Dynamic Behavior of Intermediate Adsorbates to Control Activity and Product Selectivity in Heterogeneous Catalysis: Methanol Decomposition on Pt/TiO2(110).

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/TiO2(110) surface has been clarified by combination of scanning tunneling microscopy (STM), temperature-programmed desorption (TPD), and density functional theory (DFT) calculations. The methoxy intermediates were formed by the dissociative adsorption of methanol molecules on Pt nanoparticles at room temperature followed by spillover to the TiO2(110) support surface. TPD results showed that the methoxy intermediates were thermally decomposed at >350 K on the Pt sites to produce CO (dehydrogenation) and CH4 (C-O bond scission). A decrease of the Pt nanoparticle density lowered the activity for the decomposition reaction and increased the selectivity toward CH4, which indicates that the reaction is controlled by diffusion and reverse spillover of the methoxy intermediates. Time-lapse STM imaging and DFT calculations revealed that the methoxy intermediates migrate on the five-fold coordinated Ti (Ti5c) sites along the [001] or [11¯0] direction with the aid of hydrogen adatoms bonded to the bridging oxygens (Obr) and can move over the entire surface to seek and find active Pt sites. This work offers an in-depth understanding of the important role of intermediate adsorbate migration in the control of the catalytic performance in oxide-supported metal catalysts.

One-Step Preparation of Fe/N/C Single-Atom Catalysts Containing Fe-N4 Sites from an Iron Complex Precursor with 5,6,7,8-Tetraphenyl-1,12-Diazatriphenylene Ligands.

Fe/N/C single-atom catalysts containing Fe-Nx 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-N4 sites in an Fe/N/C catalyst. One-step pyrolysis of the iron complex with carbon black forms atomically dispersed Fe-N4 sites without iron aggregates. X-ray absorption spectroscopy (XAS) and electrochemical measurements revealed that the iron complex with N3-coordination is more effectively converted to Fe-N4 sites catalyzing ORR with a TOF value of 0.21 e site-1 s-1 at 0.8 V vs. RHE. This indicates that the formation of Fe-N4 sites is controlled by precise tuning of the chemical structure of the iron complex precursor.

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. Although range-extended XAFS was expected by the rejection of Au fluorescence arising from the Au substrate, a small glitch was found in the Au L3 edge because of the sudden change of the complex refraction index of the Au substrate at the Au edge. This abnormal spectrum feature can be removed by reflectivity correction using Au foil absorption data. BCLA combined with TRF-XAFS spectroscopy (BCLA + TRF-XAFS) is a new technique for the in situ surface analysis of highly dispersed systems even in the presence of a liquid overlayer.

Model building analysis - a novel method for statistical evaluation of Pt L3-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. We have performed in situ highly sensitive BCLA-empowered Back Illuminated EXAFS (BCLA + BI-EXAFS) measurements on Pt alloy nanoparticles. We obtained high quality Pt L3-edge data. We have devised a novel analytical method (model building analysis) to determine the structure of multi-component nanoparticles from just a single absorption edge. The generation of large numbers of structural models and their comparison with EXAFS fits allows us to determine the structures of Pt-containing nanoparticles, catalysts for the oxygen reduction reaction. Our results show that PtCo, PtCoN and AuPtCoN form a Pt-shell during electrochemical dealloying and that the ORR activity is directly proportional to the Pt-Pt bond length.

Photoinduced anisotropic distortion as the electron trapping site of tungsten trioxide by ultrafast W L1-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 WO3 was observed by W L1 edge XAFS spectroscopy using an XFEL. An anisotropic local distortion around the W atom could reproduce well the spectral features at a delay time of 100 ps after photoexcitation based on full potential multiple scattering calculations. The distortion involved the movement of W to shrink the shortest W-O bonds and elongate the longest one. The movement of the W atom could be explained by the filling of the dxy and dzx orbitals, which were originally located at the bottom of the conduction band with photoexcited electrons.

