Olga V. Safonova

Stability and Reactivity of ϵ−χ−θ Iron Carbide Catalyst Phases in Fischer−Tropsch Synthesis: Controlling μC

The stability and reactivity of ϵ, χ, and θ iron carbide phases in Fischer-Tropsch synthesis (FTS) catalysts as a function of relevant reaction conditions was investigated by a synergistic combination of experimental and theoretical methods. Combined in situ X-ray Absorption Fine Structure Spectroscopy/X-ray Diffraction/Raman Spectroscopy was applied to study Fe-based catalysts during pretreatment and, for the first time, at relevant high pressure Fischer-Tropsch synthesis conditions, while Density Functional Theory calculations formed a fundamental basis for understanding the influence of pretreatment and FTS conditions on the formation of bulk iron carbide phases. By combining theory and experiment, it was found that the formation of θ-Fe(3)C, χ-Fe(5)C(2), and ϵ-carbides can be explained by their relative thermodynamic stability as imposed by gas phase composition and temperature. Furthermore, it was shown that a significant part of the Fe phases was present as amorphous carbide phases during high pressure FTS, sometimes in an equivalent amount to the crystalline iron carbide fraction. A catalyst containing mainly crystalline χ-Fe(5)C(2) was highly susceptible to oxidation during FTS conditions, while a catalyst containing θ-Fe(3)C and amorphous carbide phases showed a lower activity and selectivity, mainly due to the buildup of carbonaceous deposits on the catalyst surface, suggesting that amorphous phases and the resulting textural properties play an important role in determining final catalyst performance. The findings further uncovered the thermodynamic and kinetic factors inducing the ϵ-χ-θ carbide transformation as a function of the carbon chemical potential μ(C).

CO and NO2 gas sensitivity of nanocrystalline tin dioxide thin films doped with Pd, Ru and Rh

Abstract The effect of Pd, Ru and Rh doping on microstructure, electrical, and gas sensor properties of nanocrystalline tin dioxide films is studied. SnO2 and SnO2(M) (M=Pd, Ru, Rh) films of 0.9–1-μm thickness and a doping metal content of 0.07–1.6 at.% are synthesized by aerosol pyrolysis. Studies at 50–400 °C of the evolution of conductivity of noble metal-doped tin dioxide films put in contact with gas mixtures containing small amounts of CO and NO2 give evidence of strong similarities of the interaction mechanisms. Correlations between the electrical response and oxygen affinity of noble metal clusters were found.

A von Hamos x-ray spectrometer based on a segmented-type diffraction crystal for single-shot x-ray emission spectroscopy and time-resolved resonant inelastic x-ray scattering studies

We report on the design and performance of a wavelength-dispersive type spectrometer based on the von Hamos geometry. The spectrometer is equipped with a segmented-type crystal for x-ray diffraction and provides an energy resolution in the order of 0.25 eV and 1 eV over an energy range of 8000 eV-9600 eV. The use of a segmented crystal results in a simple and straightforward crystal preparation that allows to preserve the spectrometer resolution and spectrometer efficiency. Application of the spectrometer for time-resolved resonant inelastic x-ray scattering and single-shot x-ray emission spectroscopy is demonstrated.

Generating Highly Active Partially Oxidized Platinum during Oxidation of Carbon Monoxide over Pt/Al2O3: In Situ, Time-Resolved, and High-Energy-Resolution X-Ray Absorption Spectroscopy

High activity is generated by sudden formation of disordered oxidic platinum over a platinum catalyst supported on alumina (see picture). High temperature and low concentration of carbon monoxide are required to generate high activity.

Polymerization of Ethylene by Silica-Supported Dinuclear CrIIISites through an Initiation Step Involving CH Bond Activation

The insertion of an olefin into a preformed metal-carbon bond is a common mechanism for transition-metal-catalyzed olefin polymerization. However, in one important industrial catalyst, the Phillips catalyst, a metal-carbon bond is not present in the precatalyst. The Phillips catalyst, CrO3 dispersed on silica, polymerizes ethylene without an activator. Despite 60 years of intensive research, the active sites and the way the first CrC bond is formed remain unknown. We synthesized well-defined dinuclear Cr(II) and Cr(III) sites on silica. Whereas the Cr(II) material was a poor polymerization catalyst, the Cr(III) material was active. Poisoning studies showed that about 65 % of the Cr(III) sites were active, a far higher proportion than typically observed for the Phillips catalyst. Examination of the spent catalyst and isotope labeling experiments showed the formation of a Si-(μ-OH)-Cr(III) species, consistent with an initiation mechanism involving the heterolytic activation of ethylene at Cr(III) O bonds.

