Alexey Boubnov

Selective catalytic reduction of NO over Fe-ZSM-5: mechanistic insights by operando HERFD-XANES and valence-to-core X-ray emission spectroscopy.

An in-depth understanding of the active site requires advanced operando techniques and the preparation of defined catalysts. We elucidate here the mechanism of the selective catalytic reduction of NO by NH3 (NH3-SCR) over a Fe-ZSM-5 zeolite catalyst. 1.3 wt % Fe-ZSM-5 with low nuclearity Fe sites was synthesized, tested in the SCR reaction and characterized by UV-vis, X-ray absorption near edge structure (XANES), and extended X-ray absorption fine structure (EXAFS) spectroscopy. Next, this defined Fe-zeolite catalyst was studied by complementary high-energy-resolution fluorescence-detected XANES (HERFD-XANES) and valence-to-core X-ray emission spectroscopy (V2C XES) under different model in situ and realistic working (operando) conditions identical to the catalyst test bench including the presence of water vapor. HERFD-XANES uncovered that the coordination (between 4 and 5), geometry (tetrahedral, partly 5-fold), and oxidation state of the Fe centers (reduced in NH3, partly in SCR mixture, slight reduction in NO) strongly changed. V2C XES supported by DFT calculations provided important insight into the chemical nature of the species adsorbed on Fe sites. The unique combination of techniques applied under realistic reaction conditions and the corresponding catalytic data unraveled the adsorption of ammonia via oxygen on the iron site. The derived reaction model supports a mechanism where adsorbed NOx reacts with ammonia coordinated to the Fe(3+) site yielding Fe(2+) whose reoxidation is slow.

Oscillatory CO Oxidation Over Pt/Al2O3 Catalysts Studied by In situ XAS and DRIFTS

Fresh and mildly aged Pt/Al2O3 model diesel oxidation catalysts with small and large noble metal particle size have been studied during CO oxidation under lean burn reaction conditions to gain more insight into the structure and oscillatory reaction behaviour. The catalytic performance, CO adsorption characteristics using in situ DRIFTS and oxidation state using in situ XAS were correlated. Stable and pronounced oscillations only occurred over the catalyst with smaller particle sizes. Characteristic for this catalyst are low-coordinated surface Pt sites (more corner and edge atoms) which seem to become oxidized at elevated temperature as evidenced by in situ DRIFTS and in situ XAS. In situ XAS further uncovered that the oxidation of the Pt surface starts from the end of the catalyst bed and the oxidation state oscillates like the catalytic activity.

Fe and Mn‐Based Catalysts Supported on γ‐Al2O3 for CO Oxidation under O2‐Rich Conditions

MnOx and FeOx‐based catalysts supported on γ‐Al2O3 (0.1–20 wt %) were prepared by using two methods: incipient wetness impregnation and single‐step flame spray pyrolysis. The effect of the structural properties and composition on the CO oxidation activity was systematically evaluated and correlated with the preparation methods. The characterization of the samples by XRD, X‐ray absorption spectroscopy, TEM, and temperature‐programmed reduction by hydrogen revealed that, in contrast to the use of incipient wetness impregnation, flame spray pyrolysis leads to the formation of highly dispersed homogeneously distributed FeOx and MnOx species. A partial incorporation of Fe and Mn ions into the γ‐Al2O3 lattice for low metal oxide loadings and for samples prepared by flame spray pyrolysis was observed. In general, the CO oxidation activity increased with the transition metal oxide loading. Below 200 °C, Mn‐based catalysts demonstrated the highest catalytic performance. However, the addition of water decreased the performance, especially at lower temperatures, which demonstrates the competitive adsorption on the active sites. The presence of NO had no effect on the CO conversion. A significant effect of the preparation method on the catalytic performance was observed during hydrothermal aging. The superior distribution of the active species obtained by flame spray pyrolysis leads to thermally more stable catalysts.

Identification of the iron oxidation state and coordination geometry in iron oxide- and zeolite-based catalysts using pre-edge XAS analysis

Analysis of the oxidation state and coordination geometry using pre-edge analysis is attractive for heterogeneous catalysis and materials science, especially for in situ and time-resolved studies or highly diluted systems. In the present study, focus is laid on iron-based catalysts. First a systematic investigation of the pre-edge region of the Fe K-edge using staurolite, FePO4, FeO and α-Fe2O3 as reference compounds for tetrahedral Fe(2+), tetrahedral Fe(3+), octahedral Fe(2+) and octahedral Fe(3+), respectively, is reported. In particular, high-resolution and conventional X-ray absorption spectra are compared, considering that in heterogeneous catalysis and material science a compromise between high-quality spectroscopic data acquisition and simultaneous analysis of functional properties is required. Results, which were obtained from reference spectra acquired with different resolution and quality, demonstrate that this analysis is also applicable to conventionally recorded pre-edge data. For this purpose, subtraction of the edge onset is preferentially carried out using an arctangent and a first-degree polynomial, independent of the resolution and quality of the data. For both standard and high-resolution data, multiplet analysis of pre-edge features has limitations due to weak transitions that cannot be identified. On the other hand, an arbitrary empirical peak fitting assists the analysis in that non-local transitions can be isolated. The analysis of the oxidation state and coordination geometry of the Fe sites using a variogram-based method is shown to be effective for standard-resolution data and leads to the same results as for high-resolution spectra. This method, validated by analysing spectra of reference compounds and their well defined mixtures, is finally applied to track structural changes in a 1% Fe/Al2O3 and a 0.5% Fe/BEA zeolite catalyst during reduction in 5% H2/He. The results, hardly accessible by other techniques, show that Fe(3+) is transformed into Fe(2+), while the local Fe-O coordination number of 4-5 is maintained, suggesting that the reduction involves a rearrangement of the oxygen neighbours rather than their removal. In conclusion, the variogram-based analysis of Fe K-edge spectra proves to be very useful in catalysis research.

Structure and reducibility of a Fe/Al2O3 catalyst for selective catalytic reduction studied by Fe K-edge XAFS spectroscopy

EXAFS and pre-edge information from the Fe K-edge absorption spectra is used in this study to characterise the local environment and geometry of Fe-centres in a 1% Fe/Al2O3 model catalyst. The EXAFS results reveal clusters of 2-3 Fe oxo-moieties dispersed on the Al2O3-support. The Fe3+ centres are coordinated by 6 O-atoms in a strongly distorted octahedral geometry. This is supported by the pre-edge peak, which is far more intense than in α-Fe2O3 absorption data acquired for comparison. For preliminary investigations, catalytic tests for selective catalytic reduction (SCR) of NOx by ammonia and in situ XANES studies of Fe/Al2O3 are compared with previously published data for Fe/zeolite systems. The low SCR activity of Fe/Al2O3 (compared to Fe/zeolite catalysts) in which the Fe3+ species do not change their electronic state under SCR-relevant conditions (reference temperature 250°C in our case) correlates well to the significantly higher temperatures required to reduce these species to Fe2+. The difference in reducibility (and consequently in the SCR-activity) between the two systems probably results from differences in the structure and the electronic interaction of the Fe oxo-moieties and the particular catalyst support.