Formation and Segregation of a Pd-MgO Solid Solution Studied by X-ray Absorption Spectroscopy.

Thermal treatment of Pd nanoparticles or Pd(NH3)4(NO3)2 supported on MgO resulted in the formation of a solid solution of Pd-MgO, as evidenced by Pd K-edge X-ray absorption fine structure (XAFS). The valence of Pd in the Pd-MgO solid solution was determined to be 4+ from the comparison of X-ray absorption near edge structure (XANES) with reference compounds. A characteristic shrinkage of the Pd-O bond distance was observed in comparison with that of the nearest-neighboring Mg-O bond in MgO, which agreed with the density functional theory (DFT) calculations. The two-spike pattern was observed in the dispersion of Pd-MgO owing to the formation and successive segregation of solid solutions above 1073 K.

Formation of a Pt-MgO Solid Solution: Analysis by X-ray Absorption Fine Structure Spectroscopy.

Thermal treatment of Pt nanoparticles or Pt(acac)2 supported on MgO resulted in the formation of a solid solution of Pt-MgO, as evidenced by Pt L3-edge X-ray absorption fine structure spectroscopy. The valence of Pt in the Pt-MgO solid solution was determined to be 4+. A characteristic shrinkage of the Pt-O bond distance was observed in comparison with that of the nearest-neighboring Mg-O bond in MgO, which agreed with the density functional theory (DFT) calculations. The segregation of Pt and MgO proceeded with a further increase in the thermal treatment temperature up to 1273 K. The dispersion of Pt on MgO measured through CO adsorption was much higher than that on Al2O3 or SiO2 owing to the formation of the Pt-MgO solid solution.

Volcano-type correlation between particle size and catalytic activity on hydrodechlorination catalyzed by AuPd nanoalloy.

Although changing the size of metal nanoparticles (NPs) is a reasonable way to tune and/or enhance their catalytic activity, size-selective preparation of NPs possessing random-alloy morphology has been challenging because of the differences in the ionization potential of each metal ion. This study demonstrates a time-controlled aggregation-stabilization method for the size-selective preparation of random alloy NPs composed of Au and Pd, which are stabilized by poly(N-vinyl-2-pyrrolidone) (PVP). By adjusting the mixing time in the presence of a small amount of PVP, aggregation was induced to produce AuPd:PVP with sizes ranging between 1.2 and 8.2 nm at approximately 1 nm intervals. Transmission electron microscopy (TEM), powder X-ray diffraction (PXRD), and extended X-ray absorption fine structure (EXAFS) analyses indicated the formation of various sizes of AuPd nanoalloys, and size-dependent catalytic activity was observed when hydrodechlorination of 4-chloroanisole was performed using 2-propanol as a reducing agent. AuPd:PVP with a size of 3.1 nm exhibited the highest catalytic activity. A comparison of the absorption edges of X-ray absorption near edge structure (XANES) spectra suggested that the electronic state of the Au and Pd species correlated with their catalytic activity, presumably affecting the rate-determining step.

Direct Methylation of Benzene with Methane Catalyzed by Co/MFI Zeolite.

Cobalt-loaded MFI zeolite showed distinct activity for direct methylation of benzene with methane into toluene. High activity was found at around 0.6 of Co/Al molar ratio. Incorporation of carbon from methane into the methyl group of toluene was confirmed with isotope tracer experiments and mass spectroscopy. Ammonia infrared-mass spectroscopy temperature-programmed desorption, transmission electron microscopy, X-ray absorption near edge spectroscopy and extended X-ray absorption fine structure indicated that Lewis acidic divalent (+II of oxidation state) Co species mono-atomically dispersed on the ion exchange site of MFI zeolite was the active species.

The Impact of the Polymer Chain Length on the Catalytic Activity of Poly(N-vinyl-2-pyrrolidone)-supported Gold Nanoclusters.

Poly(N-vinyl-2-pyrrolidone) (PVP) of varying molecular weight (M w = 40-360 kDa) were employed to stabilize gold nanoclusters of varying size. The resulting Au:PVP clusters were subsequently used as catalysts for a kinetic study on the sized-dependent aerobic oxidation of 1-indanol, which was monitored by time-resolved in situ infrared spectroscopy. The obtained results suggest that the catalytic behaviour is intimately correlated to the size of the clusters, which in turn depends on the molecular weight of the PVPs. The highest catalytic activity was observed for clusters with a core size of ~7 nm, and the size of the cluster should increase with the molecular weight of the polymer in order to maintain optimal catalytic activity. Studies on the electronic and colloid structure of these clusters revealed that the negative charge density on the cluster surface also strongly depends on the molecular weight of the stabilizing polymers.

