Alkylperoxy radicals are responsible for the formation of oxygenated primary organic aerosol.

Organic aerosol (OA) is an air pollutant ubiquitous in urban atmospheres. Urban OA is usually apportioned into primary OA (POA), mostly emitted by mobile sources, and secondary OA (SOA), which forms in the atmosphere due to oxidation of gas-phase precursors from anthropogenic and biogenic sources. By performing coordinated measurements in the particle phase and the gas phase, we show that the alkylperoxy radical chemistry that is responsible for low-temperature ignition also leads to the formation of oxygenated POA (OxyPOA). OxyPOA is distinct from POA emitted during high-temperature ignition and is chemically similar to SOA. We present evidence for the prevalence of OxyPOA in emissions of a spark-ignition engine and a next-generation advanced compression-ignition engine, highlighting the importance of understanding OxyPOA for predicting urban air pollution patterns in current and future atmospheres.

Single Pd Atoms on θ-Al2O3 (010) Surface do not Catalyze NO Oxidation.

New convenient wet-chemistry synthetic routes have made it possible to explore catalytic activities of a variety of single supported atoms, however, the single supported atoms on inert substrates (e.g. alumina) are limited to adatoms and cations of Pt, Pd, and Ru. Previously, we have found that single supported Pt atoms are remarkable NO oxidation catalysts. In contrast, we report that Pd single atoms are completely inactive for NO oxidation. The diffuse reflectance infra-red spectroscopy (DRIFTS) results show the absence of nitrate formation on catalyst. To explain these results, we explored modified Langmuir-Hinshelwood type pathways that have been proposed for oxidation reactions on single supported atom. In the first pathway, we find that there is energy barrier for the release of NO2 which prevent NO oxidation. In the second pathway, our results show that there is no driving force for the formation of O=N-O-O intermediate or nitrate on single supported Pd atoms. The decomposition of nitrate, if formed, is an endothermic event.

Sb@Ni12@Sb20-/+ and Sb@Pd12@Sb20n Cluster Anions, Where n = +1, -1, -3, -4: Multi-Oxidation-State Clusters of Interpenetrating Platonic Solids.

K5Sb4 and K3Sb7 Zintl ion precursors react with Pd(PPh3)4 in ethylenediamine/toluene/PBu4+ solutions to give crystals of Sb@Pd12@Sb20n-/PBu4+ salts, where n = 3, 4. The clusters are structurally identical in the two charge states, with nearly perfect Ih point symmetry, and can be viewed as an Sb@Pd12 icosahedron centered inside of an Sb20 dodecahedron. The metric parameters suggest very weak Sb-Sb and Pd-Pd interactions with strong radial Sb-Pd bonds between the Sb20 and Pd12 shells. All-electron DFT analysis shows the 3- ion to be diamagnetic with Ih symmetry and a 1.33 eV HOMO-LUMO gap, whereas the 4- ion undergoes a Jahn-Teller distortion to an S = 1/2 D3d structure with a small 0.1 eV gap. The distortion is predicted to be small and is not discernible by crystallography. Laser desorption-ionization time-of-flight mass spectrometry (LDI-TOF MS) studies of the crystalline samples show intense parent Sb@Pd12@Sb20- ions (negative ion mode) and Sb@Pd12@Sb20+ (positive ion mode) along with series of Sb@Pd12-y@Sb20-x-/+ ions. Ni(cyclooctadiene)2 reacts with K3Sb7 in en/tol/Bu4PBr solvent mixtures to give black precipitates of Sb@Ni12@Sb20n- salts that give similar Sb@Ni12@Sb20-/+ parent ions and Sb@Ni12-y@Sb20-x-/+ degradation series in the respective LDI-TOF MS studies. The solid-state and gas-phase studies of the icosahedral Sb@M12@Sb20n-/n+ ions show that the clusters can exist in the -4, -3, -1, +1 (M = Pd) and +1, -1 (M = Ni) oxidation states. These multiple-charge-state clusters are reminiscent of redox-active fullerenes (e.g., C60n, where n = +1, 0, -1, -2, -3, -4, -5, -6).

