Catalytic ammonia synthesis on HY-zeolite-supported angstrom-size molybdenum cluster.

The development of new catalysts with high N activation ability is an effective approach for low-temperature ammonia synthesis. Herein, we report a novel angstrom-size molybdenum metal cluster catalyst for efficient ammonia synthesis. This catalyst is prepared by the impregnation of a molybdenum halide cluster complex with an octahedral Mo metal core on HY zeolite, followed by the removal of all the halide ligands by activation with hydrogen.

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Dynamic behavior of intermediate adsorbates, such as diffusion, spillover, and reverse spillover, has a strong influence on the catalytic performance in oxide-supported metal catalysts. However, it is challenging to elucidate how the intermediate adsorbates move on the catalyst surface and find active sites to give the corresponding products. In this study, the effect of the dynamic behavior of methoxy intermediate on methanol decomposition on a Pt/TiO(110) surface has been clarified by combination of scanning tunneling microscopy (STM), temperature-programmed desorption (TPD), and density functional theory (DFT) calculations.

Structure of Atomically Dispersed Pt in a SnO Thin Film under Reaction Conditions: Origin of Its High Performance in Micro Electromechanical System Gas Sensor Catalysis.

A battery-driven micro electromechanical system (MEMS) gas sensor has been developed for household safety when using natural gas. The heart of the MEMS gas sensor is a 7.5 at % Pt-SnO thin film catalyst deposited on the SnO sensor layer.

One-Step Preparation of Fe/N/C Single-Atom Catalysts Containing Fe-N Sites from an Iron Complex Precursor with 5,6,7,8-Tetraphenyl-1,12-Diazatriphenylene Ligands.

Fe/N/C single-atom catalysts containing Fe-N sites prepared by pyrolysis are promising cathode materials for fuel cells and metal-air batteries due to their high oxygen reduction reaction (ORR) activities. We have developed iron complexes containing N2- or N3-chelating coordination structures with preorganized aromatic rings in a 1,12-diazatriphenylene framework tethering bromo substituents as precursors to precisely construct Fe-N sites in an Fe/N/C catalyst. One-step pyrolysis of the iron complex with carbon black forms atomically dispersed Fe-N sites without iron aggregates.

Bent crystal Laue analyser combined with total reflection fluorescence X-ray absorption fine structure (BCLA + TRF-XAFS) and its application to surface studies.

A bent crystal Laue analyser (BCLA) is an X-ray energy analyser used for fluorescence X-ray absorption fine-structure (XAFS) spectroscopy to separate the fluorescence X-ray emission line of a target atom from the elastic scattering X-rays and other fluorescence emission lines. Here, the feasibility of the BCLA for total reflection fluorescence XAFS (TRF-XAFS), which has a long X-ray footprint on the substrate surface owing to grazing incidence, was tested. The focal line of the BCLA was adjusted on the X-ray footprint and the XAFS signal for one monolayer of Pt deposited on a 60 nm Au film with high sensitivity was obtained.

Model building analysis - a novel method for statistical evaluation of Pt L-edge EXAFS data to unravel the structure of Pt-alloy nanoparticles for the oxygen reduction reaction on highly oriented pyrolytic graphite.

Extended X-ray absorption fine structure (EXAFS) is a powerful tool to determine the local structure in Pt nanoparticles (NP) on carbon supports, active catalysts for fuel cells. Highly oriented pyrolytic graphite (HOPG) covered with Pt NP gives samples with flat surfaces that allow application of surface science techniques. However, the low concentration of Pt makes it difficult to obtain good quality EXAFS data.

Disposition of Iridium on Ruthenium Nanoparticle Supported on Ketjenblack: Enhancement in Electrocatalytic Activity toward the Electrohydrogenation of Toluene to Methylcyclohexane.

