Photocatalytic CO2 Reduction Using Ti3C2Xy (X = Oxo, OH, F, or Cl) MXene-ZrO2: Structure, Electron Transmission, and the Stability.

CO2 photoreduction using a semiconductor-based photocatalyst is a promising option for completing a new carbon-neutral cycle. The short lifetime of charges generated owing to light energy is one of the most critical problems in further improving the performance of semiconductor-based photocatalysts. This study shows the structure, electron transmission, and stability of Ti3C2Xy (X = oxo, OH, F, or Cl) MXene combined with a ZrO2 photocatalyst. Using H2 as a reductant, the photocatalytic CO formation rate increased by 6.6 times to 4.6 µmol h-1 gcat-1 using MXene (3.0 wt %)-ZrO2 compared to that using ZrO2, and the catalytic route was confirmed using 13CO2 to form 13CO. In clear contrast, using H2O (gas) as a reductant, CH4 was formed as the major product using Ti3C2Xy MXene (5.0 wt %)-ZrO2 at the rate of 3.9 µmol h-1 gcat-1. Using 13CO2 and H2O, 12CH4, 12C2H6, and 12C3H8 were formed besides H212CO, demonstrating that the C source was the partial decomposition and hydrogenation of Ti3C2Xy. Using the atomic force and high-resolution electron microscopies, 1.6 nm thick Ti3C2Xy MXene sheets were observed, suggesting ∼3 stacked layers that are consistent with the Ti-C and Ti···Ti interatomic distances of 0.218 and 0.301 nm, respectively, forming a [Ti6C] octahedral coordination, and the major component as the X ligand was suggested to be F and OH/oxo, with the temperature increasing by 116 K or higher owing to the absorbed light energy, all based on the extended X-ray absorption fine structure analysis.

Study on triphase of polymorphs TiO2 (anatase/rutile/brookite) for boosting photocatalytic activity of metformin degradation.

The elution of pharmaceutical products such as metformin at higher concentrations than the safe level in aquatic systems is a serious threat to human health and the ecosystem. Photocatalytic technology using TiO2 semiconductors potentially fixes this problem. This study aims to synthesize triphasic anatase-rutile-brookite TiO2 using ultrasound assisted sol-gel technique in the presence of acid and its application to photodegradation of metformin under UV light irradiation. Based on X-ray diffraction analysis, a TiO2 sample consisted of anatase (76%), rutile (7%), and brookite (17%) polymorph (A76R7B17) that was fully crystallized. Scanning electron microscopy (EM)-energy dispersive X-ray spectra results showed agglomerated triphasic A76R7B17 with irregular spherical clusters. Transmission EM results revealed that the crystal size of A76R7B17 was 4-14 nm. The Brunauer-Emmett-Teller analysis showed the sample's specific surface area of 149 m2 g-1. The degradation test of metformin demonstrated that the A76R7B17 exhibited a 75.4% degradation efficiency after 120 min under UV light irradiation, significantly higher than using biphasic and single-phase TiO2 photocatalysts. This difference could be attributed to the heterojunction effect of triphasic materials that effectively reduced electron-hole recombination rate as well as the combination of effective electron transfer from conduction band of brookite and anatase and the utilization of wider range of UV-visible light using rutile.

Rapid Probing of Self-Cleaning Activity on Polyester Coated by Titania-Natural Silica Nanocomposite Using Digital Image-Based Colorimetry.

