Published papers

In situ monitoring of initial oxidation of GaAs surfaces was performed under (near-) realistic oxidizing environments, using ambient-pressure X-ray photoelectron spectroscopy (AP-XPS). The surface chemical states drastically change with time. The oxidation process at the sub-nano-meter-scale exhibits a significantly small activation energy, which can be regarded as a quasi-barrier-less oxidation. This journal is

Density functional theory calculations were applied to a study on ligand effects on a Pd surface oxide formed on RhPd(100) alloy surfaces. It was found that chemical composition of the topmost layer of alloy significantly influences on the electronic structure of the Pd surface oxide. Such interlayer ligand effects are originating from the Rh−O and Pd−O interactions between the topmost layer of alloy and the Pd surface oxide. These effects give rise to substantial changes in binding energies of adsorbates and could change catalytic activity depending on atomic fraction of the Rh−Pd alloy.

NO reduction by CO on Rh(111) was investigated by near-ambient pressure X-ray photoelectron spectroscopy, mass spectrometry, and kinetic analysis. Under exposure to NO + CO mixed gases and with heating the surface from room temperature to 450 °C, NO dissociation and NO reduction reaction start simultaneously independent of gas pressure ratio of NO/CO, which indicates that NO dissociation triggers this reaction. From kinetic analyses based on observed adsorbate coverages under reaction conditions, the following two points are suggested: (i) NOhollow is a reactive species for N2 and N2O formation via N + NO reaction. (ii) At low temperatures, the N + NO reaction is dominant for N2 production, whereas above around 400 °C, the N + N reaction becomes dominant, which leads to an increase in N2 selectivity at the higher temperatures. Compared with the NO + CO reaction on Ir(111) surfaces, which exhibits a high N2 selectivity, the adsorption site of reactive NO and the availability of vacant surface sites could be key factors for the lower N2 selectivity for Rh(111).

A layered manganese oxide catalyst containing K+ cations [K/MnOx catalyst] was developed, and its ability to efficiently decompose water was demonstrated. Operando hard/tender/soft X-ray absorption fine structure (XAFS) techniques were used to investigate the function of the K/MnOx catalyst under working conditions. The Mn valency depended on the potential and the amount of K+ cation adsorption. Mn K-edge (hard X-ray) XAFS measurements for the K/MnOx catalyst suggested that the Mn in the catalyst was an Mn3+ species with an octahedral δ-MnO2 structure at a lower electrode potential, which changed reversibly to an Mn4+ species with a δ-MnO2 structure at higher potential during oxygen evolution. A similar result was obtained from operando O K-edge (soft X-ray) XAFS. The chemical state of K species was analyzed using operando K K-edge (tender X-ray) XAFS, which indicated that K+ cations were intercalated with hydrated states in the δ-MnO2 layers. These operando XAFS results demonstrated that the layered δ-MnO2 containing hydrated K+ cations functioned as efficient oxygen evolution electrocatalysts because of the presence of Mn3+ reaction sites.

The formation of interfacial metal–oxide structures on the Pt3Ni(111) bimetallic surface was investigated using scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) techniques at near-ambient pressure (NAP). Direct observation of surface images clearly shows the occurrence of surface segregation of the sub-surface Ni depending on the surrounding gas-phase conditions. Especially, the prepared topmost Pt-skin layer of the Pt3Ni(111) is altered by Ni oxide segregation that makes an interfacial Pt-NiO1−x nanostructure with dissociated oxygen. This metal–oxide interface could provide active sites for more-efficient carbon monoxide (CO) conversion processes under mixed CO/O2 gas environments; the associated specific chemical binding energy was identified using NAP-XPS. The combined operando observations from the NAP-STM and NAP-XPS on the Pt3Ni(111) surface reveal that the interfacial metal–oxide structure is strongly correlated with the origin of the enhanced catalytic activity at thermodynamic equilibrium.

The surface chemical states of Pd(100) during CO oxidation were investigated using ambient pressure x-ray photoelectron spectroscopy and mass spectroscopy. Under the reactant ratio of CO/O 2 = 0.1, i.e. an oxygen-rich reaction condition, the formation of surface oxides was observed with the onset of CO oxidation reaction at T = 525 K. As the reactant ratio (CO/O 2 ) increased from 0.1 to 1.0, ∼ 90 % surface oxides remains on surface during the reaction. Upon the formation of surface oxides, the core level shift of oxygen gas phase peak was observed, indicating that change of surface work function. As CO oxidation takes places, i.e. making a transition from CO covered surface to the oxidic surface, the work functions of surface oxide on Pd(100) and Pt(110) display opposite behavior.

