Photon Upconversion with a Low Threshold Excitation Intensity in Plain Water.

A triplet-triplet annihilation-based photon upconversion (TTA-UC) system with a low threshold excitation intensity () in plain water was developed. Water-soluble anionic porphyrin (PdTPPS) and diphenylanthracene (DCDPA) derivatives were used as light absorbers and emitter molecules, respectively, and no additives such as surfactants were required. The phosphorescence emission from PdTPPS under an excitation wavelength of 528 nm was quenched by DCDPA, resulting in triplet energy transfer, whereas fluorescence from DCDPA was observed in a short wavelength region (400-500 nm).

Mechanism of H dissociation-induced O-O bond formation via intramolecular coupling of vicinal hydroxo ligands on low-valent Ru(III) centers.

The understanding of O-O bond formation is of great importance for revealing the mechanism of water oxidation in photosynthesis and for developing efficient catalysts for water oxidation in artificial photosynthesis. The chemical oxidation of the Ru(OH)(OH) core with the vicinal OH and OH ligands was spectroscopically and theoretically investigated to provide a mechanistic insight into the O-O bond formation in the core. We demonstrate O-O bond formation at the low-valent Ru(OH) core with the vicinal OH ligands to form the Ru(μ-OOH) core with a μ-OOH bridge.

An Artificial Z-Scheme Constructed from Dye-Sensitized Metal Oxide Nanosheets for Visible Light-Driven Overall Water Splitting.

Sensitization of a wide-gap oxide semiconductor with a visible-light-absorbing dye has been studied for decades as a means of producing H from water. However, efficient overall water splitting using a dye-sensitized oxide photocatalyst has remained an unmet challenge. Here we demonstrate visible-light-driven overall water splitting into H and O using HCaNbO nanosheets sensitized by a Ru(II) tris-diimine type photosensitizer, in combination with a WO-based water oxidation photocatalyst and a triiodide/iodide redox couple.

Multi-potential-step chronocoulospectrometry for electrocatalytic water oxidation by a mononuclear ruthenium aquo complex immobilized on a mesoporous ITO electrode.

A new mononuclear Ru aquo complex [Ru(COtpy)(Hdcbpy)(OH)] with 4,4'-dicarboxy-2,2'-bipyridine (Hdcbpy) and 4'-octyloxy-2,2':6',2''-terpyridine (COtpy) ligands was synthesized to investigate electrocatalytic water oxidation by the complex immobilized on a mesoporous indium-doped tin oxide (meso-ITO) electrode using a multi-potential-step chronocoulospectrometric (MPSCCS) technique. UV-visible absorption spectroscopic data indicated that [Ru(COtpy)(dcbpy)(OH)] (RuOH) is deprotonated to [Ru(COtpy)(dcbpy)(OH)] (RuOH) on the meso-ITO surface even at pH 5.9 of the electrolyte solution.

Critical Hammett Electron-Donating Ability of Substituent Groups for Efficient Water Oxidation Catalysis by Mononuclear Ruthenium Aquo Complexes.

[Ru(Rtpy)(bpy)(HO)] (; bpy = 2,2'-bipyridine, and Rtpy = 2,2':6',2″-terpyridine derivatives) complexes with a variety of 4'-substituent groups on Rtpy were synthesized and characterized to reveal the effects of substituents on their structures, physicochemical properties, and catalytic activities for water oxidation. The geometric structures of are not considerably influenced by the electron-donating ability of the 4'-substituent groups on Rtpy. Similar multistep proton-coupled electron transfer reactions were observed for , and the redox potentials for each oxidation step tended to decrease with an increase in the electron-donating ability of the substituent, which is explained by the increased electron density on the Ru center by electron-donating groups, stabilizing the positive charge that builds up upon oxidation.

Preparation of Stable Silver Nanoparticles Having Wide Red-To-Near-Infrared Extinction.

The synthesis of silver nanoparticles (AgNPs) within the interlayer space of transparent layered titania nanosheet (TNS) films is investigated. A considerable number of silver ions (≈70% against the cation exchange capacity of the TNS) are intercalated in the TNS films using methyl-viologen-containing TNSs as a precursor. The silver ion (Ag)-containing TNS films are treated with aqueous sodium tetrahydroborate (NaBH), resulting in a gradual color change to bright blue.

Visible Light-Driven Water Oxidation on an In Situ N -Intercalated WO Nanorod Photoanode Synthesized by a Dual-Functional Structure-Directing Agent.

With a view to developing a photoanode for visible light-driven water oxidation in solar water splitting cells, pure-monoclinic WO nanorod crystals with N intercalated into the lattice were synthesized by using hydrazine with a dual functional role-as an N atom source for the in situ N intercalation and as a structure-directing agent for the nanorod architecture-to gain higher incident photon-to-current conversion efficiency at 420 nm than with most previously reported WO electrodes.

