A Molecular Z-Scheme Artificial Photosynthetic System Under the Bias-Free Condition for CO2 Reduction Coupled with Two-electron Water Oxidation: Photocatalytic Production of CO/HCOOH and H2 O2.

Bio-inspired molecular-engineered systems have been extensively investigated for the half-reactions of H2 O oxidation or CO2 reduction with sacrificial electron donors/acceptors. However, there has yet to be reported a device for dye-sensitized molecular photoanodes coupled with molecular photocathodes in an aqueous solution without the use of sacrificial reagents. Herein, we will report the integration of SnIV - or AlIII -tetrapyridylporphyrin (SnTPyP or AlTPyP) decorated tin oxide particles (SnTPyP/SnO2 or AlTPyP/SnO2 ) photoanode with the dye-sensitized molecular photocathode on nickel oxide particles containing [Ru(diimine)3 ]2+ as the light-harvesting unit and [Ru(diimine)(CO)2 Cl2 ] as the catalyst unit covalently connected and fixed within poly-pyrrole layer (RuCAT-RuC2 -PolyPyr-PRu/NiO). The simultaneous irradiation of the two photoelectrodes with visible light resulted in H2 O2 on the anode and CO, HCOOH, and H2 on the cathode with high Faradaic efficiencies in purely aqueous conditions without any applied bias is the first example of artificial photosynthesis with only two-electron redox reactions.

Molecular Characteristics of Water-Insoluble Tin-Porphyrins for Designing the One-Photon-Induced Two-Electron Oxidation of Water in Artificial Photosynthesis.

Faced with the new stage of water oxidation by molecular catalysts (MCs) in artificial photosynthesis to overcome the bottle neck issue, the "Photon-flux density problem of sunlight," a two-electron oxidation process forming H2O2 in place of the conventional four-electron oxidation evolving O2 has attracted much attention. The molecular characteristics of tin(IV)-tetrapyridylporphyrin (SnTPyP), as one of the most promising MCs for the two-electron water oxidation, has been studied in detail. The protolytic equilibria among nine species of SnTPyP, with eight pKa values on the axial ligands' water molecules and peripheral pyridyl nitrogen atoms in both the ground and excited states, have been clarified through the measurements of UV-vis, fluorescence, 1H NMR, and dynamic fluorescence decay behaviour. The oxidation potentials in the Pourbaix diagram and spin densities by DFT calculation of the one-electron oxidized form of each nine species have predicted that the fully deprotonated species ([SnTPyP(O-)2]2-) and the singly deprotonated one ([SnTPyP(OH)(O-)]-) serve as the most favourable MCs for visible light-induced two-electron water oxidation when they are adsorbed on TiO2 for H2 formation or SnO2 for Z-scheme CO2 reduction in the molecular catalyst sensitized system of artificial photosynthesis.

Optically Transparent Colloidal Dispersion of Titania Nanoparticles Storable for Longer than One Year Prepared by Sol/Gel Progressive Hydrolysis/Condensation.

The molecular catalyst sensitized system (MCSS), where an excited molecular catalyst adsorbed on a semiconductor such as TiO2 injects electrons to the conduction band of the semiconductor leading to hydrogen evolution/CO2 reduction coupled with an oxidation of water on the molecular catalyst, has been one of the most probable candidates in the approach to artificial photosynthesis. For a full utilization of visible light, however, a serious light scattering of the aqueous suspension of TiO2 in the visible region, which is generally experienced, should be avoided. Here, we report a preparation of optically transparent colloidal dispersion of TiO2 by the sol/gel reaction of TiCl4 through progressive hydrolysis/condensation under the basic condition without any calcination processes. The TiO2 nanoparticles (TiO2(NPs)) obtained were characterized as an amorphous particle (∼10-15 nm) having a microcrystal domain of anatase within several nm by XRD, Raman spectroscopies, XRF, XAFS, TG/DTA, and HRTEM, respectively. The energy-resolved distribution of carrier electron traps in TiO2(NPs) as a fingerprint of TiO2 was characterized through reversed double-beam photo-acoustic spectroscopy to have a close similarity to that of TiO2(ST-01) as well as the observation of carrier traps by transient absorption spectroscopy. Though the powder TiO2(NP) itself was not dispersed well in aqueous solution, the wet TiO2(NPs) as prepared before being dried up provided a completely transparent aqueous dispersion under the acidic condition (1 M HCl). Addition of methanol enabled the colloidal dispersion (TiO2(NPs, MeOH/H2O, 0.1 M HCl)) to keep the optical transparency for longer than 1 year (550 days), which is the first example of TiO2 dispersion storable for such a long period. TiO2(NPs, MeOH/H2O) exhibited a moderate photocatalytic reactivity of H2 evolution with a quantum yield of ∼2.6% upon 365 nm light irradiation. An optically transparent thin film of TiO2(NPs, MeOH/H2O) was also successfully prepared on a glass plate to exhibit an enhanced hydrophilicity upon UV light irradiation.