Oxidation of monometallic Pd and bimetallic Pd3Au alloy surfaces are observed by in situ ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) at an elevated pressure (100 mTorr O2 ambient). It is directly evidenced that the alloying with Au hinders the surface oxidation of Pd3Au surfaces compared with monometallic Pd surfaces. Remarkably, the oxidation behavior is clearly different between Pd3Au(111) and (100) surfaces. The (100) surface has a relatively Pd-rich surface composition, and the surface oxide layer is formed, whereas the (111) surface has a Au-rich composition, and the surface oxidation is quite limited. A combined approach of experimental and theoretical techniques reveals that Pd/Au surface composition and atomic arrangement are key factors determining the oxidation behavior.

La-loaded Al2O3 (La/Al2O3) is a practical support for three-way catalysis (TWC) reactions. Although it has been reported that the addition of La to Al2O3 results in improved thermal stability to retain high specific surface areas, its effect on the catalytic reduction of NOx (DeNOx) has not been studied systematically. Herein, we describe the role of La in La/Al2O3-supported Pd catalysts (Pd/La/Al2O3) for TWC reactions. For that purpose, we employed various in situ spectroscopic studies, including infrared (IR), X-ray absorption fine structure (XAFS), and near-ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS) in combination with density functional theory (DFT) calculations. The obtained results revealed that Pd0 species supported on La/Al2O3 are more electron-deficient compared to those on pristine Al2O3 without La(Pd/Al2O3). Kinetic studies using powdered catalysts revealed that the addition of La suppresses the poisoning effect by CO during the DeNOx reactions. In addition to the catalytic tests with powdered catalysts, monolithic honeycomb forms of the catalysts were prepared and employed for TWC reactions, which showed that Pd/La/Al2O3 exhibits higher DeNOx activity than Pd/Al2O3. In this study, we also reexamined the effective loading amount of La, which has traditionally been ∼3-5 wt % of La for TWC processes in order to retain the high specific surface area of the La/Al2O3 supports. Our investigations showed that an increased La loading (15 wt %) is even more effective for the DeNOx reactions tested in this study due to the higher reactivity toward NO and the greater suppression of the poisoning effect of CO. The developed catalyst Pd/La(15)/Al2O3 has also been tested in a commercial vehicle and has been evaluated on a practical driving mode test cycle (LA-4; city cycle of U.S. Federal and California), where it showed a better catalytic performance than the conventionally used Pd/La(3-5)/Al2O3 catalysts. Our study suggests that the loading amount of La in Pd/La/Al2O3 catalysts needs to be adjusted depending on the application systems, considering not only the support stability (surface areas) but also the promotional effect in the TWC process.

We report a newly designed compact cell to measure XAFS spectra with the conversion electron yield (CEY) method in the soft X-ray region under ambient-pressure gas conditions. Secondary electrons generated from the gas and sample by collision of X-ray-absorption-induced Auger electrons are collected by a positively biased collector electrode to obtain XAFS spectra. It was confirmed that this cell is applicable to soft X-ray surface XAFS measurements for different types of materials such as insulating organic materials and metal oxides under 1 bar gas conditions. During the measurements, photoinduced side effects were observed; i.e. photoinduced degradation of organic materials and photoinduced reduction/oxidation of metal oxides. We found that these photoinduced side effects can be sufficiently suppressed by controlling the measuring conditions. The presented measuring approach will enable surface XAFS spectra to be obtained in the soft X-ray region for various types of functional materials under ambient-pressure working conditions. This journal is

The origin of the synergistic catalytic effect between metal catalysts and reducible oxides has been debated for decades. Clarification of this effect, namely, the strong metal-support interaction (SMSI), requires an understanding of the geometric and electronic structures of metal-metal oxide interfaces under operando conditions. We show that the inherent lattice mismatch of bimetallic materials selectively creates surface segregation of subsurface metal atoms. Interfacial metal-metal oxide nanostructures are then formed under chemical reaction environments at ambient pressure, which thus increases the catalytic activity for the CO oxidation reaction. Our in situ surface characterizations using ambient-pressure scanning tunneling microscopy and ambient-pressure x-ray photoelectron spectroscopy exhibit (i) a Pt-skin layer on the Pt-Ni alloyed surface under ultrahigh vacuum, (ii) selective Ni segregation followed by the formation of NiO1−x clusters under oxygen gas, and (iii) the coexistence of NiO1−x clusters on the Pt-skin during the CO oxidation reaction. The formation of interfacial Pt-NiO1−x nanostructures is responsible for a highly efficient step in the CO oxidation reaction. Density functional theory calculations of the Pt3Ni(111) surface demonstrate that a CO molecule adsorbed on an exposed Pt atom with an interfacial oxygen from a segregated NiO1−x cluster has a low surface energy barrier of 0.37 eV, compared with 0.86 eV for the Pt(111) surface.

