Rapid-Scan Operando Infrared Spectroscopy

Novel methodology, referred to as rapid-scan operando, has been demonstrated to be a highly powerful tool for studying reaction mechanisms in heterogeneous catalysis, because it combines rapid scan for IR monitoring in the milliseconds time frame and operando methodology. As proof of concept, the NOx–CO and NOx–H2 reactions were studied as model catalyzed reactions with practical interest for removal of NOx in diesel exhausts. Rapid-scan operando experiments confirmed state-of-the-art knowledge concerning the reaction mechanisms and, more importantly, allowed us to elucidate, for the first time, the different roles of the surface hydroxy groups depending on the reductant used (CO or H2). Moreover, this new tool was used to distinguish the behavior of carbonates and nitrites under reaction conditions that could not be monitored by conventional IR spectroscopy approaches owing to overlap of their absorbance bands.Financial support from Generalitat Valenciana (Project PROMETEOII/2014/010 and grant BEST/2014/250), Spanish Ministry of Economy and Competitiveness (Projects CTQ2012–30703 and MAT2014–61992-EXP, and grant PRX14/00249), and the European Union (FEDER funding)

Pt/CexPr1−xO2 (x = 1 or 0.9) NOx storage–reduction (NSR) catalysts

Model Pt/Ce0.9Pr0.1O2 and Pt/CeO2 NOx storage–reduction catalysts were prepared via nitrate calcination, co-precipitation and carbon-templating routes. Raman spectroscopic data obtained on the catalysts indicated that the introduction of praseodymium into the ceria lattice increased the concentration of defect sites (vacancies), arising from the higher reducibility of the Pr4+ cation compared to Ce4+. For the Pr-promoted samples, H2-TPR profiles contained high temperature bulk reduction peaks which were less pronounced compared with their ceria analogs, indicating that the presence of praseodymium enhances oxygen mobility due to the creation of lattice defects. Under lean-rich cycling conditions, the cycle-averaged NOx conversion of the Pt/Ce0.9Pr0.1O2 samples was in each case substantially higher than that of the Pt/CeO2 analog, amounting to a difference of 10–15% in the absolute NOx conversion in some cases. According to DRIFTS data, a double role can be assigned to Pr doping; on the one hand, Pr accelerates the oxidation of adsorbed NOx species during the lean periods. On the other hand, Pr doping destabilizes the adsorbed NOx species during the rich periods, and the kinetics of nitrate decomposition are faster on Pt/Ce0.9Pr0.1O2, leading to improved catalyst regeneration. These results suggest that ceria-based mixed oxides incorporating Pr are promising materials for NOx storage–reduction catalysts intended for low temperature operation.The financial support of Generalitat Valenciana (predoctoral stay BEFPI/2012), the Spanish Ministry of Economy and Competitiveness (Project CTQ2012-30703), and co-financing by FEDER resources is acknowledged. Partial financial support was also provided by the National Science Foundation and the U.S. Department of Energy (DOE) under award no. CBET-1258742

Ceria-zirconia particles wrapped in a 2D carbon envelope: improved low-temperature oxygen transfer and oxidation activity

Engineering the interface between different compo-nents of heterogeneous catalysts at nanometer level canradically alter their performances.This is particularly true forceria-based catalysts where the interactions are critical forobtaining materials with enhanced properties.Here we showthat mechanical contact achieved by high-energy milling ofCeO2–ZrO2powders and carbon soot results in the formationof acore of oxide particles wrapped in athin carbon envelope.This 2D nanoscale carbon arrangement greatly increases thenumber and quality of contact points between the oxide andcarbon. Consequently,the temperatures of activation andtransfer of the oxygen in ceria are shifted to exceptionally lowtemperatures and the soot combustion rate is boosted. Thestudy confirms the importance of the redox behavior of ceria-zirconia particles in the mechanism of soot oxidation andshows that the organization of contact points at the nanoscalecan significantly modify the reactivity resulting in unexpectedproperties and functionalities.Postprint (published version

Combined removal of diesel soot particulates and NOx over CeO2–ZrO2 mixed oxides

CeO2 and Ce–Zr mixed oxides with different Ce:Zr ratios were prepared; characterised by Raman spectroscopy, XRD, TEM, N2 adsorption at −196 ◦C, and H2-TPR; and tested for soot oxidation under NOx/O2. Among the different mixed oxides, Ce0.76Zr0.24O2 provided the best results. Ce0.76Zr0.24O2 presented greater activity than pure CeO2 for soot oxidation by NOx/O2 when both catalysts were calcined at 500 ◦C (soot oxidation rates at 500 ◦C are 14.9 and 11.4 μgsoot/s, respectively), and the catalytic activity of CeO2 decayed significantly with calcination temperature (from 500 to 1000 ◦C), whereas Ce0.76Zr0.24O2 presented enhanced thermal stability at temperatures as high as 1000 ◦C. In addition, Ce0.76Zr0.24O2 catalysed the reduction of NOx by soot at around 500 ◦C more efficiently than CeO2, thereby contributing to the decreased NOx emission level. The catalytic activity of CeO2 and Ce0.76Zr0.24O2 for soot oxidation by NOx/O2 depended on the textural properties (BET area; crystallite size), but other properties of the oxides, such as redox behaviour and/or enhanced lattice oxygen mobility, also played a significant role.Spanish Ministry of Education and Science (Project CTQ2005-01358) and the ABL contract funded by the Ramon y Cajal Program and the Generalitat Valenciana

Preparation, characterisation and testing of CuO/Ce0.8Zr0.2O2 catalysts for NO oxidation to NO2 and mild temperature diesel soot combustion

CuO/ceria-zirconia catalysts have been prepared, deeply characterised (N2 adsorption–desorption isotherms at −196 °C, XRD, Raman spectroscopy, XPS, TEM and H2-TPR) and tested for NO oxidation to NO2 in TPR conditions, and for soot combustion at mild temperature (400 °C) in a NOx/O2 stream. The behaviour has been compared to that of a reference Pt/alumina commercial catalyst. The ceria-zirconia support was prepared by the co-precipitation method, and different amounts of copper (0.5, 1, 2, 4 and 6 wt%) were loaded by incipient wetness impregnation. The results revealed that copper is well-dispersed onto the ceria-zirconia support for the catalysts with low copper loading and CuO particles were only identified by XRD in samples with 4 and 6% of copper. A very low loading of copper increases significantly the activity for the NO oxidation to NO2 with regard to the ceria-zirconia support and an optimum was found for a 4% CuO/ceria-zirconia composition, showing a very high activity (54% at 348 °C). The soot combustion rate at 400 °C obtained with the 2% CuO/ceria-zirconia catalyst is slightly lower to that of 1% Pt/alumina in terms of mass of catalyst but higher in terms of price of catalyst.Financial support of Generalitat Valenciana (Prometeo/2009/047 project), the Spanish Ministry of Economy and Competitiveness (CTQ2012-30703project) and the UE (FEDER funding)