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. (2) Determination of the 3D structure of the metal species on an oxide powder surface is hardly possible. To overcome these difficulties, we have developed the premodified surface method, where prior to metal deposition, the oxide surface is premodified with a functional organic molecule that can strongly coordinate to a metal atom. This method has successfully provided a single metal dispersion on an oxide single-crystal surface with the 3D structure precisely determined by polarization-dependent total reflection fluorescence X-ray absorption fine structure (PTRF-XAFS). Here we describe our recent results on ultra-high dispersions of various metal atoms on TiO2 (110) surfaces premodified with mercapto compounds, and show the possibility of fine tuning and orientation control of the surface metal 3D structures.

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. We applied the technique to submonolayer (∼1014  atoms cm-2 ) Pt on HOPG and successfully obtained high signal/noise in situ XAFS data in combination with back-illuminated fluorescence XAFS (BI-FXAFS) spectroscopy. This technique allows in situ XAFS measurements of flat electrode surfaces to be performed in the presence of electrolytes.

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. At temperatures between 373 and 673 K and coverages above 0.1 monolayer, we found a 7 × 7   R 19.1 ∘ structure, but above 673 K, other complex structures were created. These structures seemed to correlate with each other and we reinterpret a 7 × 7   R 19.1 ∘ structure of P adsorbed on Ni(111) based on the similarities of these surface structures. The new rectangular structure for the 7 × 7   19.1 ∘ is discussed in relation to the Ni2P local structure.

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 TiO2 : A Highly Versatile and Chemoselective Catalyst for the Hydrogenation of Carboxylic Acid Derivatives and the N-Methylation of Amines Using H2 and CO2.

Herein, we report a heterogeneous TiO2 -supported Re catalyst (Re/TiO2 ) 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 H2 and CO2 . Initially, Re/TiO2 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/TiO2 did not produce dearomatized byproducts. DFT studies suggested that the high selectivity for the formation of alcohols in favor of the hydrogenation of aromatic rings is ascribed to the higher affinity of Re towards the COOCH3 group than to the benzene ring. Moreover, Re/TiO2 showed a wide substrate scope for the hydrogenation reaction (19 examples). Subsequently, this Re/TiO2 catalyst was applied to the hydrogenation of amides, the N-methylation of amines, and the N-alkylation of amines with carboxylic acids or esters.

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. The Pd species distribution was in agreement with the simulated thermal distribution. Temperature control was crucial to maintain the high performance of the gas sensor. The improved sensor allows homogeneous heating and has a lifetime of more than 5 years.

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.

Deprotonation of a dinuclear copper complex of 3,5-diamino-1,2,4-triazole for high oxygen reduction activity.

A dinuclear copper(II) complex of 3,5-diamino-1,2,4-triazole is one of the highly active copper-based catalysts for the oxygen reduction reaction (ORR) in basic solutions. Our in situ X-ray absorption near edge structure measurements revealed that deprotonation of the triazole ligand might cause coordination geometrical changes, resulting in the enhancement of the ORR activity.

In situ back-side illumination fluorescence XAFS (BI-FXAFS) studies on platinum nanoparticles deposited on a HOPG surface as a model fuel cell: a new approach to the Pt-HOPG electrode/electrolyte interface.

We measured the in situ polarization-dependent X-ray absorption fine structure of platinum nanoparticles (PtNPs) deposited on a flat highly oriented pyrolytic graphite (HOPG) substrate under electrochemical conditions using a back-side illumination method. In this method, the thin HOPG substrate with PtNPs deposited on one side was used as a window for incident and fluorescent X-rays, as well as an electrode. A bent crystal Laue analyzer (BCLA) was applied to the extraction of the Pt Lα fluorescent X-ray signals from strong scattered X-rays. Pt L3 edge XAFS spectra were observed for various electrode potentials and polarization directions.

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

The development of new catalysts with high N2 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 Mo6 metal core on HY zeolite, followed by the removal of all the halide ligands by activation with hydrogen. In this activation, the size of the Mo6 cluster (ca. 7 Å) is almost retained. The resulting angstrom-size cluster shows catalytic activity for ammonia synthesis from N2 and H2, and the reaction proceeds continuously even at 200 °C under 5.0 MPa. DFT calculations suggest that N[triple bond, length as m-dash]N bond cleavage is promoted by the cooperation of the multiple molybdenum sites.

Characterization of Pt-doped SnO2 catalyst for a high-performance micro gas sensor.