Iridium (Ir) exhibits a good efficiency for reduction of NO under excess O 2 coexisting conditions at temperatures higher than 250 °C. On the other hand, the advantage is lost at lower temperatures below 250 °C under O 2 existence, compared to any other platinum group metals. In this study, adsorption behavior of NO on Ir(111) single-crystal surfaces under excess O 2 coexisting conditions at the temperatures from room temperature to 250 °C has been studied by in-situ X-ray Photoelectron Spectroscopy (XPS). It is revealed that the coexisting O 2 induces formation of a high-density chemisorbed atomic oxygen (O) phase and the atomic O phase suppresses adsorption of NO at on-top sites significantly, which suggests that the suppression of NO adsorption causes a decrease in the ability of NO reduction at the lower temperatures.

The electrolysis of water using renewable energy is a promising approach to developing a sustainable hydrogen-based economy. To improve the efficiency of this process, it will be necessary to develop highly active electrocatalysts that promote the oxygen evolution reaction (OER). In the present study, the OER activity of a nickel oxide electrocatalyst was dramatically improved following the addition of a diamine to the electrolyte solution during electrodeposition. Operando UV/vis absorption spectroscopy was used to assess a number of nickel catalysts containing various diamines and other organic compounds. The data indicate that Ni(ii) complexes were formed with the diamines during electrodeposition. Consequently, the catalytic activity of these materials was enhanced based on increased concentrations of active reaction sites for the OER process. Ni K-edge X-ray absorption spectra showed that these catalysts were composed of γ-NiOOH with a Ni3.6+ valence state. The coordination of the diamine molecules to the γ-NiOOH produced structural distortion that contributed to improved OER activity. This structural distortion is likely the most important factor in enhancing the OER activity of inorganic-organic composite catalysts.

Changes in the chemical states of the sulfonic groups of Nafion in a model polymer electrolyte fuel cell under an oxygen/hydrogen gas atmosphere were studied using sulfur K-edge XANES spectroscopy. First, the chemical state changes in the sulfonic acid groups of both cathode and anode electrodes due to humidity under oxygen/hydrogen gas flow were observed. Reversible spectral changes ascribed to the hydration and dehydration of the sulfonic acid group were observed at both electrodes. This result is similar to the experimental results obtained without introducing oxygen (helium/hydrogen). On the anode, some of the sulfonic acid groups were decomposed to atomic sulfur adsorbed on platinum (Sad) and the amount increased with time. On the cathode, the formation of Sad was suppressed under the oxygen atmosphere. Next, the effects of oxygen gas introduction onto Sad were examined. Sad was at once formed on both electrodes under dry conditions without an oxygen supply. By supplying oxygen gas, Sad on the cathode disappears. Therefore, the catalyst of the cathode has the ability to recover against the poisoning Sad, while that on the anode accumulates.

Characterization of Mo species on Rh metal particles in Rh-MoOx/C catalyst for C-O hydrogenolysis reactions was carried out with in situ ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) and density functional theory (DFT) calculations. The as-prepared Rh-MoOx/C sample with high oxidation states of Rh3+, Rh4+ and Mo6+ was reduced with 0.2 Torr of H2. All the Rh species and most Mo species were reduced to Rh0 and Mo4+ during the heating to 570 K. The thickness of the Mo layers after the reduction was calculated by a numerical analysis based on the XPS intensity ratio and a uniform adlayer stacking model. The calculated averaged thickness was about 0.3 nm, suggesting the formation of Mo species with a monolayer order on the metallic Rh particle surface. The O 1s XPS showed the presence of Mo-OH and Mo-O oxygen species with a ratio of 1.4 in reduced Rh-MoOx/C. Considering the presence of residual Mo6+ species with a large number of Mo6+-O bonds, the ratio of Mo4+-OH to Mo4+-O is estimated to be 2, suggesting the formation of MoO(OH)2. The DFT calculations of various monomeric MoOxHy species on the Rh(111) surface were carried out, and the stability was examined by the ab initio thermodynamic approach. The relative stability is changed when the surface coverage of hydrogen atoms is taken into account. The MoO(OH)2 species is calculated to be the most stable species in the presence of surface hydrogens over a wide range of conditions, including those for the catalytic reaction (ca. 400 K, 100-1 MPa H2).

The interactions between oxygen and Rh-Pd bimetallic alloy surfaces were investigated using surface sensitive experimental techniques and density functional theory calculations. The alloy surfaces were oxidized under 10-5 Torr and 100 mTorr oxygen upon heating above 250 °C. A thin Rh oxide layer was preferentially formed on a Rh1Pd9(100) surface, while a thin Pd oxide layer was formed on a Rh1Pd9(111) surface, though the Rh oxide is thermodynamically more stable irrespective of the surface orientation. Chemical analyses revealed that the initial Rh fraction for the (111) surface was significantly lower than that for the (100) surface, which suggests that the oxidized element on the surface is kinetically selected depending on the near surface initial composition.