Superior Inorganic Ion Cofactors of Tetraborate Species Attaining Highly Efficient Heterogeneous Electrocatalysis for Water Oxidation on Cobalt Oxyhydroxide Nanoparticles.

A heterogeneous catalyst incorporating an inorganic ion cofactor for electrochemical water oxidation was exploited using a CoO(OH) nanoparticle layer-deposited electrode. The significant catalytic current for water oxidation was generated in a NaBO solution at pH 9.4 when applying 0.

Mechanistic Insight into Reversible Core Structural Changes of Dinuclear μ-Hydroxoruthenium(II) Complexes with a 2,8-Di-2-pyridyl-1,9,10-anthyridine Backbone Prior to Water Oxidation Catalysis.

proximal,proximal-(p,p)-[Ru(tpy)LXY] (tpy = 2,2';6',2″-terpyridine, L = 5-phenyl-2,8-di-2-pyridyl-1,9,10-anthyridine, and X and Y = other coordination sites) yields the structurally and functionally unusual Ru(μ-OH)Ru core, which is capable of catalyzing water oxidation with key water insertion to the core (Inorg. Chem. 2015, 54, 7627).

Light Energy Accumulation from Pyrene Derivative to Tris(bipyridine)ruthenium on Clay Surface.

A novel type of energy donor-acceptor system on a clay surface has been prepared. The energy transfer between an energy-donating cationic pyrene derivative (An-Py) and an energy-accepting tris(bipyridine)ruthenium complex (Ru) on the clay surface was investigated using absorption, emission, and lifetime measurements. An obvious energy transfer was observed, and one Ru molecule quenched the emission from five molecules of An-Py with an emission quenching efficiency of 85% on the clay surface.

Dual-Functional Surfactant-Templated Strategy for Synthesis of an In Situ N -Intercalated Mesoporous WO Photoanode for Efficient Visible-Light-Driven Water Oxidation.

N -Intercalated crystalline mesoporous tungsten trioxide (WO ) was synthesized by a thermal decomposition technique with dodecylamine (DDA) as a surfactant template with a dual role as an N-atom source for N intercalation, alongside its conventional structure-directing role (by micelle formation) to induce a mesoporous structure. N physisorption analysis showed that the specific surface area (57.3 m  g ) of WO templated with DDA (WO -DDA) is 2.

In Situ Synthesis of Gold Nanoparticles without Aggregation in the Interlayer Space of Layered Titanate Transparent Films.

Combinations of metal oxide semiconductors and gold nanoparticles (AuNPs) have been investigated as new types of materials. The in situ synthesis of AuNPs within the interlayer space of semiconducting layered titania nanosheet (TNS) films was investigated here. Two types of intermediate films (i.

Carbonate Ions Induce Highly Efficient Electrocatalytic Water Oxidation by Cobalt Oxyhydroxide Nanoparticles.

Synthetic models of oxygen evolving complex (OEC) are used not only to gain better understanding of the mechanism and the roles of cofactors for water oxidation in photosynthesis, but also as water oxidation catalysts to realize artificial photosynthesis, which is anticipated as a promising solar fuel production system. However, although much attention has been paid to the composition and structure of active sites for development of heterogeneous OEC models, the cofactors, which are essential for water oxidation by the photosynthetic OEC, remain little studied. The high activity of CoO(OH) nanoparticles for electrocatalytic water oxidation is shown to be induced by a CO cofactor.

Characterization of Interfacial Charge-Transfer Photoexcitation of Polychromium-Oxo-Electrodeposited TiO as an Earth-Abundant Photoanode for Water Oxidation Driven by Visible Light.

Polychromium-oxo-deposited TiO (Cr O /TiO ) electrodes were fabricated by a simple electrochemical technique by using different TiO basal electrodes (anatase, rutile, and mixed polymorphic phases P25) as earth-abundant photoanodes for visible-light-driven water oxidation. The high-resolution transmission electron microscopy (HR-TEM) observation illustrated that an Cr O layer with approximately 2-3 nm thickness was formed on the surface of the crystalline TiO particles. Upon visible-light irradiation of the electrodes, the photoanodic current based on water oxidation was generated at the Cr O /TiO electrodes.

Intercrystal self-assembly for the design of high-quality nickel molybdate nanocrystals.

Nanowire of nickel molybdate hydrate, being recognized as an emerging supercapacitor material, was synthesized from the intercrystal self-assembly process (commonly referred to as oriented aggregation or attachment). The detailed lattice image of a NiMoO4·0.75H2O nanowire and the intermediate nanostructure before reaching the interplanar binding were successfully captured by means of high-resolution transmission and scanning electron microscopies.

New Series of Dinuclear Ruthenium(II) Complexes Synthesized Using Photoisomerization for Efficient Water Oxidation Catalysis.