Titania-silica nanocomposites (TiO2-SiO2) show outstanding performance and is very well applied in photocatalysis. In this research, SiO2 extracted from Bengkulu beach sand will be used as a supporting material of the TiO2 photocatalyst for application to polyester fabrics. TiO2-SiO2 nanocomposite photocatalysts were synthesized using the sonochemical method. The coating of the TiO2-SiO2 material on polyester was carried out using the sol-gel-assisted sonochemistry method. The method of determining self-cleaning activity uses a digital image-based colorimetric (DIC) method, which is much simpler than using an analytical instrument. The scanning electron microscopy-energy dispersive X-ray spectroscopy results showed that the sample particles adhered to the fabric surface and the best particle distribution was shown in pure SiO2 and 1:0.5 TiO2-SiO2 nanocomposites. Analysis of Fourier-transform infrared (FTIR) spectroscopy proved the presence of Ti-O and Si-O bonds as well as the typical spectrum of polyester, which indicated that the fabric had been successfully coated with nanocomposite particles. The analysis of the contact angle of the liquid on the polyester surface showed a significant change in the properties of the TiO2 and SiO2 pure coated fabrics, but changes occur only slightly in the other samples. Self-cleaning activity against the degradation of methylene blue dye has been successfully carried out using DIC measurement. The test results showed that the best self-cleaning activity was shown by TiO2-SiO2 nanocomposite with a ratio of 1:0.5 with the degradation ratio reaching 96.8%. Furthermore, the self-cleaning property remains after the washing process, which shows excellent washing resistance.

Efficient and Selective Interplay Revealed: CO2 Reduction to CO over ZrO2 by Light with Further Reduction to Methane over Ni0 by Heat Converted from Light.

The reaction mechanism of CO2 photoreduction into methane was elucidated by time-course monitoring of the mass chromatogram, in situ FTIR spectroscopy, and in situ extended X-ray absorption fine structure (EXAFS). Under 13 CO2 , H2 , and UV/Vis light, 13 CH4 was formed at a rate of 0.98 mmol h-1 gcat -1 using Ni (10 wt %)-ZrO2 that was effective at 96 kPa. Under UV/Vis light irradiation, the 13 CO2 exchange reaction and FTIR identified physisorbed/chemisorbed bicarbonate and the reduction because of charge separation in/on ZrO2 , followed by the transfer of formate and CO onto the Ni surface. EXAFS confirmed exclusive presence of Ni0 sites. Then, FTIR spectroscopy detected methyl species on Ni0 , which was reversibly heated to 394 K owing to the heat converted from light. With D2 O and H2 , the H/D ratio in the formed methane agreed with reactant H/D ratio. This study paves the way for using first row transition metals for solar fuel generation using only UV/Vis light.

Stabilizing Atomically Dispersed Catalytic Sites on Tellurium Nanosheets with Strong Metal-Support Interaction Boosts Photocatalysis.

The utilization of appropriate supports for constructing single-atom-catalysts is of vital importance to achieve high catalytic performances, as the strong mutual interactions between the atomically dispersed metal atoms and supports significantly influence their electronic properties. Herein, it is reported that atomic cobalt species (ACS) anchored 2D tellurium nanosheets (Te NS) can act as a highly active single-atom cocatalyst for boosting photocatalytic H2 production and CO2 reduction reactions under visible light irradiation, wherein Te NS serves as the ideal support material to bridge the light absorbers and ACS catalytic sites for efficient electron transfer. X-ray absorption near-edge structure spectroscopy reveals that the ACS are built by a Co center coordinated with five CoO bonding, which are anchored on Te NS through one CoTe bonding. The strong mutual interaction between the Te NS and ACS alters the electronic structure of Te NS, inducing the introduction of intermediate energy states, which act as trap sites to accommodate the photogenerated electrons for promoting photocatalytic reactions. This work may inspire further capability in designing other Te-based single-atom-catalysts for highly efficient solar energy conversion.

Dual Photocatalytic Roles of Light: Charge Separation at the Band Gap and Heat via Localized Surface Plasmon Resonance To Convert CO2 into CO over Silver-Zirconium Oxide.

