing each other. With a catalyst in solution, water oxidation occurs at one FTO electrode under a sufficient bias to drive O2 formation by the catalyst; the O2 formed then diffuses to the second FTO electrode poised at a potential sufficiently negative to drive O2 reduction. A comparison of the current versus time response at each electrode enables determination of the Faradaic efficiency for O2 production with high concentrations of supporting electrolyte important for avoiding capacitance effects between the electrodes. The C-G technique was applied to electrocatalytic water oxidation by 1 in the presence of the electron-transfer mediator Ru(bpy)3(2+) in both unbuffered aqueous solutions and with the added buffer bases HCO3(-), HPO4(2-), imidazole, 1-methylimidazole, and 4-methoxypyridine. HCO3(-) and HPO4(2-) facilitate water oxidation by atom-proton transfer (APT), which gave Faradaic yields of 100%. With imidazole as the buffer base, coordination to the catalyst inhibited water oxidation. 1-Methylimidazole and 4-methoxypyridine gave O2 yields of 55% and 76%, respectively, with the lower Faradaic efficiencies possibly due to competitive C-H oxidation of the bases. O2 evolution by catalyst 2 was evaluated at pH 12 with 0.1 M PO4(3-) and at pH 7 in a 0.1 M H2PO4(-)/HPO4(2-) buffer. At pH 12, at an applied potential of 0.8 V vs SCE, water oxidation by the Ru(IV)(O)(2+) form of the catalyst gave O2 in 73% yield. In a pH 7 solution, water oxidation at 1.4 V vs SCE, which is dominated by Ru(V)(O)(3+), gave O2 with an efficiency of 100%. The lower efficiency for Ru(IV)(O)(2+) at pH 12 may be due to competitive oxidation of a polypyridyl ligand.

One-electron activation of water oxidation catalysis.

Rapid water oxidation catalysis is observed following electrochemical oxidation of [Ru(II)(tpy)(bpz)(OH)](+) to [Ru(V)(tpy)(bpz)(O)](3+) in basic solutions with added buffers. Under these conditions, water oxidation is dominated by base-assisted Atom Proton Transfer (APT) and direct reaction with OH(-). More importantly, we report here that the Ru(IV)═O(2+) form of the catalyst, produced by 1e(-) oxidation of [Ru(II)(tpy)(bpz)(OH2)](2+) to Ru(III) followed by disproportionation to [Ru(IV)(tpy)(bpz)(O)](2+) and [Ru(II)(tpy)(bpz)(OH2)](2+), is also a competent water oxidation catalyst. The rate of water oxidation by [Ru(IV)(tpy)(bpz)(O)](2+) is greatly accelerated with added PO4(3-) with a turnover frequency of 5.4 s(-1) reached at pH 11.6 with 1 M PO4(3-) at an overpotential of only 180 mV.

Electrocatalytic water oxidation by a monomeric amidate-ligated Fe(III)-aqua complex.

The six-coordinate Fe(III)-aqua complex [Fe(III)(dpaq)(H2O)](2+) (1, dpaq is 2-[bis(pyridine-2-ylmethyl)]amino-N-quinolin-8-yl-acetamido) is an electrocatalyst for water oxidation in propylene carbonate-water mixtures. An electrochemical kinetics study has revealed that water oxidation occurs by oxidation to Fe(V)(O)(2+) followed by a reaction first order in catalyst and added water, respectively, with ko = 0.035(4) M(-1) s(-1) by the single-site mechanism found previously for Ru and Ir water oxidation catalysts. Sustained water oxidation catalysis occurs at a high surface area electrode to give O2 through at least 29 turnovers over an 15 h electrolysis period with a 45% Faradaic yield and no observable decomposition of the catalyst.

Water oxidation and oxygen monitoring by cobalt-modified fluorine-doped tin oxide electrodes.

Electrocatalytic water oxidation occurs at fluoride-doped tin oxide (FTO) electrodes that have been surface-modified by addition of Co(II). On the basis of X-ray photoelectron spectroscopy and transmission electron microscopy measurements, the active surface site appears to be a single site or small-molecule assembly bound as Co(II), with no evidence for cobalt oxide film or cluster formation. On the basis of cyclic voltammetry measurements, surface-bound Co(II) undergoes a pH-dependent 1e(-)/1H(+) oxidation to Co(III), which is followed by pH-dependent catalytic water oxidation. O2 reduction at FTO occurs at -0.33 V vs NHE, allowing for in situ detection of oxygen as it is formed by water oxidation on the surface. Controlled-potential electrolysis at 1.61 V vs NHE at pH 7.2 resulted in sustained water oxidation catalysis at a current density of 0.16 mA/cm(2) with 29,000 turnovers per site over an electrolysis period of 2 h. The turnover frequency for oxygen production per Co site was 4 s(-1) at an overpotential of 800 mV at pH 7.2. Initial experiments with Co(II) on a mesoporous, high-surface-area nanoFTO electrode increased the current density by a factor of ~5.