The atomic scale structure and its dependence on Pt concentration of a Pt-doped SnO2 (Pt-SnO2) thin film produced by a sputter-deposition method was investigated, which showed high-performance as a methane gas sensor. Extended X-ray absorption fine structure (EXAFS) and X-ray diffraction (XRD) analyses showed that Pt-SnO2 has a rutile structure similar to SnO2 crystals at less than 10 at% Pt where the Pt ion was located at the Sn position in the rutile structure. There was no evidence that Pt metal clusters were formed in the Pt-SnO2 films. The Pt-SnO2 structure became amorphous at greater than 11 at% Pt. We found a good correlation between the methane activity and local structure of Pt.

Fine tuning and orientation control of surface Cu complexes on TiO2(110) premodified with mercapto compounds: the effect of different mercapto group positions.

Three-dimensional structures of vacuum-deposited Cu species formed on TiO2(110) surfaces premodified with three mercaptobenzoic acid (MBA) isomers were studied using polarization-dependent total reflection fluorescence X-ray absorption fine structure (PTRF-XAFS). We explored the possibility of fine tuning and orientation control of the surface Cu structures, including their coordination and configuration against the surface, according to the different mercapto group positions of the three MBA isomers (o-, m-, and p-MBA). Almost linear S-Cu-O (lattice O of TiO2) surface compounds were formed on the three MBA-modified TiO2(110) surfaces; however, the orientation of the Cu species on the o- and m-MBA-modified TiO2(110) surfaces (40-45° inclined from the surface normal) was different from that on the p-MBA-modified TiO2(110) surface (60° from the surface normal). This work suggests that the selection of a different MBA isomer for premodification of a single crystal TiO2(110) surface enables fine tuning and orientation control of surface Cu complexes.

Evidence of nonelectrochemical shift reaction on a CO-tolerant high-entropy state Pt-Ru anode catalyst for reliable and efficient residential fuel cell systems.

A randomly mixed monodispersed nanosized Pt-Ru catalyst, an ultimate catalyst for CO oxidation reaction, was prepared by the rapid quenching method. The mechanism of CO oxidation reaction on the Pt-Ru anode catalyst was elucidated by investigating the relation between the rate of CO oxidation reaction and the current density. The rate of CO oxidation reaction increased with an increase in unoccupied sites kinetically formed by hydrogen oxidation reaction, and the rate was independent of anode potential. Results of extended X-ray absorption fine structure spectroscopy showed the combination of N(Pt-Ru)/(N(Pt-Ru) + N(Pt-Pt)) ≑ M(Ru)/(M(Pt) + M(Ru)) and N(Ru-Pt)/(N(Ru-Pt) + N(Ru-Ru)) ≑ M(Pt)/(M(Ru) + M(Pt)), where N(Pt-Ru)(N(Ru-Pt)), N(Pt-Pt)(N(Ru-Ru)), M(Pt), and M(Ru) are the coordination numbers from Pt(Ru) to Ru(Pt) and Pt (Ru) to Pt (Ru) and the molar ratios of Pt and Ru, respectively. This indicates that Pt and Ru were mixed with a completely random distribution. A high-entropy state of dispersion of Pt and Ru could be maintained by rapid quenching from a high temperature. It is concluded that a nonelectrochemical shift reaction on a randomly mixed Pt-Ru catalyst is important to enhance the efficiency of residential fuel cell systems under operation conditions.

Operando QEXAFS studies of Ni2P during thiophene hydrodesulfurization: direct observation of Ni-S bond formation under reaction conditions.

Structural changes in Ni(2)P/MCM-41 were followed by quick extended X-ray absorption fine structure (QEXAFS) and were directly related to changes in X-ray absorption near-edge structure (XANES) which had been used earlier for the study of the active catalyst phase. An equation is proposed to correct the transient QEXAFS spectra up to second-order in time to remove spectral distortions induced by structural changes occurring during measurements. A good correlation between the corrected QEXAFS and the XANES spectral changes was found, giving support to the conclusions derived from the XANES in the previous work, namely that the formation of a Ni-S bond in a surface NiPS phase is involved in the active site for the hydrodesulfurization reaction.