Confirmation of 13CO2 photoconversion into a 13C-product is crucial to produce solar fuel. However, the total reactant and charge flow during the reaction is complex; therefore, the role of light during this reaction needs clarification. Here, we chose Ag-ZrO2 photocatalysts because beginning from adventitious C, negligible products are formed using them. The reactants, products, and intermediates at the surface were monitored via gas chromatography-mass spectrometry and FTIR, whereas the temperature of Ag was monitored via Debye-Waller factor obtained by in situ extended X-ray absorption fine structure. With exposure to 13CO2, H2, and UV-visible light, 13CO selectively formed, while 8.6% of the 12CO mixed in the product due to the formation of 12C-bicarbonate species from air that exchanged with the 13CO2 gas-phase during a 2 h reaction. By choosing the light activation wavelength, the CO2 photoconversion contribution ratio was charge separated at the ZrO2 band gap (λ < 248 nm): 70%, localized at the Ag surface plasmon resonance (LSPR) (330 < λ < 580 nm): 28%, and characterized by a thermal energy of 295 K: 2%. LSPR at the Ag surface was converted to heat at temperatures of up to 392 K, which provided an efficient supply of activated H species to the bicarbonate species, combined with separated electrons and holes above the ZrO2, which generated CO at a rate of 0.66 µmol h-1 gcat-1 with approximately zero order kinetics. Photoconversion of 13CO2 using moisture was also possible. Water photo-oxidation step above ZrO2 was rate-limited, and the side reactions that formed H2 above the Ag were successfully suppressed instead to produce CO via the Mg2+ addition to trap CO2 at the surface.

Why Is Water More Reactive Than Hydrogen in Photocatalytic CO2 Conversion at Higher Pressures? Elucidation by Means of X-Ray Absorption Fine Structure and Gas Chromatography-Mass Spectrometry.

Photocatalytic conversion of CO2 into mainly methane using Pd/TiO2 photocatalyst proceeded faster at 0.80 MPa using water rather than hydrogen as a reductant. The former reaction (CO2 + water) consists of two steps: first, water photosplitting and second, the latter reaction (CO2 + hydrogen). It was paradoxical that total steps proceeded faster than each step based on simple kinetics. To elucidate the reason, Pd and Ti K-edge X-ray absorption fine structure (XAFS) was monitored during CO2 photoconversion using H2 or moisture and the exchange reaction of 13CO2 at Pd/TiO2 surface was also monitored. As a result, the coordination number, N(Ti-O) and N[Ti(-O-)Ti] values, decreased from original values for TiO2 crystalline (6 and 12) to 4.9-5.7 and 9.7-10.6 under CO2 and moisture, respectively, in contrast to significantly smaller decreases under CO2 and H2 and under Ar. The exchange of gas-phase 13CO2 with preadsorbed 12CO2 reached the equilibrium in ~20 h with a rate constant of 0.20 h-1. The reason of the higher activity using water rather than H2 could be explained owing to the oxygen vacancy (O v ) sites as confirmed by XAFS. The reaction of TiO2 surface with water formed O v sites responsible for water oxidation, specially separated from Pd nanoparticle sites for CO2 reduction. In contrast, Pd nanoparticle sites were competed by CO2 and H species, and the photoconversion of CO2 was suppressed at the elevated pressure of CO2 + H2.

A photofuel cell comprising titanium oxide and silver(I/0) photocatalysts for use of acidic water as a fuel.

A photofuel cell comprising two photocatalysts TiO2 and Ag-TiO2 is demonstrated. The open circuit voltage, short circuit current, and maximum electric power of the PFC were 1.59 V, 74 µA, and 14 µW, respectively. The electron flow was rectified due to the Schottky barrier between TiO2 and Ag nanoparticles.

Catalytic conversion of carbon dioxide into dimethyl carbonate using reduced copper-cerium oxide catalysts as low as 353 K and 1.3 MPa and the reaction mechanism.