Heterobimetallic Zeolite, InV-ZSM-5, Enables Efficient Conversion of Biomass Derived Ethanol to Renewable Hydrocarbons.

Direct catalytic conversion of ethanol to hydrocarbon blend-stock can increase biofuels use in current vehicles beyond the ethanol blend-wall of 10-15%. Literature reports describe quantitative conversion of ethanol over zeolite catalysts but high C2 hydrocarbon formation renders this approach unsuitable for commercialization. Furthermore, the prior mechanistic studies suggested that ethanol conversion involves endothermic dehydration step. Here, we report the complete conversion of ethanol to hydrocarbons over InV-ZSM-5 without added hydrogen and which produces lower C2 (<13%) as compared to that over H-ZSM-5. Experiments with C2H5OD and in situ DRIFT suggest that most of the products come from the hydrocarbon pool type mechanism and dehydration step is not necessary. Thus, our method of direct conversion of ethanol offers a pathway to produce suitable hydrocarbon blend-stock that may be blended at a refinery to produce fuels such as gasoline, diesel, JP-8, and jet fuel, or produce commodity chemicals such as BTX.

Remarkable NO oxidation on single supported platinum atoms.

Our first-principles density functional theoretical modeling suggests that NO oxidation is feasible on fully oxidized single θ-Al2O3 supported platinum atoms via a modified Langmuir-Hinshelwood pathway. This is in contrast to the known decrease in NO oxidation activity of supported platinum with decreasing Pt particle size believed to be due to increased platinum oxidation. In order to validate our theoretical study, we evaluated single θ-Al2O3 supported platinum atoms and found them to exhibit remarkable NO oxidation activity. A comparison of turnover frequencies (TOF) of single supported Pt atoms with those of platinum particles for NO oxidation shows that single supported Pt atoms are as active as fully formed platinum particles. Thus, the overall picture of NO oxidation on supported Pt is that NO oxidation activity decreases with decreasing Pt particle size but accelerates when Pt is present only as single atoms.

CO oxidation on supported single Pt atoms: experimental and ab initio density functional studies of CO interaction with Pt atom on θ-Al2O3(010) surface.

Although there are only a few known examples of supported single-atom catalysts, they are unique because they bridge the gap between homogeneous and heterogeneous catalysis. Here, we report the CO oxidation activity of monodisperse single Pt atoms supported on an inert substrate, θ-alumina (Al2O3), in the presence of stoichiometric oxygen. Since CO oxidation on single Pt atoms cannot occur via a conventional Langmuir-Hinshelwood scheme (L-H scheme) which requires at least one Pt-Pt bond, we carried out a first-principles density functional theoretical study of a proposed pathway which is a variation on the conventional L-H scheme and inspired by the organometallic chemistry of platinum. We find that a single supported Pt atom prefers to bond to O2 over CO. CO then bonds with the oxygenated Pt atom and forms a carbonate which dissociates to liberate CO2, leaving an oxygen atom on Pt. Subsequent reaction with another CO molecule regenerates the single-atom catalyst. The energetics of the proposed mechanism suggests that the single Pt atoms will get covered with CO3 unless the temperature is raised to eliminate CO2. We find evidence for CO3 coverage at room temperature supporting the proposed mechanism in an in situ diffuse reflectance infrared study of CO adsorption on the catalyst's supported single atoms. Thus, our results clearly show that supported Pt single atoms are catalytically active and that this catalytic activity can occur without involving the substrate. Characterization by electron microscopy and X-ray absorption studies of the monodisperse Pt/θ-Al2O3 are also presented.

Aberration-corrected STEM imaging of Ag on gamma-Al2O3.

Ag on gamma-alumina is a promising catalyst for hydrocarbon selective catalytic reduction in lean-burn gasoline and diesel engines for transportation applications. Although much is known about the mechanism of NOx reduction and the various intermediates, little agreement exists on the nature of the active silver species. In the present work, aberration-corrected STEM has provided new information about the nature of Ag on alumina both as impregnated and following treatments at various temperatures with exposure to simulated exhaust gas. Ex situ techniques have provided new insights into the evolution of Ag on alumina following exposure to temperature and simulated exhaust gas.