Comparative Study of Exsolved and Impregnated Ni Nanoparticles Supported on Nanoporous Perovskites for Low-Temperature CO Oxidation.

This study investigated the redox exsolution of Ni nanoparticles from a nanoporous La0.52Sr0.28Ti0.94Ni0.06O3 perovskite. The characteristics of exsolved Ni nanoparticles including their size, population, and surface concentration were deeply analyzed by environmental scanning electron microscopy (ESEM), transmission electron microscopy-energy dispersive X-ray spectroscopy (TEM-EDX) mapping, and hydrogen temperature-programmed reduction (H2-TPR). Ni exsolution was triggered in hydrogen as early as 400 °C, with the highest catalytic activity for low-temperature CO oxidation achieved after a reduction step at 500 °C, despite only a 10% fraction of Ni exsolved. The activity and stability of exsolved nanoparticles were compared with their impregnated counterparts on a perovskite material with a similar chemical composition (La0.65Sr0.35TiO3) and a comparable specific surface area and Ni loading. After an aging step at 800 °C, the catalytic activity of exsolved Ni nanoparticles at 300 °C was found to be 10 times higher than that of impregnated ones, emphasizing the thermal stability of Ni nanoparticles prepared by redox exsolution.

Climbing the Hydrogen Evolution Volcano with a NiTi Shape Memory Alloy.

Alkaline water electrolysis is a sustainable way to produce green hydrogen using renewable electricity. Even though the rates of the cathodic hydrogen evolution reaction (HER) are 2-3 orders of magnitude less under alkaline conditions than under acidic conditions, the possibility of using non-precious metal catalysts makes alkaline HER appealing. We identify a novel and facile route for substantially improving HER performance via the use of commercially available NiTi shape memory alloys, which upon heating undergo a phase transformation from the monoclinic martensite to the cubic austenite structure. While the room-temperature performance is modest, austenitic NiTi outperforms Pt (which is the state-of-the-art HER electrocatalyst) in terms of current density by ≤50% at 80 °C. Surface ensembles presented by the austenite phase are computed with density functional theory to bind hydrogen more weakly than either metallic Ni or Ti and to have binding energies ideally suited for HER.

Protection of NOx Sensors from Sulfur Poisoning in Glass Furnaces by the Optimization of a "SO2 Trap".

Electrochemical NOx sensors based on yttria-stabilized zirconia (YSZ) provide a reliable onboard way to control NOx emissions from glass-melting furnaces. The main limitation is the poisoning of this sensor by sulfur oxides (SOx) contained in the stream. To overcome this drawback, an "SO2 trap" with high SOx storage capacity and low affinity to NOx is required. Two CuO/BaO/SBA-15 traps with the same CuO loading (6.5 wt.%) and different BaO loadings (5 and 24.5 wt.%, respectively) were synthetized, thoroughly characterized and evaluated as SO2 traps. The results show that the 6.5%CuO/5%BaO/SBA-15 trap displays the highest SO2 adsorption capacity and can fully adsorb SO2 for a specific period of time, while additionally displaying a very low NO adsorption capacity. A suitable quantity of this material located upstream of the sensor could provide total protection of the NOx sensor against sulfur poisoning in glass-furnace exhausts.

Atmospheric photochemistry and secondary aerosol formation of urban air in Lyon, France.

Photochemical aging of volatile organic compounds (VOCs) in the atmosphere is an important source of secondary organic aerosol (SOA). To evaluate the formation potential of SOA at an urban site in Lyon (France), an outdoor experiment using a Potential Aerosol Mass (PAM) oxidation flow reactor (OFR) was conducted throughout entire days during January-February 2017. Diurnal variation of SOA formations and their correlation with OH radical exposure (OHexp), ambient pollutants (VOCs and particulate matters, PM), Relative Humidity (RH), and temperature were explored in this study. Ambient urban air was exposed to high concentration of OH radicals with OHexp in range of (0.2-1.2)×1012 molecule/(cm3•sec), corresponding to several days to weeks of equivalent atmospheric photochemical aging. The results informed that urban air at Lyon has high potency to contribute to SOA, and these SOA productions were favored from OH radical photochemical oxidation rather than via ozonolysis. Maximum SOA formation (36 µg/m3) was obtained at OHexp of about 7.4 × 1011molecule/(cm3•sec), equivalent to approximately 5 days of atmospheric oxidation. The correlation between SOA formation and ambient environment conditions (RH & temperature, VOCs and PM) was observed. It was the first time to estimate SOA formation potential from ambient air over a long period in urban environment of Lyon.

In Situ Observation of Nanoparticle Exsolution from Perovskite Oxides: From Atomic Scale Mechanistic Insight to Nanostructure Tailoring.

Understanding and controlling the formation of nanoparticles at the surface of functional oxide supports is critical for tuning activity and stability for catalytic and energy conversion applications. Here, we use a latest generation environmental transmission electron microscope to follow the exsolution of individual nanoparticles at the surface of perovskite oxides, with ultrahigh spatial and temporal resolution. Qualitative and quantitative analysis of the data reveals the atomic scale processes that underpin the formation of the socketed, strain-inducing interface that confers exsolved particles their exceptional stability and reactivity. This insight also enabled us to discover that the shape of exsolved particles can be controlled by changing the atmosphere in which exsolution is carried out, and additionally, this could also produce intriguing heterostructures consisting of metal-metal oxide coupled nanoparticles. Our results not only provide insight into the in situ formation of nanoparticles but also demonstrate the tailoring of nanostructures and nanointerfaces.