Synthesis of dimethyl carbonate (DMC) from CO2 and methanol under milder reaction conditions was performed using reduced cerium oxide catalysts and reduced copper-promoted Ce oxide catalysts. Although the conversion of methanol was low (0.005-0.11%) for 2 h of reaction, DMC was synthesized as low as 353 K and at total pressure of as low as 1.3 MPa using reduced Cu-CeO2 catalyst (0.5 wt% of Cu). The apparent activation energy was 120 kJ mol(-1) and the DMC synthesis rates were proportional to the partial pressure of CO2. An optimum amount of Cu addition to CeO2 was 0.1 wt% for DMC synthesis under the conditions at 393 K and total pressure of 1.3 MPa for 2 h (conversion of methanol: 0.15%) due to the compromise of two effects of Cu: the activation of H2 during reduction prior to the kinetic tests and the block (cover) of the surface active site. The reduction effects in H2 were monitored through the reduction of Ce(4+) sites to Ce(3+) based on the shoulder peak intensity at 5727 eV in the Ce L3-edge X-ray absorption near-edge structure (XANES). The Ce(3+) content was 10% for reduced CeO2 catalyst whereas it increased to 15% for reduced Cu-CeO2 catalyst (0.5 wt% of Cu). Moreover, the content of reduced Ce(3+) sites (10%) associated with the surface O vacancy (defect sites) decreased to 5% under CO2 at 290 K for reduced Cu-CeO2 catalyst (0.1 wt% of Cu). The adsorption step of CO2 on the defect sites might be the key step in DMC synthesis and thus the DMC synthesis rate dependence on the partial pressure of CO2 was proportional. Subsequent H atom subtraction steps from methanol at the neighboring surface Lewis base sites should combine two methoxy species to the adsorbed CO2 to form DMC, water, and restore the surface O vacancy.

X-ray absorption fine structure combined with X-ray fluorescence spectroscopy. Monitoring of vanadium sites in mesoporous titania, excited under visible light by selective detection of vanadium Kbeta5,2 fluorescence.

The photocatalytic role of vanadium doped in mesoporous TiO2 has not been clarified. Valence state-sensitive V Kbeta5,2-selecting (5462.9 eV) X-ray absorption fine structure (XAFS) was used to monitor the V sites in mesoporous TiO2 for ethanol dehydration under equilibrium in situ conditions and visible light-illumination. First, the feasibility of discriminating V(IV) sites from a 1:1 physical mixture of standard V(IV) and V(V) inorganic compounds was demonstrated, by tuning the secondary fluorescence spectrometer to 5459.0 eV. The chemical shift of V Kbeta5,2 emission between V(IV) and V(V) sites was 1.0 eV. The selection of valence states V(IV) and V(V) was 100% and 80%, respectively. The redox states for ethanol dehydration over mesoporous TiO2 excited in visible light were suggested to be V(III) and V(IV). The chemical shift between valence states V(III) and V(IV) was greater (3.2 eV). On the basis of V Kbeta5,2 emission and V Kbeta5,2-selecting XAFS spectra tuned to the V Kbeta5,2 peak, we determined that the fresh mesoporous V-TiO2 catalyst has a valence state of V(IV). The vanadium sites were partially reduced by the dissociative adsorption of ethanol under visible light, but they still stay within the emission-energy ranges for standard V(IV) compounds. These partially reduced vanadium sites were reoxidized in oxygen under visible light. Finally, direct XAFS observation of photoreduced V(III) sites was attempted by tuning the fluorescence spectrometer to 5456.3 eV for partially reduced mesoporous V-TiO2. Valence state V(III) was selected for 60% of the spectrum in the mixture of V(III) (minor) and V(IV) (dominant) valence states.

Sulfur K-edge extended X-ray absorption fine structure spectroscopy of homoleptic thiolato complexes with Zn(II) and Cd(II).