Heat trapping in a nano-layered microenvironment: estimation of temperature by thermal sensing molecules.

We have previously found reversible photo-induced expansion and contraction of organic/inorganic clay hybrids, and even sliding of niobate nano-sheets at the macroscopic level of organic/inorganic niobate hybrids, induced by the molecular photo-isomerization of the polyfluoroalkylated azobenzene derivative (C3F-Azo-C6H) intercalated within the interlayer, which is viewed as an artificial muscle model unit. Based on systematic investigations of the steady state photo-isomerization and transient behavior of the reaction, we comprehended that the phenomena is caused by trapping of excess energy liberated during the isomerization, as well as the relaxation processes upon excitation of azobenzene chromophores in the interlayers of the hybrid. In this paper, quantitative estimation of transient 'heat' trapped in various microenvironments has been studied by each co-intercalation of temperature sensing dye molecules - rhodamine B (RhB) or tris(bipyridine)ruthenium(ii) chloride (Rubpy) with C3F-Azo-C6H within clay (SSA) nano-layers. The amount of dye molecules co-intercalated was kept to trace amounts that did not alter the bi-layered structure of the hybrid. The temperature of the microenvironment surrounding the probe molecules was estimated from the emission lifetime analysis. The evidently reduced emission lifetimes in C3F-Azo-C6H/SSA and C3H-Azo-C6H/SSA hybrids in the film state, indicated the elevation of temperature of the microenvironment upon excitation of the chromophores, which demonstrated our previous hypothesis rationalizing that the high reactivity of isomerization in the hybrid film state is caused by heat trapping via multi-step dissipation of the excess energy. With the hybrid of a hydrocarbon analogue (C3H-Azo-C6H), a distinct difference in temperature gradient was found to show the crucial role of the perfluoroalkyl chain of the surfactant that traps the excess energy to retard its dissipation leading to three-dimensional morphological motion.

Synthesis of a photo-responsive single-walled nanoscroll and its photo-reactivity in a nano-layered microenvironment.

A photo-responsive nanoscroll composed of niobate nanosheets and a polyfluoroalkyl azobenzene derivative (C3F-Azo-C6H) is one of the most interesting layered materials because the reversible winding and unwinding motion could be efficiently induced by photo-irradiations. Previously, we have studied a double-walled nanoscroll (DWNS) of niobate that could be synthesized by the intercalation of a cationic polyfluorinated surfactant only into the interlayer I of the layered niobate among the two interlayers, I and II. In this study, we have successfully synthesized another novel photo-responsive single-walled nanoscroll (SWNS) of niobate by a stepwise guest-guest ion-exchange method. All niobate nanosheets that were exfoliated at both interlayers I and II were efficiently converted to nanoscrolls by the intercalation of C3F-Azo-C6H. The synthetic yield has been quantitatively estimated. Though the photo-isomerization reaction of C3F-Azo-C6H was induced in the SWNS, its photo-reactivity was the lowest when compared with those of the nanosheet-stacked film and the DWNS. The photo-reactivity of C3F-Azo-C6H decreased in the order of DWNS > nanosheet-stacked film > SWNS. The different flexibility of the layered miroenvironment might influence the photo-reactivity of C3F-Azo-C6H in the niobate hybrid. The SWNS exhibited a reversible expansion and shrinkage of its interlayer spaces upon photo-irradiation, while the winding and unwinding motion was not observed, contrary to the DWNS. The direction of the expansion and shrinkage of the interlayer of the SWNS was opposite to those of the nanosheet-stacked film and the DWNS. Based on the experimental results, the tilt angle of C3F-Azo-C6H against the nanosheet surface and the matching structures of the top and bottom surfaces of the nanosheet could be the probable key factors that control the photo-reactivity of C3F-Azo-C6H in the layered microenvironment; the morphological changes of the nano hybrids was also discussed.

Promotive Effect of Bicarbonate Ion on Two-Electron Water Oxidation to Form H2 O2 Catalyzed by Aluminum Porphyrins.

