In Situ Structural Determination of a Homogeneous Ruthenium Racemization Catalyst and Its Activated Intermediates Using X-Ray Absorption Spectroscopy

The activation process of a known Ru-catalyst, dicarbonyl(pentaphenylcyclopentadienyl)ruthenium chloride, has been studied in detail using time resolved in situ X-ray absorption spectroscopy. The data provide bond lengths of the species involved in the process as well as information about bond formation and bond breaking. On addition of potassium tert-butoxide, the catalyst is activated and an alkoxide complex is formed. The catalyst activation proceeds via a key acyl intermediate, which gives rise to a complete structural change in the coordination environment around the Ru atom. The rate of activation for the different catalysts was found to be highly dependent on the electronic properties of the cyclopentadienyl ligand. During catalytic racemization of 1-phenylethanol a fast-dynamic equilibrium was observed.     

Experimental Evidence for the Incorporation of Two Metals at Equivalent Lattice Positions in Mixed-Metal Metal–Organic Frameworks

Metal–organic frameworks containing multiple metals distributed over crystallographically equivalent framework positions (mixed-metal MOFs) represent an interesting class of materials, since the close vicinity of isolated metal centers often gives rise to synergistic effects. However, appropriate characterization techniques for detailed investigations of these mixed-metal metal–organic framework materials, particularly addressing the distribution of metals within the lattice, are rarely available. The synthesis of mixed-metal FeCuBTC materials in direct syntheses proved to be difficult and only a thorough characterization using various techniques, like powder X-ray diffraction, X-ray absorption spectroscopy and electron paramagnetic resonance spectroscopy, unambiguously evidenced the formation of a mixed-metal FeCuBTC material with HKUST-1 structure, which contained bimetallic Fe−Cu paddlewheels as well as monometallic Cu−Cu and Fe−Fe units under optimized synthesis conditions. The in-depth characterization showed that other synthetic procedures led to impurities, which contained the majority of the applied iron and were impossible or difficult to identify using solely standard characterization techniques. Therefore, this study shows the necessity to characterize mixed-metal MOFs extensively to unambiguously prove the incorporation of both metals at the desired positions. The controlled positioning of metal centers in mixed-metal metal–organic framework materials and the thorough characterization thereof is particularly important to derive structure–property or structure–activity correlations.     

Structure determination and magnetic studies of triazole chelated Co(II) coordination polymers

Two cobalt(II) halide complexes with 1,2,4-triazole as a ligand were synthesized. Their structures were determined by extended x-ray absorption fine structure (EXAFS) and powder x-ray diffraction (XRD). Both complexes [Co(Htrz)Cl₂]_n ( 1 ) and {[Co(Htrz)₂(trz)]BF₄}_n ( 2 ) form one-dimensional polymeric chain and the distances of Co⋯Co are 3.3521(2) Å and 3.8629(2) Å, respectively. The Htrz and Cl⁻ are bridging ligands to connect two Co(II) ions in 1 , and the local environment of Co site is in a distorted octahedron with {CoN₂Cl₄} core. In complex 2 , two Htrz and one trz are bridging ligands to connect two Co(II) ions, and the local geometry of Co is in a pseudo octahedron with {CoN₆} core. The analysis of Co L_II,III-edge XAS indicates that the Co(II) of both complexes are at high spin state with t_2g⁵e_g² configuration and the crystal field strength (10Dq) is about 1.2 eV. The broken-symmetry DFT calculations indicate that antiferromagnetic coupling state of Co⋯Co is the most stable state in both complexes; and the coupling constants of 1 and 2 are −0.32 cm⁻¹ and −3.70 cm⁻¹, respectively. Based on the distances of Co⋯Co and coupling constants, such antiferromagnetic interaction is achieved through triazole ligands.     

X-ray absorption spectroscopy study and photocatalyst application of CuO and Cu0.9Ti0.1O nanoparticles

We report detailed investigations on the electronic structure and photocatalyst application of CuO and Cu_0.9Ti_0.1O nanoparticles (NPs). The NPs were prepared by co-precipitation method and subsequent annealing. Crystal structure and morphology of the NPs were investigated by synchrotron X-ray diffraction and high resolution transmission electron microscope, respectively. The local atomic structure around the Cu atoms was investigated by the extended X-ray absorption fine structure (EXAFS) at the Cu K-edge. Electronic structure determination was done using near edge X-ray absorption fine structure (NEXAFS) at the O K-edge, Cu L-edge, Cu K-edge and Ti L-edge. From the structural and electronic structure investigations, it is inferred that the Ti substitutes the Cu in CuO lattice without forming any secondary phases and the valence state of Cu is not affected by the Ti substitution; however the Cu – O bond length is found to be shorten in the Ti doped sample. As prepared NPs exhibit excellent photocatalyst application toward the degradation of methyl orange (MO) and potassium dichromate (PD) pollutant dyes under the visible light irradiation. The mechanism of the photodegradation of MO and PD pollutants, by the smaller sized CuO and larger sized Cu_0.9Ti_0.1O NPs, is briefly discussed.     

Muffin‐tin potentials in EXAFS analysis

Muffin‐tin potentials are the standard tool for calculating the potential surface of a cluster of atoms for use in the analysis of extended X‐ray absorption fine‐structure (EXAFS) data. The set of Cartesian coordinates used to define the positions of atoms in the cluster and to calculate the muffin‐tin potentials is commonly also used to enumerate the scattering paths used in the EXAFS data analysis. In this paper, it is shown that these muffin‐tin potentials are sufficiently robust to be used to examine quantitatively contributions to the EXAFS data from scattering geometries not represented in the original cluster.     