Electrohydrogenation of toluene (TL) to methylcyclohexane (MCH) has been recognized as a promising technology for the hydrogenation process in the organic hydride hydrogen storage system. Recently, we found that the Ketjenblack (KB)-supported Ru-Ir alloy electrocatalyst showed a high electrocatalytic activity for the electrohydrogenation of TL to MCH, and there was the synergy of Ir electrocatalysis for the formation of adsorbed hydrogen species (H) (H + e → H) and Ru catalysis for hydrogenation of TL (6H + TL → MCH). In this paper, the Ir-modified Ru nanoparticle supported on KB (Ir/Ru/KB) electrocatalyst was synthesized by using a modified spontaneous deposition method.

A new interpretation of the √7×√7 R19.1° structure for P adsorbed on a Ni(111) surface.

We have studied P adsorption on Ni(111), a system which shows complex adsorbate structures. We determined the phase diagram of the surface P adsorbed on Ni(111). At low coverage, amorphous P was observed.

An Al-doped SrTiO photocatalyst maintaining sunlight-driven overall water splitting activity for over 1000 h of constant illumination.

Photocatalytic water splitting is a viable approach to the large-scale production of renewable solar hydrogen. The apparent quantum yield for this reaction has been improved, but the lifespan of photocatalysts functioning under sunlight at ambient pressure have rarely been examined, despite the critical importance of this factor in practical applications. Herein, we show that Al-doped SrTiO (SrTiO:Al) loaded with a RhCrO (rhodium chromium oxide) cocatalyst splits water with an apparent quantum yield greater than 50% at 365 nm.

Photoinduced anisotropic distortion as the electron trapping site of tungsten trioxide by ultrafast W L-edge X-ray absorption spectroscopy with full potential multiple scattering calculations.

Understanding the excited state of photocatalysts is significant to improve their activity for water splitting reaction. X-ray absorption fine structure (XAFS) spectroscopy in X-ray free electron lasers (XFEL) is a powerful method to address dynamic changes in electronic states and structures of photocatalysts in the excited state in ultrafast short time scales. The ultrafast atomic-scale local structural change in photoexcited WO was observed by W L edge XAFS spectroscopy using an XFEL.

Premodified Surface Method to Obtain Ultra-Highly Dispersed Metals and their 3D Structure Control on an Oxide Single-Crystal Surface.

Precise control of the three-dimensional (3D) structure of highly dispersed metal species such as metal complexes and clusters attached to an oxide surface has been important for the development of next-generation high-performance heterogeneous catalysts. However, this is not easily achieved for the following reasons. (1) Metal species are easily aggregated on an oxide surface, which makes it difficult to control their size and orientation definitely.

Development of Surface Fluorescence X-Ray Absorption Fine Structure Spectroscopy Using a Laue-Type Monochromator.

Surface fluorescence X-ray absorption fine structure (XAFS) spectroscopy using a Laue-type monochromator has been developed to acquire structural information about metals with a very low concentrate on a flat highly oriented pyrolytic graphite (HOPG) surface in the presence of electrolytes. Generally, surface fluorescence XAFS spectroscopy is hindered by strong scattering from the bulk, which often chokes the pulse counting detector. In this work, we show that a bent crystal Laue analyzer (BCLA) can efficiently remove the scattered X-rays from the bulk even in the presence of solution.

The challenge of constructing an international XAFS database.

The present state of XAFS databases, particularly in Japan, and proposals for future directions are presented. International collaboration is important for enlarging the database for further development of XAFS spectroscopy.

Rhenium-Loaded TiO : A Highly Versatile and Chemoselective Catalyst for the Hydrogenation of Carboxylic Acid Derivatives and the N-Methylation of Amines Using H and CO.

Herein, we report a heterogeneous TiO -supported Re catalyst (Re/TiO ) that promotes various selective hydrogenation reactions, which includes the hydrogenation of esters to alcohols, the hydrogenation of amides to amines, and the N-methylation of amines, by using H and CO . Initially, Re/TiO was evaluated in the context of the selective hydrogenation of 3-phenylpropionic acid methyl ester to afford 3-phenylpropanol (pH2 =5 MPa, T=180 °C), which revealed a superior performance over other catalysts that we tested in this study. In contrast to other typical heterogeneous catalysts, hydrogenation reactions with Re/TiO did not produce dearomatized byproducts.

