Hayato Yuzawa

A heterogeneous palladium catalyst hybridised with a titanium dioxide photocatalyst for direct C–C bond formation between an aromatic ring and acetonitrile

A palladium catalyst hybridised with a titanium dioxide photocatalyst can promote cyanomethylation of an aromatic ring by using acetonitrile, where the photocatalyst activates acetonitrile to form a cyanomethyl radical before the C-C bond formation using the palladium catalyst.

Probing Interfacial Water on Nanodiamonds in Colloidal Dispersion.

The structure of interfacial water layers around nanoparticles dispersed in an aqueous environment may have a significant impact on their reactivity and on their interaction with biological species. Using transmission soft X-ray absorption spectroscopy in liquid, we demonstrate that the unoccupied electronic states of oxygen atoms from water molecules in aqueous colloidal dispersions of nanodiamonds have a different signature than bulk water. X-ray absorption spectroscopy can thus probe interfacial water molecules in colloidal dispersions. The impacts of nanodiamond surface chemistry and concentration on interfacial water electronic signature are discussed.

In operando observation system for electrochemical reaction by soft X-ray absorption spectroscopy with potential modulation method

In order to investigate local structures of electrolytes in electrochemical reactions under the same scan rate as a typical value 100 mV/s in cyclic voltammetry (CV), we have developed an in operando observation system for electrochemical reactions by soft X-ray absorption spectroscopy (XAS) with a potential modulation method. XAS spectra of electrolytes are measured by using a transmission-type liquid flow cell with built-in electrodes. The electrode potential is swept with a scan rate of 100 mV/s at a fixed photon energy, and soft X-ray absorption coefficients at different potentials are measured at the same time. By repeating the potential modulation at each fixed photon energy, it is possible to measure XAS of electrochemical reaction at the same scan rate as in CV. We have demonstrated successful measurement of the Fe L-edge XAS spectra of aqueous iron sulfate solutions and of the change in valence of Fe ions at different potentials in the Fe redox reaction. The mechanism of these Fe redox processes is discussed by correlating the XAS results with those at different scan rates.

Anti-Markovnikov hydration of alkenes over platinum-loaded titanium oxide photocatalyst

Hydration of various alkenes proceeded over a platinum-loaded titanium oxide photocatalyst. It is notable that, unlike conventional acid-catalysts, the photocatalyst preferentially promoted the hydration according to the anti-Markovnikov rule. The results of some reaction experiments and semiempirical molecular orbital calculations suggested the reaction path of this hydration as follows: an electrophilic surface oxygen radical species formed on the photoexcited titanium oxide attacks a carbon double bond of the alkene to produce an intermediate, followed by the addition of a hydrogen radical formed on the platinum sites to produce an alcohol. The anti-Markovnikov selectivity for each investigated alkene would be determined by the stability of the radical intermediate.

Direct Introduction of OH Group to sp2-Carbon on Platinum-Loaded Titanium Oxide Photocatalyst

Photocatalytic oxidation of various organic compounds by using molecular oxygen has been broadly investigated as a valuable synthetic route, but the application has been still limited because the active oxygen species from the molecular oxygen are usually difficult to be controlled. In this short review, we describe two kinds of photocatalytic oxygenation with H2O molecule as a source of OH group; i.e., photocatalytic hydroxylation of aromatic ring and photocatalytic hydration of alkene, on Pt/TiO2 photocatalyst. In both reactions, a photoformed active oxygen species attacks to the sp2-carbon to form a reaction intermediate. In the aromatic ring hydroxylation, the elimination of the H atom from the intermediate proceeds while the conjugate double bond of the aromatic ring maintains. In the alkene hydration, the addition of the H radical to the intermediate results in forming an alcohols molecule with the saturation of the double bond. In the former case, the electrophilic property of the active oxygen species predominantly determines the orientation of the OH group in the produced phenols. On the other hand, in the latter case, the thermodynamic stability of the intermediate radical species leads the active oxygen species preferentially to the terminal sp2-carbon, which makes it possible to provide the unique regioselectivity of alcohol according to the anti-Markovnikov rule.

Interaction between Water and Alkali Metal Ions and Its Temperature Dependence Revealed by Oxygen K-Edge X-ray Absorption Spectroscopy

Interaction between water molecules and alkali metal ions in aqueous salt solutions has been studied by the oxygen K-edge soft X-ray absorption spectroscopy (XAS) in transmission mode. In the measurement of several alkali halide aqueous solutions with different alkali chlorides (Li, Na, and K) and different sodium halides (Cl, Br, and I), the pre-edge component arising from the hydration water molecules shows a blue shift in peak energy as strongly depending on cations but not on anions. In the temperature dependent measurement, the pre-edge component arising from water molecules beyond the first hydration shell shows the same behavior as that of pure liquid water. On the other hand, the pre-edge component arising from water molecules in the first hydration shell of Li+ ions is not evidently dependent on the temperature, indicating that the hydration water molecules are more strongly bound with Li+ ions than the other water molecules. These experimental results are supported by the results of radial distribution functions of the first hydration shell and their temperature dependence, evaluated by molecular dynamics simulations.

Intermolecular Interactions of Pyridine in Liquid Phase and Aqueous Solution Studied by Soft X-ray Absorption Spectroscopy

Abstract Intermolecular interactions of pyridine in liquid and in aqueous solution are studied by using soft X-ray absorption spectroscopy (XAS) at the C, N, and O K-edges. XAS of liquid pyridine shows that the N 1s→π* peak is blue shifted and the C 1s→π* peak of the meta and para sites is red shifted, respectively, as compared with XAS of pyridine gas. These shifts in liquid are smaller than those in clusters, indicating that the intermolecular interaction of liquid pyridine is weaker than that of pyridine cluster, as supported by the combination of quantum chemical calculations of the core excitation and molecular dynamics simulations of the liquid structure. On the other hand, XAS spectra of aqueous pyridine solutions (C5H5N)x(H2O)1−x measured at different molar fractions show that in the pyridine rich region, x>0.7, the C and N 1s→π* peak energies are not so different from pure liquid pyridine (x=1.0). In this region, antiparallel displaced structures of pyridine molecules are dominant as in pure pyridine liquid. In the O K-edge XAS, the pre-edge peaks sensitive to the hydrogen bond (HB) network of water molecules show the red shift of −0.15 eV from that of bulk water, indicating that small water clusters with no large-scale HB network are formed in the gap space of structured pyridine molecules. In the water rich region, 0.7>x, the N 1s→π* peaks and the O 1s pre-edge peaks are blue shifted, and the C 1s→π* peaks of the meta and para sites are red-shifted by increasing molar fraction of water. The HB network of bulk water is dominant, but quantum chemical calculations indicate that small pyridine clusters with the HB interaction between the H atom in water and the N atom in pyridine are still existent even in very dilute pyridine solutions.

Temperature-Dependent Structural Changes in Liquid Benzene

Benzene is the simplest aromatic molecule with intermolecular π-π interactions. Because ordered liquids are key structures used to study chemical and biological phenomena in the liquid state, ordered structures of benzene confined in nanopores have been extensively studied, whereas those in the liquid state are still unknown. In this study, we address fundamental questions regarding whether ordered structures of benzene are formed in the liquid state by using carbon K-edge X-ray absorption spectroscopy (XAS) as a sensitive local probe. By comparing unexpected temperature behaviors of the π* peak in XAS spectra with model calculations, we have investigated temperature-dependent changes of ordered structures in liquid benzene caused by the increase in abundance of the parallel sandwich orientation relative to parallel displaced structures for the higher temperature. These results are confirmed by infrared spectroscopy with additional support of vibrational mode calculations.