Two-electron water oxidation initiated by one-electron oxidation of aluminum porphyrins (AlTMPyP) is an alternative water oxidation to the conventional four-electron pathway and could help to avoid the bottleneck subject of photon-flux density in artificial photosynthesis. Here, a dramatic enhancement of the reactivity by bicarbonate ion in the two-electron water oxidation to form H2 O2 is reported. An addition of sodium carbonate (Na2 CO3 ) controlled both catalytic current and product selectivity of the two-electron water oxidation to enhance the activity of AlTMPyP at pH≈10-11. Controlled potential electrolysis experiments at different concentrations of Na2 CO3 (10-100 mm) showed that peroxide selectivity was improved up to approximately 73 % by the increase of [Na2 CO3 ] added to the system. The promotion of the reaction cycle was induced by an enhanced dynamic capturing of H2 O2 from the hydroperoxy complex of AlTMPyP through an attack of a bicarbonate ion. The detailed electrochemical studies and product selectivity indicated that the bicarbonate ion served as a good cofactor for producing H2 O2 from water. At stronger alkaline conditions (pH 12.5), however, a retardative effect of the addition of Na2 CO3 on the catalytic reactivity was observed.

Which types of clay minerals fix cesium ions effectively? the "cavity-charge matching effect".

How can radioactive Cs+ ions be removed from aqueous solution? From this perspective, the adsorption of Cs+ was investigated by using five types of clay minerals possessing different charge exchange capacities. The fixation ability for Cs+ depended on the charge exchange capacity of the clay minerals. Phlogopite and vermiculite, where the number of charges is almost equal to half the number of siloxane ditrigonal cavities in the structure, exhibited a strong Cs+ fixation ability among these clay minerals. In these clay minerals, effective interlayer collapse, which leads to quasi-irreversible adsorption of Cs+, is expected from the introduction of Cs+ into the layer space. This is named the "cavity-charge matching effect". This study clarifies why only phlogopite and vermiculite can fix Cs+ quite strongly among various types of clay minerals. These findings are beneficial for removing radioactive Cs+ ions from the environment using clay minerals through the cavity-charge matching effect.

Solar Water Splitting Utilizing a SiC Photocathode, a BiVO4 Photoanode, and a Perovskite Solar Cell.

We have successfully demonstrated solar water splitting using a newly fabricated photoelectrochemical system with a Pt-loaded SiC photocathode, a CoOx -loaded BiVO4 photoanode, and a perovskite solar cell. Detection of the evolved H2 and O2 with a 100 % Faradaic efficiency indicates that the observed photocurrent was used for water splitting. The solar-to-hydrogen (STH) efficiency was 0.55 % under no additional bias conditions.

One Electron-Initiated Two-Electron Oxidation of Water by Aluminum Porphyrins with Earth's Most Abundant Metal.

We report herein a new molecular catalyst for efficient water splitting, aluminum porphyrins (tetra-methylpyridiniumylporphyrinatealuminum: AlTMPyP), containing earth's most abundant metal as the central ion. One-electron oxidation of the aluminum porphyrin initiates the two-electron oxidation of water to form hydrogen peroxide as the primary reaction product with the lowest known overpotential (97 mV). The aluminum-peroxo complex was detected by a cold-spray ionization mass-spectrometry in high-resolution MS (HRMS) mode and the structure of the intermediate species was further confirmed using laser Raman spectroscopy, indicating the hydroperoxy complex of AlTMPyP to be the key intermediate in the reaction. The two-electron oxidation of water to form hydrogen peroxide was essentially quantitative, with a Faradaic efficiency of 99 %. The catalytic reaction was found to be highly efficient, with a turnover frequency up to ∼2×104  s-1 . A reaction mechanism is proposed involving oxygen-oxygen bond formation by the attack of a hydroxide ion on the oxyl-radical-like axial ligand oxygen atom in the one-electron-oxidized form of AlTMPyP(O- )2 , followed by a second electron transfer to the electrode.

Photo-induced morphological winding and unwinding motion of nanoscrolls composed of niobate nanosheets with a polyfluoroalkyl azobenzene derivative.

Photo-responsive nanoscrolls can be successfully fabricated by mixing a polyfluoroalkyl azobenzene derivative and a niobate nanosheet, which is exfoliated from potassium hexaniobate. In this study, we have found that the photo-responsive nanoscroll shows a morphological motion of winding and unwinding, which is basically due to the nanosheet sliding within the nanoscroll, by efficient photo-isomerization reactions of the intercalated azobenzene in addition to the interlayer distance change of the nanoscrolls. The relative nanosheet sliding of the nanoscroll is estimated to be ca. 280 nm from the AFM morphology analysis. The distance of the sliding motion is over 20 times that of the averaged nanosheet sliding in the azobenzene/niobate hybrid film reported previously. Photo-responsive nanoscrolls can be expected to be novel photo-activated actuators and artificial muscle model materials.