In situ environmental HRTEM discloses low temperature carbon soot oxidation by ceria-zirconia at the nanoscale.

The very close contact between ceria-zirconia and carbon soot allows the detection of oxygen transfer from ceria-zirconia to carbon by in situ Environmental HRTEM already at low temperatures. This highlights the outstanding redox behavior and soot oxidation potential of ceria-zirconia when suitable carbon-catalyst arrangements are generated at the nanoscale.

Well-defined palladium-ceria interfacial electronic effects trigger CO oxidation.

Metal-support electronic interactions were investigated in CO oxidation by using a Pd/CeO2 model catalyst with well-defined interfaces, and electron transfer from Pd cubes to CeO2 nanorods through interfaces triggered CO oxidation at low temperature where standalone Pd and CeO2 are inert.

Physico-Chemical Characterization of Fine and Ultrafine Particles Emitted during Diesel Particulate Filter Active Regeneration of Euro5 Diesel Vehicles.

Diesel particulate filters (DPFs) are commonly employed in modern passenger cars to comply with current particulate matter (PM) emission standards. DPFs requires periodic regeneration to remove the accumulated matter. During the process, high-concentration particles, in both nucleation and accumulation modes, are emitted. Here, we report new information on particle morphology and chemical composition of fine (FPs) and ultrafine particles (UFPs) measured downstream of the DPF during active regeneration of two Euro 5 passenger cars. The first vehicle was equipped with a close-coupled diesel oxidation catalyst (DOC) and noncatalyzed DPF combined with fuel borne catalyst and the second one with DOC and a catalyzed-diesel particle filter (CDPF). Differences in PM emission profiles of the two vehicles were related to different after treatment design, regeneration strategies, and vehicle characteristics and mileage. Particles in the nucleation mode consisted of ammonium bisulfate, sulfate and sulfuric acid, suggesting that the catalyst desulfation is the key process in the formation of UFPs. Larger particles and agglomerates, ranging from 90 to 600 nm, consisted of carbonaceous material (soot and soot aggregates) coated by condensable material including organics, ammonium bisulfate and sulfuric acid. Particle emission in the accumulation mode was due to the reduced filtration efficiency (soot cake oxidation) throughout the regeneration process.

Tuning the Structure of Platinum Particles on Ceria In†Situ for Enhancing the Catalytic Performance of Exhaust Gas Catalysts.

A dynamic structural behavior of Pt nanoparticles on the ceria surface under reducing/oxidizing conditions was found at moderate temperatures (<500 °C) and exploited to enhance the catalytic activity of Pt/CeO2 -based exhaust gas catalysts. Redispersion of platinum in an oxidizing atmosphere already occurred at 400 °C. A protocol with reducing pulses at 250-400 °C was applied in a subsequent step for controlled Pt-particle formation. Operando X-ray absorption spectroscopy unraveled the different extent of reduction and sintering of Pt particles: The choice of the reductant allowed the tuning of the reduction degree/particle size and thus the catalytic activity (CO>H2 >C3 H6 ). This dynamic nature of Pt on ceria at such low temperatures (250-500 °C) was additionally confirmed by in situ environmental transmission electron microscopy. A general concept is proposed to adjust the noble metal dispersion (size, structure), for example, during operation of an exhaust gas catalyst.

Electrochemical promotion of propane oxidation on Pt deposited on a dense ß″-Al2O3 ceramic Ag(+) conductor.

A new kind of electrochemical catalyst based on a Pt porous catalyst film deposited on a ß″-Al2O3 ceramic Ag(+) conductor was developed and evaluated during propane oxidation. It was observed that, upon anodic polarization, the rate of propane combustion was significantly electropromoted up to 400%. Moreover, for the first time, exponential increase of the catalytic rate was evidenced during galvanostatic transient experiment in excellent agreement with EPOC equation.

Effect of diesel oxidation catalysts on the diesel particulate filter regeneration process.

A Diesel Particulate Filter (DPF) regeneration process was investigated during aftertreatment exhaust of a simulated diesel engine under the influence of a Diesel Oxidation Catalyst (DOC). Aerosol mass spectrometry analysis showed that the presence of the DOC decreases the Organic Carbon (OC) fraction adsorbed to soot particles. The activation energy values determined for soot nanoparticles oxidation were 97 ± 5 and 101 ± 8 kJ mol(-1) with and without the DOC, respectively; suggesting that the DOC does not facilitate elementary carbon oxidation. The minimum temperature necessary for DPF regeneration was strongly affected by the presence of the DOC in the aftertreatment. The conversion of NO to NO(2) inside the DOC induced the DPF regeneration process at a lower temperature than O(2) (ΔT = 30 K). Also, it was verified that the OC fraction, which decreases in the presence of the DOC, plays an important role to ignite soot combustion.