A new series of proximal,proximal-[Ru2(tpy)2(L)XY](n+) (p,p-Ru2XY, tpy = 2,2':6',2″-terpyridine, L = 5-phenyl-2,8-di(2-pyridyl)-1,9,10-anthyridine, X and Y = other coordination sites) were synthesized using photoisomerization of a mononuclear complex. The p,p-Ru2XY complexes undergo unusual reversible bridge-exchange reactions to generate p,p-Ru2(μ-Cl), p,p-Ru2(μ-OH), and p,p-Ru2(OH)(OH2) with μ-Cl, μ-OH, as well as hydroxo and aquo ligands at X and Y sites of p,p-Ru2XY, respectively. The geometric and electronic structures of these complexes were characterized based on UV-vis and (1)H NMR spectra, X-ray crystallography, and density functional theory (DFT) calculations.

Sustainable synthesis of niobia thin films with open mesopore channels.

The current approaches to electrochemically synthesizing valve metal-derived nanochannel films with longitudinal nanospaces aligned at a right angle to planar substrates rely on highly toxic fluoride compounds and require severe reaction conditions. Herein, we report on a fluoride-free, room-temperature electrochemical synthesis of a genuine mesoporous niobia thin film from the parent metal. The electrochemical reaction is driven by only a 1 V bias with respect to a Pt counter electrode in an aqueous solution.

Open pore architecture of an ordered mesoporous IrO2 thin film for highly efficient electrocatalytic water oxidation.

We report the first accessible channel-like open pore architecture of ordered 2D hexagonal mesoporous IrO2 films and its utilization as an efficient anode for electrocatalytic water oxidation. A well-ordered mesostructure of circa 7 nm pores were obtained by a facile one-pot soft-templating strategy, employing a [Ir(OH)6](2-) precursor stabilized by a triblock copolymer "Pluronic F127" as a pore-directing template. A mesoporous IrO2 film calcined at 400 °C (∼70 nm thick) affords a high surface area of 512 m(2)  cm(-3) and 2 times higher O2 evolution during the electrocatalytic water oxidation relative to an untemplated IrO2 coating film.

Remarkable stimulation of emission quenching on a clay surface.

Tetra-cationic pyrene derivative (Py(4+)) and tris(bipyridine)ruthenium(II) (Ru(2+)) were hybridized onto the surface of a synthesized clay. We observed the remarkable stimulation of excited Py(4+) emission quenching on the clay surface, with a very large apparent quenching rate constant (kq = 7.4 ± 0.

A visible-light harvesting system for CO2 reduction using a Ru(II) -Re(I) photocatalyst adsorbed in mesoporous organosilica.

A photocatalytic system for CO2 reduction exhibiting visible-light harvesting was developed by preparing a hybrid consisting of a supramolecular metal complex as photocatalyst and periodic mesoporous organosilica (PMO) as light harvester. A Ru(II) Re(I) binuclear complex (RuRe) with methylphosphonic acid anchor groups was adsorbed on acridone or methylacridone embedded in the walls of PMO mesochannels to yield the hybrid structure. The embedded organic groups absorbed visible light, and the excitation energy was funneled to the Ru units.

Unique and facile solvothermal synthesis of mesoporous WO3 using a solid precursor and a surfactant template as a photoanode for visible-light-driven water oxidation.

Mesoporous tungsten trioxide (WO3) was prepared from tungstic acid (H2WO4) as a tungsten precursor with dodecylamine (DDA) as a template to guide porosity of the nanostructure by a solvothermal technique. The WO3 sample (denoted as WO3-DDA) prepared with DDA was moulded on an electrode to yield efficient performance for visible-light-driven photoelectrochemical (PEC) water oxidation. Powder X-ray diffraction (XRD) data of the WO3-DDA sample calcined at 400°C indicate a crystalline framework of the mesoporous structure with disordered arrangement of pores.

Hybridization between periodic mesoporous organosilica and a Ru(II) polypyridyl complex with phosphonic acid anchor groups.

A new method for the hybridization of a ruthenium(II) polypyridyl complex ([Ru(bpy)2((CH2PO3H2)2-bpy)](2+) (RuP2(2+): bpy =2,2'-bipyridine; (CH2PO3H2)2-bpy =2,2'-bipyridine-4,4'di(metylphosphonic acid)) with biphenylene-bearing periodic mesoporous organosilica (Bp-PMO made from 4,4'bis(triethoxysilyl)biphenyl [(C2H5O)3Si-(C6H4)2-Si(OC2H5)3]) was developed. Efficient and secure fixation of the ruthenium(II) complex with methylphosphonic acid groups (RuP2(2+)) in the mesopores of Bp-PMO occurred. This method introduced up to 660 μmol of RuP2(2+) in 1 g of Bp-PMO.

Visible-light-driven water oxidation at a polychromium-oxo-electrodeposited TiO2 electrode as a new type of earth-abundant photoanode.

A polychromium-oxo-deposited TiO2 electrode was fabricated as an earth-abundant photoanode for visible-light-driven water oxidation by a simple electrochemical technique. The photoelectrocatalytic water oxidation could occur based on a specific interfacial charge transfer (IFCT) from a Cr(III) to the TiO2 conduction band.