Capturing local structure modulations of photoexcited BiVO by ultrafast transient XAFS.

Ultrafast excitation of photocatalytically active BiVO was characterized by femto- and picosecond transient X-ray absorption fine structure spectroscopy. An initial photoexcited state (≪500 fs) changed to a metastable state accompanied by a structural change with a time constant of ∼14 ps. The structural change might stabilize holes on oxygen atoms since the interaction between Bi and O increases.

Structural analysis of strontium in human teeth treated with surface pre-reacted glass-ionomer filler eluate by using extended X-ray absorption fine structure analysis.

The bioactive effects of strontium released from surface pre-reacted glass-ionomer (S-PRG) fillers may aid in caries prevention. In this study, the local structure of strontium taken up by teeth was estimated by extended X-ray absorption fine structure analysis. Immersing teeth into S-PRG filler eluate increased the strontium content in enamel and dentin by more than 100 times.

Degradation mechanism of a high-performance real micro gas sensor, as determined by spatially resolved XAFS.

Of late, battery-driven high-performance gas sensors have gained acceptability in practical usage, whose atomic-scale structure has been revealed by μ-fluorescence X-ray absorption fine structure analysis. We studied the chemical distribution of Pd species in the Pd/Al2O3 catalyst overlayer in the real gas sensor at various degrees of deterioration. In a freshly prepared sensor, all Pd species were in the PdO form; in a heavily deteriorated sensor, Pd/Al2O3 in the external region changed to metallic Pd particles, while the PdO structure in the inner region near the heater remained unchanged.

Dynamics of Photoelectrons and Structural Changes of Tungsten Trioxide Observed by Femtosecond Transient XAFS.

The dynamics of the local electronic and geometric structures of WO3 following photoexcitation were studied by femtosecond time-resolved X-ray absorption fine structure (XAFS) spectroscopy using an X-ray free electron laser (XFEL). We found that the electronic state was the first to change followed by the local structure, which was affected within 200 ps of photoexcitation.

Ultrathin inorganic molecular nanowire based on polyoxometalates.

The development of metal oxide-based molecular wires is important for fundamental research and potential practical applications. However, examples of these materials are rare. Here we report an all-inorganic transition metal oxide molecular wire prepared by disassembly of larger crystals.

A high-temperature in situ cell with a large solid angle for fluorescence X-ray absorption fine structure measurement.

We present the design and performance of a high-temperature in situ cell with a large solid angle for fluorescence X-ray absorption fine structure (XAFS) spectra. The cell has a large fluorescence XAFS window (116 mm(ϕ)) near the sample in the cell, realizing a large half-cone angle of 56°. We use a small heater (25 × 35 mm(2)) to heat the sample locally to 873 K.

Interconvertible multiple photoluminescence color of a gold(i) isocyanide complex in the solid state: solvent-induced blue-shifted and mechano-responsive red-shifted photoluminescence.

In this study, we report the interconvertible tetracolored solid state photoluminescence of gold(i) isocyanide complex upon various external stimuli through solid state structural changes. Soaking complex in acetone yields blue emission as a result of the formation of . The subsequent removal of acetone yields through a crystal-to-crystal phase transition, which exhibits green emission.

Improvement of a Real Gas-Sensor for the Origin of Methane Selectivity Degradation by µ-XAFS Investigation.

We have directly investigated the chemical state of the Pd species in a real μ-gas sensor device by examining the μ-fluorescence X-ray absorption fine structure. The μ-gas sensor device was heavily damaged by a heating process in which the temperature was ill-controlled, resulting in decrease of methane selectivity. We found that the PdO in the fresh μ-gas sensor was reduced to Pd metal particles as the methane selectivity decreased.