The Effect of Electrical Polarization on Electronic Structure in LSM Electrodes: An Operando XAS, RIXS and XES Study

The influence of electrical polarization on Mn in La0.5Sr0.5MnO3±δ electrodes has been investigated by operando High Energy Resolved Fluorescence Detected X-Ray Absorption Near-Edge Structure (HERFD-XANES) spectroscopy, Kβ X-ray Emission Spectroscopy (XES) and Resonant Inelastic X-ray Scattering (RIXS) at the Mn K-edge. The study of polarization induced changes in the electronic properties and structure has been carried out at 500°C in 10–20% O2 with electrical polarization applied in the range from −850 mV to 800 mV. Cathodic polarizations in the range −600 mV to −850 mV induced a shift in the Mn K edge energy towards lower energies. The shift is assigned to a decrease in the average Mn oxidation state, which based on Kβ XES changes from 3.4 at open circuit voltage to 3.2 at −800 mV applied potential. Furthermore, RIXS rendered pronounced changes in the population of the Mn 3d orbitals, due to filling of the Mn d-orbitals during the cathodic polarization. Overall, the study experimentally links the electrical polarization of LSM electrodes to the structural and electronic properties of Mn - these properties are expected to be of major importance for the electrocatalytic performance of LSM electrode towards the oxygen reduction reaction

The 16th International Conference on X-ray Absorption Fine Structure (XAFS16)

This preface of the proceedings volume of the 16th International Conference on X- ray Absorption Fine Structure (XAFS16) gives a glance on the five days of cutting-edge X-ray science which were held in Karlsruhe, Germany, August 23 - 28, 2015. In addition, several satellite meetings took place in Hamburg, Berlin and Stuttgart, a Sino-German workshop, three data analysis tutorials as well as special symposia on industrial catalysis and XFELs were held at the conference venue

Emission of Toxic HCN During NOx Removal by Ammonia SCR in the Exhaust of Lean-Burn Natural Gas Engines

Reducing greenhouse gas and pollutant emissions is one of the most stringent priorities of our society to minimize their dramatic effects on health and environment. Natural gas (NG) engines, in particular at lean conditions, emit less CO$_{2}$ in comparison to combustion engines operated with liquid fuels but NG engines still require emission control devices for NO$_{x}$ removal. Using state‐of‐the‐art technologies for selective catalytic reduction (SCR) of NO$_{x}$ with NH$_{3}$, we evaluated the interplay of the reducing agent NH$_{3}$ and formaldehyde, which is always present in the exhaust of NG engines. Our results show that a significant amount of highly toxic hydrogen cyanide (HCN) is formed. All catalysts tested partially convert formaldehyde to HCOOH and CO. Additionally, they form secondary emissions of HCN due to catalytic reactions of formaldehyde and its oxidation intermediates with NH$_{3}$. With the present components of the exhaust gas aftertreatment system the HCN emissions are not efficiently converted to non‐polluting gases. The development of more advanced catalyst formulations with improved oxidation activity is mandatory to solve this novel critical issue

Cobalt-based Nanoreactors in Combined Fischer-Tropsch Synthesis and Hydroprocessing: Effects on Methane and CO2_{2} Selectivity

Fischer-Tropsch synthesis: Four types of bi-functional catalysts with cobalt nanoparticles supported on meso- or microporous silicates or aluminosilicates are investigated regarding the obtained CO$_{2}$ and CH$_{4l}$ selectivity under low-temperature Fischer-Tropsch reaction conditions. In situ x-ray absorption spectroscopy results under industrially relevant conditions reveal that strong cobalt-support interactions and oxidized cobalt species are the main factors determining the selectivity depending on the specific support material used. The production of liquid hydrocarbons from syngas (CO and H$_{2}$) via the combined Fischer-Tropsch (FT) synthesis and hydroprocessing (HP) is a promising strategy to provide valuable chemicals and fuels based on renewable feedstocks. High yields of liquid products are essential for industrial implementation since short-chain side products like methane and CO$_{2}$ reduce the overall carbon efficiency, which holds true especially for bi-functional Co/zeolite catalysts. In order to investigate the influence of the support material properties on the methane and CO$_{2}$ selectivities in the combined FT and HP reaction, we synthesized four well-defined catalyst materials with similar cobalt particle sizes. The active material is supported on either meso- or microporous silicates or aluminosilicates. The catalytic properties are investigated in FT experiments at industrially relevant conditions (20 bar, 200–260 °C) and correlated with in situ x-ray absorption spectroscopy results to determine the chemical environment responsible for the selectivity observed. The origin of the high methane selectivity detected for crystalline and amorphous aluminosilicate was mainly traced back to the strong cobalt-support interactions. The high CO$_{2}$ selectivity, observed only for crystalline zeolite materials, is driven by the presence of oxidized cobalt species, while the acidic support in combination with micropores and possible overcracking leads to the observed drop in the C$_{5+}$ selectivity

Thermal ageing phenomena and strategies towards reactivation of NO x - storage catalysts

The thermal ageing and reactivation of Ba/CeO2 and Ba/Al2O3 based NO x -storage/ reduction (NSR) catalysts was studied on model catalysts and catalyst systems at the engine. The mixed oxides BaAl2O4 and BaCeO3, which lower the storage activity, are formed during ageing above 850°C and 900°C, respectively. Interestingly, the decomposition of BaCeO3 in an atmosphere containing H2O/NO2 leads again to NO x -storage active species, as evidenced by comparison of fresh, aged and reactivated Pt-Ba/CeO2 based model catalysts. This can be technically exploited, particularly for the Ba/CeO2 catalysts, as reactivation studies on thermally aged Ba/CeO2 and Ba/Al2O3 based NSR catalysts on an engine bench showed. An on-board reactivation procedure is presented, that improved the performance of a thermally aged catalyst significantl

The Influence of Active Phase Loading on the Hydrodeoxygenation (HDO) of Ethylene Glycol over Promoted MoS2_{2}/MgAl2_{2}O4_{4} Catalysts

The hydrodeoxygenation (HDO) of ethylene glycol over MgAl$_{2}$O$_{4}$ supported NiMo and CoMo catalysts with around 0.8 and 3 wt% Mo loading was studied in a continuous flow reactor setup operated at 27 bar H$_{2}$ and 400 °C. A co-feed of H2S of typically 550 ppm was beneficial for both deoxygenation and hydrogenation and for enhancing catalyst stability. With 2.8-3.3 wt% Mo, a total carbon based gas yield of 80-100 % was obtained with an ethane yield of 36-50 % at up to 118 h on stream. No ethylene was detected. A moderate selectivity towards HDO was obtained, but cracking and HDO were generally catalyzed to the same extent by the active phase. Thus, the C2/C1 ratio of gaseous products was 1.1-1.5 for all prepared catalysts independent on Mo loading (0.8-3.3 wt%), but higher yields of C1-C3 gas products were obtained with higher loading catalysts. Similar activities were obtained from Ni and Co promoted catalysts. For the low loading catalysts (0.83-0.88 wt% Mo), a slightly higher hydrogenation activity was observed over NiMo compared to CoMo, giving a relatively higher yield of ethane compared to ethylene. Addition of 30 wt% water to the ethylene glycol feed did not result in significant deactivation. Instead, the main source of deactivation was carbon deposition, which was favored at limited hydrogenation activity and thus, was more severe for the low loading catalysts