Suzuki Coupling Reactions Catalyzed by PdO Dispersed on Dealuminated Y Zeolite in Air under Ambient Conditions.

Suzuki coupling reactions are performed using PdO loaded on dealuminated Y (USY) zeolite. The reaction between bromobenzene and phenylboronic acid is complete in 15 min at room temperature in air, with a turnover number of 1300. The reaction can be repeated at least five times by using 1 wt % Pd. Inductively coupled plasma analysis does not reveal the dissolution of Pd from products, even if the reaction is repeated up to four times. Pd K-edge extended X-ray absorption fine structure analysis reveals the presence of molecular-like PdO and a mixture of Pd(0) -PdO before and after the reaction, respectively. This is probably because Pd stabilized by Al sites is present at the II sites of the Y-type zeolite, as estimated using first-principles calculations. Conversely, Pd species change to PdO clusters after repeated reactions in air using the thermally treated sample.

Hydrodeoxygenation of vicinal OH groups over heterogeneous rhenium catalyst promoted by palladium and ceria support.

Heterogeneous ReOx-Pd/CeO2 catalyst showed excellent performance for simultaneous hydrodeoxygenation of vicinal OH groups. High yield (>99%), turnover frequency (300 h(-1)), and turnover number (10,000) are achieved in the reaction of 1,4-anhydroerythritol to tetrahydrofuran. This catalyst can be applied to sugar alcohols, and mono-alcohols and diols are obtained in high yields (≥85%) from substrates with even and odd numbers of OH groups, respectively. The high catalytic performance of ReOx-Pd/CeO2 can be assigned to rhenium species with +4 or +5 valence state, and the formation of this species is promoted by H2/Pd and the ceria support.

Selective hydrogenation of lactic acid to 1,2-propanediol over highly active ruthenium-molybdenum oxide catalysts.

Modification of Ru/C with a small amount of MoOx (RuMoOx /C) enhanced the catalytic activity in the hydrogenation of L-lactic acid to form 1,2-propanediol and maintained high selectivity. The turnover frequency based on the amount of Ru over the optimized RuMoOx /C catalyst (Mo/Ru molar ratio=1:16) was 114 h(-1) at 393 K, which was about 4 times higher than that over Ru/C. The same effect of MoOx was obtained over RuMoOx /SiO2 , although RuMoOx /SiO2 showed slightly lower activity than that of RuMoOx /C. RuMoOx /C achieved a high yield of 95 % in 18 h at 393 K and was applicable to various carboxylic acids to provide the corresponding alcohols in high yields. Modification with MoOx also brought about suppression of racemization and (S)-1,2-propanediol was obtained in high enantiomeric excess at 353 K. Based on kinetic analysis and characterization data, such as XRD, TEM, CO adsorption by a volumetric method, FTIR spectroscopy, and X-ray absorption spectroscopy, for RuMoOx /C and RuMoOx /SiO2 , the catalyst structure and reaction mechanism are proposed.

Enhancement in the catalytic activity of Pd/USY in the heck reaction induced by H2 bubbling.

Pd was loaded on ultra stable Y (USY) zeolites prepared by steaming NH(4)-Y zeolite under different conditions. Heck reactions were carried out over the prepared Pd/USY. We found that H2 bubbling was effective in improving not only the catalytic activity of Pd/USY, but also that of other supported Pd catalysts and Pd(OAc)2. Moreover, the catalytic activity of Pd/USY could be optimized by choosing appropriate steaming conditions for the preparation of the USY zeolites; Pd loaded on USY prepared at 873 K with 100% H2O gave the highest activity (TOF = 61,000 h⁻¹), which was higher than that of Pd loaded on other kinds of supports. The prepared Pd/USY catalysts were applicable to the Heck reactions using various kinds of substrates including bromo- and chloro-substituted aromatic and heteroaromatic compounds. Characterization of the acid properties of the USY zeolites revealed that the strong acid site (OH(strong)) generated as a result of steaming had a profound effect on the catalytic activity of Pd.

Highly dispersed Pd species active in the Suzuki-Miyaura reaction.

Structures of Pd/zeolites immersed in solvents were measured by in situ X-ray absorption fine structure (XAFS). Systematic studies revealed that the selection of an appropriate support (USY-zeolite), thermal treatment temperature of USY, solvent (o-xylene), H(2) partial pressure (6%), and the use of a Pd amine complex affect the structure of Pd. As a result, we found that monomeric Pd can be obtained in the USY support with H(2) bubbling in o-xylene. The structural properties of Pd correlate well with its catalytic performance in the Suzuki-Miyaura coupling reactions; a very high TON of up to 11,000,000 was obtained over the monomeric Pd.