Synthesis of double-wall nanoscrolls intercalated with polyfluorinated cationic surfactant into layered niobate and their magnetic alignment.

The orientation of nanomaterials with an anisotropic nature such as nanoscrolls is very important for realizing their efficient and sophisticated functions in devices, including nanostructured electrodes in artificial photosynthetic cells. In this study, we successfully synthesized a nanoscroll by intercalation of a cationic polyfluorinated surfactant into the interlayer spaces of layered niobate and successfully controlled its orientation by applying an external magnetic field in water. The exfoliated niobate nanosheets were efficiently rolled-up to form nanoscrolls, which have a fine layered structure (d020 = 3.64 nm), by mixing with heptafluorobutanoylaminoethylhexadecyldimethylammonium bromide (C3F-S) in water, whereas the corresponding hydrocarbon analogue (C3H-S) did not form nanoscrolls. The synthetic yield for the purified and isolated nanoscrolls from the nanosheets was estimated to be 62% by weight. It was confirmed by atomic force microscopy (AFM) that most of the niobate nanosheets (98%) were converted to nanoscrolls. An external magnetic field was applied to the nanoscrolls to force them to align. After the magnetic treatment, the orientation of the nanoscrolls was investigated by small angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). The non-uniform ring distribution of the SAXS patterns indicates that the nanoscrolls dispersed in water were aligned well on applying the magnetic field. The long axis of the nanoscroll was oriented in the direction of the applied field and long nanoscrolls were aligned more efficiently. When the intercalated C3F-S molecules were removed from the nanoscrolls by treating with an acid, the resultant nanoscrolls did not exhibit magnetic alignment, strongly suggesting that C3F-S plays an important role in the orientation control of the nanoscrolls by the magnetic field.

Synthesis of water-soluble silicon-porphyrin: protolytic behaviour of axially coordinated hydroxy groups.

A new water-soluble silicon(IV)-tetra(4-carboxyphenyl)porphyrin (SiTCPP) with silicon(iv), the second most abundant element on Earth, in the center of porphyrin was synthesized. Fundamental properties including protolytic behaviour of axially coordinating hydroxy groups, and electrochemical behaviour were characterized. The properties were compared with those of silicon(IV)-tetra(2,4,6-trimethylphenyl)porphyrin (SiTMP) and silicon(IV)-tetra(4-trifluoromethylphenyl)porphyrin (SiTFMPP) and discussed in respect to the electron donating/withdrawing effect of the substituents. Two axially coordinating hydroxy groups of SiTCPP exhibit a four-step protolytic behaviour under the acidic conditions along with a single step protolysis of peripheral carboxyl groups. Though SiTCPP and SiTFMPP did not show any reactivity in the photochemical oxygenation of a substrate with K2PtCl6 as a sacrificial electron acceptor, the first oxidation wave in the electrochemical process of SiTCPP and SiTFMPP showed catalytic behaviour in aqueous acetonitrile solution at any pH condition, in contrast to SiTMP which has only a reversible oxidation wave under neutral and weakly acidic conditions. The criteria for the electrochemical oxidative activation of water and the photooxygenation of the substrate were obtained. The higher oxidation wave of Si-porphyrins than ∼0.86 volt vs. SHE is required for the electrochemical oxidation of water, while suitable protecting groups such as a methyl substituent is a requisite for the photochemical oxygenation with K2PtCl6 as a sacrificial electron acceptor.

Dense Deposition of Gold Nanoclusters Utilizing a Porphyrin/Inorganic Layered Material Complex as the Template.

We examined the deposition of gold clusters through the reduction of a gold precursor sensitized by nonaggregated, assembled porphyrin molecules on an inorganic layered material surface in order to develop a novel strategy for constructing assemblies of gold clusters. Visible light irradiation on nonaggregated, assembled porphyrin on the inorganic surface in the presence of the gold precursor and an electron donor induced the deposition of gold NPs on the surface of the inorganic layered material. Uniform gold clusters, with an average diameter of 1.5 nm, were deposited on the surface without aggregation. The average interparticle distance between adjacent gold clusters (center to center) was 2.3 nm, which agrees well with the average intermolecular distance of the nonaggregated, assembled porphyrin molecules on the inorganic surface. Thus, the generated gold clusters appear to reflect the nonaggregated, assembled structure of the porphyrin molecules on the inorganic surface. This method, termed the photosensitized template reduction (PTR) method, is a useful and novel technique for the deposition of metal nanoparticles on the surfaces of supporting materials.

