Dmitry E. Doronkin

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.

Facile synthesis of surface N-doped Bi2O2CO3: Origin of visible light photocatalytic activity and in situ DRIFTS studies

Bi2O2CO3 nanosheets with exposed {001} facets were prepared by a facile room temperature chemical method. Due to the high oxygen atom density in {001} facets of Bi2O2CO3, the addition of cetyltrimethylammonium bromide (CTAB) does not only influence the growth of crystalline Bi2O2CO3, but also modifies the surface properties of Bi2O2CO3 through the interaction between CTAB and Bi2O2CO3. Nitrogen from CTAB as dopant interstitially incorporates in the Bi2O2CO3 surface evidenced by both experimental and theoretical investigations. Hence, the formation of localized states from NO bond improves the visible light absorption and charge separation efficiency, which leads to an enhancement of visible light photocatalytic activity toward to the degradation of Rhodamine B (RhB) and oxidation of NO. In addition, the photocatalytic NO oxidation over Bi2O2CO3 nanosheets was successfully monitored for the first time using in situ diffuse reflectance infrared Fourier-transform spectroscopy (DRIFTS). Both bidentate and monodentate nitrates were identified on the surface of catalysts during the photocatalytic reaction process. The application of this strategy to another relevant bismuth based photocatalyst, BiOCl, demonstrated that surface interstitial N doping could also be achieved in this case. Therefore, our current route seems to be a general option to modify the surface properties of bismuth based photocatalysts.

Ti0 nanoparticles via lithium-naphthalenide-driven reduction

Metallic titanium (Ti(0)) nanoparticles, 1.5 ± 0.4 nm in diameter, are obtained via lithium naphthalenide ([LiNaph])-driven reduction of TiCl4× 2THF in tetrahydrofuran (THF). HRTEM, fast Fourier transformation (FFT), optical spectra and X-ray absorption near edge structure (XANES) confirm their chemical composition. Besides their pyrophoric properties, their high reactivity is validated by direct transformation of Ti(0) into TiC maintaining the size.

Reactivity of Surface Nitrates in H2-Assisted SCR of NOx Over Ag/Al2O3 Catalyst

The role of nitrate ad-species in H2-assisted SCR over Ag/Al2O3 was compared in NH3-SCR and n-C6H14-SCR processes. It was found that nitrates could be reduced by NH3 or n-C6H14 at similar rates with H2 co-feeding which indicates a common rate-limiting step. However, contributions of surface nitrate reduction to the overall NH3-SCR or n-C6H14-SCR are different as revealed by comparing the rates of nitrate reduction with the rates of steady-state processes. The rate of the steady-state n-C6H14-SCR is virtually identical to the rate of surface nitrate reduction suggesting a significant contribution of the surface nitrates reduction to the overall n-C6H14-SCR process. On the other hand, the steady-state rate of NH3-SCR is by ~15 times higher, which indicates that the reduction of surface nitrates plays a marginal role in the overall NH3-SCR.

Platinum loaded tin dioxide: a model system for unravelling the interplay between heterogeneous catalysis and gas sensing

The presented work combines state-of-the-art material characterization with operando spectroscopy to unravel the complex structure–function-relationships which determine the gas sensing properties of Pt-loaded SnO2. It was found that platinum forms nanometer-sized oxide clusters at the tin dioxide surface, which act as the major reaction sites for CO oxidation strongly increasing the reactivity of the material. There is no direct correlation between the materials reactivity and gas sensing performance: oxidation catalysis requires an efficient CO oxidation and restoration of the initial state, while gas sensing requires reversible changes of the initial state, which can be translated into an electrical signal. The Pt content of the material and the atmospheric conditions determine whether CO oxidation or CO sensing dominate. In addition, this work demonstrates that for the Pt loaded samples the gas sensing properties are controlled by a Fermi-level control mechanism: the electronic coupling of the two oxides determines the charge transport in the sensing layer, which now depends on composition of the platinum phase.

Bifunctional hybrid catalysts derived from Cu/Zn-based nanoparticles for single-step dimethyl ether synthesis

Well-defined colloidal Cu/Zn-based nanoparticles were synthesized and employed as precursors for the methanol active component in bifunctional syngas-to-dimethyl ether (STD) catalysts. The experiments were conducted using simulated biomass-derived, CO-rich syngas (H2 : CO ratio of 1 : 1) in a single continuous-flow reactor by combining the two catalytically active components (i.e., Cu/ZnO for methanol synthesis and γ-Al2O3 for its subsequent dehydration). Two different synthetic pathways were developed for synthesizing the colloidal Cu/Zn-based nanoparticles, while ensuring close contacts between the Cu nanoparticles and the Zn phase. Pure Cu nanoparticles were used as a reference. A series of bifunctional STD catalysts was prepared, where the nanoparticles were either directly supported on the dehydration catalyst or integrated into the STD catalyst by physical mixing. With this approach, active catalysts for the STD reaction with high DME selectivity were obtained.

Combination of Ag/Al2O3 and Fe-BEA for High-Activity Catalyst System for H2-Assisted NH3-SCR of NO x for Light-Duty Diesel Car Applications

Low-temperature active Ag/Al2O3 and high-temperature active Fe-BEA zeolite were combined and tested for H2-assisted NH3-selective catalytic reduction (SCR) of NOx. The catalysts were either washcoated onto separate monoliths that were placed up- or downstream of each other (dual-brick layout) or washcoated on top of each other in a sandwiched layout (dual-layer). Our results showed that it is highly preferred to have Ag/Al2O3 as the upstream or outer layer catalyst. Fe-BEA showed a high NH3 oxidation giving an NH3 deficit over the Ag/Al2O3. Ag/Al2O3 formed NO2 which enhanced the activity over Fe-BEA through the “fast”-SCR reaction when Fe-BEA was placed downstream or as inner layer. When no H2, which is needed for the SCR reaction over Ag/Al2O3, was added, the dual-layer layout was preferred. The shorter diffusion distance between the layers is a probable explanation.

Transient structural and catalytic behaviour of Pt-particles probed by operando spectroscopy during a realistic driving cycle

Pt-based diesel oxidation catalysts were investigated for CO oxidation activity under rapid transient temperature conditions based on a realistic driving cycle, which is presently a focal point in exhaust gas aftertreatment. Experiments were performed in a microreactor setup allowing rapid heating/cooling coupled with operando Turbo X-ray absorption spectroscopy (T-XAS) and on-line product analysis by mass spectrometry. Significant differences were observed in catalyst structure and performance depending on the temperature ramp rate. Particularly for Pt/Al2O3, the Pt oxidation state followed a dynamic hysteresis profile during CO oxidation light-off and light-out. In contrast, in Pt–CeO2/Al2O3, ceria acted as an oxygen storage buffer, reducing the width of the Pt oxidation/reduction hysteresis loop as a function of the temperature ramp rate. Ceria also supplied oxygen to the Pt surface, helping to maintain high activity during cooling down and at lower temperatures during transient conditions. This study shows the potential insights into the reaction mechanism available when considering transient temperature as an experimental condition during operando spectroscopic studies in exhaust gas catalysis. The current method is applicable to virtually any rapid transient temperature driving cycle.