Extended X‐ray absorption fine structure and multiple‐scattering simulation of nickel dithiolene complexes Ni[S2C2(CF3)2]2n (n = −2, −1, 0) and an olefin adduct Ni[S2C2(CF3)2]2(1‐hexene)

A series of Ni dithiolene complexes Ni[S₂C₂(CF₃)]₂ⁿ (n = ?2, ?1, 0) ( 1 , 2 , 3 ) and a 1‐hexene adduct Ni[S₂C₂(CF₃)₂]₂(C₆H₁₂) ( 4 ) have been examined by Ni K‐edge X‐ray absorption near‐edge structure (XANES) and extended X‐ray absorption fine‐structure (EXAFS) spectroscopies. Ni XANES for 1 – 3 reveals clear pre‐edge features and approximately +0.7 eV shift in the Ni K‐edge position for `one‐electron' oxidation. EXAFS simulation shows that the Ni—S bond distances for 1 , 2 and 3 (2.11–2.16 Å) are within the typical values for square planar complexes and decrease by ～0.022 Å for each `one‐electron' oxidation. The changes in Ni K‐edge energy positions and Ni—S distances are consistent with the `non‐innocent' character of the dithiolene ligand. The Ni—C interactions at ～3.0 Å are analyzed and the multiple‐scattering parameters are also determined, leading to a better simulation for the overall EXAFS spectra. The 1‐hexene adduct 4 presents no pre‐edge feature, and its Ni K‐edge position shifts by ?0.8 eV in comparison with its starting dithiolene complex 3 . Consistently, EXAFS also showed that the Ni—S distances in 4 elongate by ～0.046 Å in comparison with 3 . The evidence confirms that the neutral complex is `reduced' upon addition of olefin, presumably by olefin donating the π‐electron density to the LUMO of 3 as suggested by UV/visible spectroscopy in the literature.     

Energy‐resolved electron‐yield XAS studies of nanoporous CoAlPO‐18 and CoAlPO‐34 catalysts

Energy‐resolved electron‐yield X‐ray absorption spectroscopy is a promising technique for probing the near‐surface structure of nanomaterials because of its ability to discriminate between the near‐surface and bulk of materials. So far, the technique has only been used in model systems. Here, the local structural characterization of nanoporous cobalt‐substituted aluminophosphates is reported and it is shown that the technique can be employed for the study of open‐framework catalytically active systems. Evidence that the cobalt ions on the surface of the crystals react differently to those in the bulk is found.     

Local structure of core/shell nanocrystalline particles produced by surfactant-assisted ball milling of Fe powder in paraffin

Surfactant-assisted ball milling of the Fe powder in paraffin has been used for fabrication of core–shell nanocrystalline particles. The local atomic structure of the bulk and surface layers of the mechanically milled particles has been studied using X-ray absorption spectroscopic techniques with synchrotron radiation from the DORIS storage ring at DESY, Hamburg. Regardless of milling environment composition, the as-prepared powders were shown to be characterized by a significant drop in the EXAFS signal intensity and coordination numbers of the Fe–Fe pairs due to the formation of nanocrystalline state in the particles. It has been shown that an addition of perfluorononanoic acid as a surfactant has a more prominent effect on the structure of the shell layers. The effect is revealed as an appearance of light element atoms (O, F, C) in the local atomic environment of the Fe atoms due to formation of oxide, carbide and adsorbed structures of different types in the particle shell.     

Adsorption of Eu(III) on titanate nanotubes studied by a combination of batch and EXAFS technique

The effects of pH,contact time and natural organic ligands on radionuclide Eu(Ⅲ) adsorption and mechanism on titanate nanotubes(TNTs) are studied by a combination of batch and extended X-ray absorption fine structure(EXAFS) techniques.Macroscopic measurements show that the adsorption is ionic strength dependent at pH < 6.0,but ionic strength independent at pH > 6.0.The presence of humic acid(HA) /fulvic acid(FA) increases Eu(Ⅲ) adsorption on TNTs at low pH,but reduces Eu(Ⅲ) adsorption at high pH.The results of EXAFS analysis indicate that Eu(Ⅲ) adsorption on TNTs is dominated by outer-sphere surface complexation at pH < 6.0,whereas by inner-sphere surface complexation at pH > 6.0.At pH < 6.0,Eu(Ⅲ) consists of ～ 9 O atoms at REu?O ≈ 2.40  in the first coordination sphere,and a decrease in NEu-O with increasing pH indicates the introduction of more asymmetry in the first sphere of adsorbed Eu(Ⅲ).At long contact time or high pH values,the Eu(Ⅲ) consists of ～2 Eu at REu-Eu ≈ 3.60  and ～ 1 Ti at REu-Ti ≈ 4.40 ,indicating the formation of inner-sphere surface complexation,surface precipitation or surface polymers.Surface adsorbed HA/FA on TNTs modifies the species of adsorbed Eu(Ⅲ) as well as the local atomic structures of adsorbed Eu(Ⅲ) on HA/FA-TNT hybrids.Adsorbed Eu(Ⅲ) on HA/FA-TNT hybrids forms both ligand-bridging ternary surface complexes(Eu-HA/FA-TNTs) as well as surface complexes in which Eu(Ⅲ) remains directly bound to TNT surface hydroxyl groups(i.e.,binary Eu-TNTs or Eu-bridging ternary surface complexes(HA/FA-Eu-TNTs)).The findings in this work are important to describe Eu(Ⅲ) interaction with nanomaterials at molecular level and will help to improve the understanding of Eu(Ⅲ) physicochemical behavior in the natural environment.     

Bayesian Analysis of Exafs Data

In this paper we demonstrate the use of Bayesian analysis methods for the analysis of EXAFS data. We will discuss the physical parameters that may be estimated by the method and demonstrate the applicability of the method to Molybdenum coordination compounds.