The sulfur K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy is applied to homoleptic thiolato complexes with Zn(II) and Cd(II), (Et(4)N)[Zn(SAd)(3)] (1), (Et(4)N)(2)[{Zn(ScHex)(2)}(2)(mu-ScHex)(2)] (2), (Et(4)N)(2)[{Cd(ScHex)(2)}(2)(mu-ScHex)(2)] (3), (Et(4)N)(2)[{Cd(ScHex)}(4)(mu-ScHex)(6)] (4), [Zn(mu-SAd)(2)](n) (5), and [Cd(mu-SAd)(2)](n) (6) (HSAd=1-adamantanethiol, HScHex=cyclohexanethiol). The EXAFS results are consistent with the X-ray crystal data of 1-4. The structures of 5 and 6, which have not been determined by X-ray crystallography, are proposed to be polynuclear structures on the basis of the sulfur K-edge EXAFS, far-IR spectra, and elemental analysis. Clear evidences of the S...S interactions (between bridging atoms or neighboring sulfur atoms) and the S...C(far) interactions (in which C(far) atom is next to carbon atom directly bonded to sulfur atom) were observed in the EXAFS data for all complexes and thus lead to the reliable determination of the structures of 5 and 6 in combination with conventional zinc K-edge EXAFS analysis for 5. This new methodology, sulfur K-edge EXAFS, could be applied for the structural determination of in vivo metalloproteins as well as inorganic compounds.

X-ray absorption fine structure combined with X-ray fluorescence spectrometry. Improvement of spectral resolution at the absorption edges of 9-29 keV.

X-ray absorption near-edge structure (XANES) suffers from core-hole lifetime broadening at a higher energy absorption edge, such as Sn K (29 keV, Gamma(K) = 8.49 eV). To overcome this problem, emitted Sn Kalpha1 fluorescence from sample was counted using high-energy-resolution fluorescence spectrometer in the XANES measurements. Experimental energy resolution (5.0 eV) was consistent with theoretical values based on the Rowland configuration of the spectrometer. The absorption edge became steeper compared to conventional spectra. The white-line peak due to Sn(II) species became remarkably sharper and more intense in the Sn Kalpha1-detecting Sn K-edge XANES for Pt-Sn/SiO2. To support the semiclassical theory of resonant Raman scattering for the explanation of observed elimination of lifetime width, more resolved XANES data at Cu K, Pb L3, and Sn K in this work were convoluted (filtered) with a Lorentzian of each core-hole lifetime width. The processed data resembled generally well corresponding XANES spectrum measured in transmission mode. The verification based on ab initio XANES calculations was also performed.

Characterization of intercalated iron(III) nanoparticles and oxidative adsorption of arsenite on them monitored by x-ray absorption fine structure combined with fluorescence spectrometry.

This paper first deals with the screening and optimization of Fe(III)-based adsorbents for arsenic adsorption from 0.2 to 16 ppm test solutions of arsenite/arsenate. The best adsorption capacity has been reported on alpha-FeO(OH) on an adsorbent weight basis. Better results were found on intercalated Fe-montmorillonites for arsenite adsorption below the equilibrium dissolved As concentration of 310 ppb and for arsenate adsorption in all of the concentrations studied. Next, the speciation of As adsorbed was performed by As K-edge x-ray absorption fine structure (XAFS) combined with high-energy-resolution fluorescence spectrometry. Major oxidative adsorption of arsenite was observed on Fe-montmorillonite from the 0.2-16 ppm test solutions. The reasons for the higher capacity of arsenic adsorption and oxidative adsorption of arsenite on Fe-montmorillonite are discussed.

Chiral self-dimerization of vanadium complexes on a SiO2 surface for asymmetric catalytic coupling of 2-naphthol: structure, performance, and mechanism.