Remarkable enhancement of the photoreactivity of a polyfluoroalkyl azobenzene derivative in an organic-inorganic nano-layered microenvironment.

Organic-inorganic hybrids composed of polyfluoroalkyl azobenzene surfactant (abbreviated as C3F-Azo-C6H) and inorganic layered compounds are able to undergo reversible three-dimensional morphology changes such as interlayer space changes and nanosheet sliding in a giant scale due to reversible trans-cis isomerization of the azobenzene moiety upon photo-irradiation. In this paper, we have systematically studied the relationship between the layered hybrid microstructures of C3F-Azo-C6H-clay and their photoreactivity for understanding the mechanism of the photo-induced morphology change. The photoreactivity was found to be very much affected by the surrounding microenvironments. As compared with it in solution, the cis-trans photo-isomerization in C3F-Azo-C6H-clay nano-layered film was substantially enhanced with the quantum yield exceeding unity (Φ = 1.9), while the trans-cis isomerization was rather retarded. The corresponding hydrocarbon analogue of the azobenzene surfactant (C3H-Azo-C6H) did not show such an enhancement. The enhancement was discussed in terms of a cooperative effect among adjacent azobenzene moieties along with polyfluoroalkyl chains and the inorganic clay nanosheet to prevent a dissipation of the excess energy being liberated during the photo-isomerization within the nano-layered microenvironment.

Plasmon-assisted water splitting using two sides of the same SrTiO3 single-crystal substrate: conversion of visible light to chemical energy.

A plasmon-induced water splitting system that operates under irradiation by visible light was successfully developed; the system is based on the use of both sides of the same strontium titanate (SrTiO3) single-crystal substrate. The water splitting system contains two solution chambers to separate hydrogen (H2) and oxygen (O2). To promote water splitting, a chemical bias was applied by regulating the pH values of the chambers. The quantity of H2 evolved from the surface of platinum, which was used as a reduction co-catalyst, was twice the quantity of O2 evolved from an Au-nanostructured surface. Thus, the stoichiometric evolution of H2 and O2 was clearly demonstrated. The hydrogen-evolution action spectrum closely corresponds to the plasmon resonance spectrum, indicating that the plasmon-induced charge separation at the Au/SrTiO3 interface promotes water oxidation and the subsequent reduction of a proton on the backside of the SrTiO3 substrate. The chemical bias is significantly reduced by plasmonic effects, which indicates the possibility of constructing an artificial photosynthesis system with low energy consumption.

Direct detection of key reaction intermediates in photochemical CO2 reduction sensitized by a rhenium bipyridine complex.

Photochemical CO2 reduction sensitized by rhenium-bipyridyl complexes has been studied through multiple approaches during the past several decades. However, a key reaction intermediate, the CO2-coordinated Re-bipyridyl complex, which should govern the activity of CO2 reduction in the photocatalytic cycle, has never been detected in a direct way. In this study on photoreduction of CO2 catalyzed by the 4,4'-dimethyl-2,2'-bipyridine (dmbpy) complex, [Re(dmbpy)(CO)3Cl] (1), we successfully detect the solvent-coordinated Re complex [Re(dmbpy)(CO)3DMF] (2) as the light-absorbing species to drive photoreduction of CO2. The key intermediate, the CO2-coordinated Re-bipyridyl complex, [Re(dmbpy)(CO)3(COOH)], is also successfully detected for the first time by means of cold-spray ionization spectrometry (CSI-MS). Mass spectra for a reaction mixture with isotopically labeled (13)CO2 provide clear evidence for the incorporation of CO2 into the Re-bipyridyl complex. It is revealed that the starting chloride complex 1 was rapidly transformed into the DMF-coordinated Re complex 2 through the initial cycle of photoreduction of CO2. The observed induction period in the time profile of the CSI-MS signals can well explain the subsequent formation of the CO2-coordinated intermediate from the solvent-coordinated Re-bipyridyl complex. An FTIR study of the reaction mixture in dimethyl sulfoxide clearly shows the appearance of a signal at 1682 cm(-1), which shifts to 1647 cm(-1) for the (13)CO2-labeled counterpart; this is assigned as the CO2-coordinated intermediate, Re(II)-COOH. Thus, a detailed understanding has now been obtained for the mechanism of the archetypical photochemical CO2 reduction sensitized by a Re-bipyridyl complex.