Speciation of iodine in solid environmental samples by iodine K-edge XANES: application to soils and ferromanganese oxides.

A method was developed for speciation of iodine in solid materials using X-ray absorption near-edge structure (XANES). This method was used to identify the iodine species (mainly inorganic iodine) in environmental samples. It was shown that the XANES spectra of iodide and iodate sorbed within solid materials can be simulated by the linear combination of the spectra of iodide and iodate ions in water. The distribution coefficient (Kd) between soil and water was obtained independently for iodide and iodate, based on iodine speciation both in the solid phase, by XANES, and in the aqueous phase, by HPLC-ICP-MS. It was found that the Kd of iodate is larger than that of iodide by a factor of more than six, showing the more soluble nature of iodide. It was suggested that iodate can form in soil even when iodide is injected into the soil-water system under conditions within the iodide-stable field of the Eh-pH diagram of iodine. This is caused by the much higher affinity of iodate for solid surfaces than iodide. In soil samples under various water saturation conditions, or various Eh conditions, the iodide fraction in water increases with decreasing Eh, which results in an increase in the dissolved total iodine fraction in soil water. The speciation method using XANES was also applied to iodine in a natural soil sample and marine ferromanganese oxides. It is suggested that iodine K-edge XANES is a promising tool for determining the iodide/iodate ratio in natural solid samples, which contributes to better understanding of the behavior of iodine at the Earth's surface.

Quick XAFS studies on the Y-type zeolite supported Au catalysts for CO-O2 reaction.

Au/zeolite catalysts prepared with a deposition-precipitation method were characterized with quick XAFS (QXAFS) in combination with IR. The data were correlated with the catalytic performance in the CO-O(2) reaction conducted at 273 K. On the basis of the XANES analysis of Au loaded on H-Y, the deposited Au(2)O(3) was observed at the initial stage. The transformation of Au(2)O(3) to form metal Au clusters was observed at 473 K in a H(2) atmosphere. The fact was supported by the IR measurement of adsorbed CO and the subsequent reaction with O(2). Detailed clustering process of Au supported catalysts could be directly followed by EXAFS analysis. The growth of metal Au proceeded via the formation of a Au(55) cluster at 473 K. Then it agglomerated to give metal Au with diameter of 2 nm at 723 K. The addition of H(2) was effective to retard the sintering of Au clusters. A similar phenomenon was observed over Au loaded on USY zeolite. In marked contrast to the H-Y and USY supports, significantly agglomerated Au particles generated on Na-Y zeolite, indicating the importance of the presence of acid sites in keeping the Au clusters with highly dispersed form. The performance of 5 wt % Au loaded on H-Y and USY in the CO-O(2) reaction was remarkably sensitive to the pretreatment temperature and the gas atmosphere. The catalyst pretreated with hydrogen showed a two-spike pattern with respect to the pretreatment temperature. Namely, the optimum activity was observed after the pretreatment at 373 and 723 K, where the temperatures corresponded to the generation of Au(2)O(3) and metal Au clusters with 2 nm diameter as evidenced by QXAFS analysis, respectively. The reason for enhancement of the activity of Au/H-Y by the addition of H(2) in the pretreatment step could be attributed to the formation of metal Au with appropriate size. In contrast to the H-Y and USY support, Au loaded on Na-Y prepared under the same condition was almost inactive in the reaction due to the formation of aggregated metal Au.

Energy-Dispersive XAFS Studies on the Spontaneous Dispersion of PdO and the Formation of Stable Pd Clusters in Zeolites.

Spontaneous dispersion and clustering processes of Pd were measured by means of the energy-dispersive EXAFS method. The spontaneous dispersion of bulky metal Pd into highly dispersed PdO was directly observed on the H-type zeolite in the atmosphere of O2. In contrast to H-type zeolites, simple oxidation of the agglomerated Pd was observed on Na-ZSM-5. The structural change of Pd was followed in the atmosphere of hydrogen. The clustering processes of metal Pd depended on the kind of zeolite, and these were categorized into three groups. The first group, i.e., Na-ZSM-5 and H-beta, showed monotonic agglomeration of metal Pd by increasing the reduction temperature. The second group consisted of H-ZSM-5 and H-mordenite where the formation of Pd6 clusters was found. On these zeolites, the generation of Pd6 clusters was reversibly observed upon the repetition of reduction and oxidation treatments. The third group consisted of H-Y and USY zeolites where the formation of Pd13 clusters was observed. From these findings, it was concluded that the crystal structure and acid sites of zeolites had profound influences on the dynamic behavior and the genesis of Pd clusters with various structures.