Vanadium monomers with chiral tridentate Schiff-base ligands were supported on SiO(2) through a chemical reaction with surface silanols, where we found a new chirality creation by the self-dimerization of the vanadyl complexes on the surface. The chiral self-dimerization and the role of surface silanols in the self-assembly were investigated by means of X-ray absorption near-edge structure (XANES), extended X-ray absorption fine structure (EXAFS), diffuse-reflectance ultraviolet/visible (DR-UV/VIS), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FT-IR), electron spin resonance (ESR), and density functional theory (DFT) calculations. The surface vanadyl complexes had a distorted square-pyramidal conformation with a V=O bond. FT-IR spectra revealed that the Ph-O moiety of Schiff-base ligands was converted to Ph-OH by a surface-concerted reaction between the vanadium precursors and surface SiOH groups. The Ph-OH in an attached vanadyl complex interacted with a COO moiety of another vanadyl complex by hydrogen bonding to form a self-dimerized structure at the surface. The interatomic distance of V-V in the surface self-assembly was evaluated to be 0.40 +/- 0.05 nm by ESR after O(2) adsorption. The self-dimerized V structure on SiO(2) was modeled by DFT calculations, which demonstrated that two vanadium monomers with Ph-OH linked together by two hydrogen bonds and their V=O groups were directed opposite to each other. The surface self-dimerization of the vanadium precursors fixes the direction of the V=O bond and the plane of the Schiff-base ligand. Thus, a new chiral reaction field was created by two types of chirality: the chiral Schiff-base ligand and the chiral V center. We have also found that the chiral self-dimerized vanadyl complexes exhibit remarkable catalytic performance for the asymmetric oxidative coupling of 2-naphthol: 96% conversion, 100% selectivity to 1,1'-binaphthol (BINOL), and 90% enantiomeric excess (ee). Increasing the vanadium loading on SiO(2) caused a dramatic swell of enantioselectivity, and the maximum 90% ee was observed on the supported catalyst with the full coverage of the vanadyl complex (3.4 wt % vanadium). This value is equivalent to the maximum ee reported in homogeneous catalysis for the coupling reaction. Furthermore, the supported vanadium dimers were reusable without loss of the catalytic performance. To our knowledge, this is the first heterogeneous catalyst for the asymmetric oxidative coupling of 2-naphthol.

X-ray absorption fine structure combined with x-ray fluorescence spectrometry. Part 15. Monitoring of vanadium site transformations on titania and in mesoporous titania by selective detection of the vanadium K alpha1 fluorescence.

X-ray absorption fine structure combined with X-ray fluorescence spectrometry was applied to various V+TiO2 hybrid samples. Emitted V K alpha1 fluorescence from the sample was selectively counted by using a high-energy-resolution (0.4 eV) spectrometer equipped with a Ge(331) crystal. Two advantages of this method, extremely high signal/background ratio and the compatibility of measurements in the atmosphere of reaction gas (in situ study in relation to heterogeneous catalysis), were effective at the V K-edge. Structure transformation of the V sites was spectroscopically followed for the V/TiO2 catalyst. The monooxo tetrahedral vanadate site was demonstrated to exist at 473 K. It transformed into dispersed species of 5-fold coordination in ambient air and further into polymeric VO(x) species in 0.85 kPa of water at 290 K. In the presence of 3.2 kPa of 2-propanol, dissociative adsorption of 2-propanol on the dispersed V species was strongly suggested at 290-473 K. In situ structure changes of V sites on TiO2 were reported by means of XAFS for the first time. The V(V) sites for the V/TiO2 catalysts were essentially identical with those for V supported on mesoporous (high-surface-area) TiO2 and V-TiO2 sample prepared by the sol-gel method. However, predominant V(IV) sites were found for mesoporous V-TiO2. The V(IV) sites substituted on the Ti sites of TiO2. When the molar ratio of V/Ti increased from 1/100 to 1/5.0, major octahedral V sites in the TiO2 matrix looked to transform into tetrahedral ones.

Nitric Oxide Reduction by Carbon Monoxide over Supported Hexaruthenium Cluster Catalysts. 1. The Active Site Structure That Depends on Supporting Metal Oxide and Catalytic Reaction Conditions.