Proton transfers are key elementary steps in ethylene polymerization on isolated chromium(III) silicates

Significance The Phillips catalyst—CrOx/SiO2—produces 40–50% of global high-density polyethylene, yet several fundamental mechanistic controversies surround this catalyst. What is the oxidation state and nuclearity of the active Cr sites? How is the first Cr–C bond formed? How does the polymer propagate and regulate its molecular weight? Here we show through combined experimental (infrared, ultraviolet-visible, X-ray near edge absorption spectroscopy, and extended X-ray absorption fine structures) and density functional theory modeling approaches that mononuclear tricoordinate Cr(III) sites immobilized on silica polymerize ethylene by the classical Cossee–Arlman mechanism. Initiation (C–H bond activation) and polymer molecular weight regulation (the microreverse of C–H activation) are controlled by proton transfer steps. Mononuclear Cr(III) surface sites were synthesized from grafting [Cr(OSi(OtBu)3)3(tetrahydrofurano)2] on silica partially dehydroxylated at 700 °C, followed by a thermal treatment under vacuum, and characterized by infrared, ultraviolet-visible, electron paramagnetic resonance (EPR), and X-ray absorption spectroscopy (XAS). These sites are highly active in ethylene polymerization to yield polyethylene with a broad molecular weight distribution, similar to that typically obtained from the Phillips catalyst. CO binding, EPR spectroscopy, and poisoning studies indicate that two different types of Cr(III) sites are present on the surface, one of which is active in polymerization. Density functional theory (DFT) calculations using cluster models show that active sites are tricoordinated Cr(III) centers and that the presence of an additional siloxane bridge coordinated to Cr leads to inactive species. From IR spectroscopy and DFT calculations, these tricoordinated Cr(III) sites initiate and regulate the polymer chain length via unique proton transfer steps in polymerization catalysis.

SNBL, a dedicated beamline for combined in situ X-ray diffraction, X-ray absorption and Raman scattering experiments

X-ray diffraction, X-ray absorption spectroscopy and Raman scattering are commonly used for studies of crystal and electronic structure of materials. All three techniques have their strong points and limitations but by combining them into one experimental set-up it is possible to exploit their complementarities. The biggest advantage of such a multi-technique approach lies in the observation of dynamic processes. This is where (quasi-)simultaneous data acquisition with different techniques ensures a perfect correlation between these measurements. As a result, one obtains information about the materials structure, which goes beyond the sum obtained by individual experimental methods. The success of the multiple technique approach depends strongly on the rigorous optimisation of all related experimental details. In this article, we describe some of these crucial methodological solutions implemented at Swiss-Norwegian beamline.

Effect of combined Pd and Cu doping on microstructure, electrical and gas sensor properties of nanocrystalline tin dioxide

The effect of combined Pd and Cu doping on microstructure, electrical and gas sensor properties of nanocrystalline tin dioxide was studied. SnO2, SnO2(PdO), SnO2(CuO), and SnO2(PdO+CuO) films thickness of 0.8–1 μm with doping metal content 0.5–1.6 at.% were synthesized by aerosol pyrolysis. An average SnO2 grain size decreased with the addition of both Pd and Cu. The resistance measurements at 77–373 K showed that all types of doping induce resistivity increase accompanied by the appearance of conductivity activation process. Conductivity transients in the presence of CO were studied at 323–523 K. For the samples doped with Pd the sensor response to CO was found to be comparable with the resistivity increment induced by Pd incorporation into SnO2 matrix. To reveal the effect of CO on the conductivity the low temperature resistance was measured for the films in non-equilibrium state reached by cooling down the film exposed to CO at T=523 K. Experimental data proved that CO adsorption may be regarded as a factor neutralizing the Pd doping action on the films conductivity. The catalytic effect of Pd clusters was found in the interaction of SnO2(PdO+CuO) films with CO.

Dopants in nanocrystalline tin dioxide

The review surveys studies aimed at constructing new materials for gas sensors based on nanocrystalline tin dioxide. The influence of doping with various impurities (Pt, Pd, Ru, Rh, Cu, Ni, or Fe) on the composition, microstructure, and electrophysical and sensor properties of nanocrystalline SnO2 was discussed. The conditions for the preparation of powders and thick and thin SnO2 films by the wet chemical method and aerosol pyrolysis of organometallic compounds are reported. The mechanism of interaction of pure and doped nanocrystalline SnO2 with a gas phase was analyzed based on the data from Mossbauer, Auger electron, and X-ray photoelectron spectroscopy and the results of in situ Raman spectroscopy, XANES, and conductivity measurements.

Catalytically Active and Spectator Ce3+ in Ceria-Supported Metal Catalysts†

Identification of active species and the rate-determining reaction steps are crucial for optimizing the performance of oxygen-storage materials, which play an important role in catalysts lowering automotive emissions, as electrode materials for fuel cells, and as antioxidants in biomedicine. We demonstrated that active Ce(3+) species in a ceria-supported platinum catalyst during CO oxidation are short-lived and therefore cannot be observed under steady-state conditions. Using time-resolved resonant X-ray emission spectroscopy, we quantitatively correlated the initial rate of Ce(3+) formation under transient conditions to the overall rate of CO oxidation under steady-state conditions and showed that ceria reduction is a kinetically relevant step in CO oxidation, whereas a fraction of Ce(3+) was present as spectators. This approach can be applied to various catalytic processes involving oxygen-storage materials and reducible oxides to distinguish between redox and nonredox catalytic mechanisms.