Ruthenium site structures supported on metal oxide surfaces were designed by reacting organometallic Ru cluster [Ru6C(CO)16](2-) or [Ru6(CO)18](2-) with various metal oxides, TiO2, Al2O3, MgO, and SiO2. The surface Ru site structure, formed under various catalyst preparation and reaction conditions, was investigated by the Ru K-edge extended X-ray absorption fine structure (EXAFS). Samples of [Ru6C(CO)16](2-)/TiO2(anatase) and [Ru6C(CO)16](2-)/TiO2(rutile) were found to retain the original Ru6C framework when heated in the presence of NO (2.0 kPa) or NO (2.0 kPa) + CO (2.0 kPa) at 423 K, i.e., catalytic reaction conditions for NO decomposition. At 523 K, the Ru-Ru bonds of the Ru6C framework were cleaved by the attack of NO. In contrast, the Ru site became spontaneously dispersed over TiO2 (anatase). When being supported over TiO2 (mesoporous), MgO, or Al2O3, the Ru6C framework split into fragments in gaseous NO or NO + CO even at 423 K. The Ru6 framework of [Ru6(CO)18](2-) was found to break easily into smaller ensembles in the presence of NO and/or CO at 423 K on support. Taking into consideration the realistic environments in which these catalysts will be used, we also examined the effect of water and oxygen. When water was introduced to the sample [Ru6C(CO)16](2-)/TiO2(anatase) at 423 K, it did not have any effects on the stabilized Ru6C framework structure. In the presence of oxygen gas, however, the Ru hexanuclear structure decomposed into isolated Ru cations bound to surface oxygen atoms of TiO2 (anatase).

Structure of low concentrations of vanadium on TiO2 determined by XANES and ab initio calculations.

The major local structure of low concentrations (1-3 wt% V) of vanadium on TiO2 was determined to have two terminal oxo groups and in total five oxygen coordination by means of vanadium K-edge XANES and ab initio calculations of XANES spectra.

Nanoparticles of amorphous ruthenium sulfide easily obtainable from a TiO2-supported hexanuclear cluster complex [Ru6C(CO)16]2-: a highly active catalyst for the reduction of SO2 with H2.

TiO(2)-supported ruthenium-metal particles were derived from an anionic hexanuclear carbido carbonyl cluster [Ru(6)C(CO)(16)](2-) and compared with those prepared conventionally by impregnation of TiO(2) with a solution of RuCl(3) followed by reduction with H(2). The average sizes of the metal particles in both systems are similar, that is, 12 A for molecular cluster-derived particles and 15 A for those derived from the RuCl(3) precursor, although the size distribution is sharper in the former case. These supported particles efficiently promote the reduction of SO(2) with H(2) to give elemental sulfur. Their active form is ruthenium sulfide as confirmed by EXAFS and X-ray diffraction measurements. The nanoscale ruthenium sulfide particles, which originated from the cluster complex, have an amorphous character and show activity even at low temperature (463 K), whereas ruthenium sulfide formed from RuCl(3)-derived metal dispersion is a pyrite-type RuS(2) crystallite and needs a temperature above 513 K to effect the same catalysis. Amorphous ruthenium sulfide maintains its nano-sized scale (approximately 14 A) regardless of the reaction temperature, while RuS(2) crystallite aggregates to form larger nonuniform particles.

X-ray absorption fine structure combined with fluorescence spectrometry for monitoring trace amounts of lead adsorption in the environmental conditions.

The local structure of trace amounts of lead in an adsorbent matrix that contains a high concentration of iron and magnesium (Mg6Fe2(OH)16(CO3) x 3H2O) was successfully monitored by means of X-ray absorption fine structure spectroscopy combined with fluorescence spectrometry. A eutectic mixture of PbCO3 and Pb(OH)2 coagulated when Pb2+ was adsorbed from a 1.0 ppm aqueous solution, and in contrast, the major species was ion-exchanged Pb2+ in the case of adsorption from a 100 ppb aqueous solution. The difference was ascribed to the balance between the precipitation equilibrium for coagulation and the rate of the ion exchange reaction with surface hydroxyl groups.