Kinetic, isotopic, and infrared studies on well-defined dispersed Pt clusters are combined here with first-principle theoretical methods on model cluster surfaces to probe the mechanism and structural requirements for CO oxidation catalysis at conditions typical of its industrial practice. CO oxidation turnover rates and the dynamics and thermodynamics of adsorption-desorption processes on cluster surfaces saturated with chemisorbed CO were measured on 1-20 nm Pt clusters under conditions of strict kinetic control. Turnover rates are proportional to O(2) pressure and inversely proportional to CO pressure, consistent with kinetically relevant irreversible O(2) activation steps on vacant sites present within saturated CO monolayers. These conclusions are consistent with the lack of isotopic scrambling in C(16)O-(18)O(2)-(16)O(2) reactions, and with infrared bands for chemisorbed CO that did not change within a CO pressure range that strongly influenced CO oxidation turnover rates. Density functional theory estimates of rate and equilibrium constants show that the kinetically relevant O(2) activation steps involve direct O(2)* (or O(2)) reactions with CO* to form reactive O*-O-C*=O intermediates that decompose to form CO(2) and chemisorbed O*, instead of unassisted activation steps involving molecular adsorption and subsequent dissociation of O(2). These CO-assisted O(2) dissociation pathways avoid the higher barriers imposed by the spin-forbidden transitions required for unassisted O(2) dissociation on surfaces saturated with chemisorbed CO. Measured rate parameters for CO oxidation were independent of Pt cluster size; these parameters depend on the ratio of rate constants for O(2) reactions with CO* and CO adsorption equilibrium constants, which reflect the respective activation barriers and reaction enthalpies for these two steps. Infrared spectra during isotopic displacement and thermal desorption with (12)CO-(13)CO mixtures showed that the binding, dynamics, and thermodynamics of CO chemisorbed at saturation coverages do not depend on Pt cluster size in a range that strongly affects the coordination of Pt atoms exposed at cluster surfaces. These data and their theoretical and mechanistic interpretations indicate that the remarkable structure insensitivity observed for CO oxidation reactions reflects average CO binding properties that are essentially independent of cluster size. Theoretical estimates of rate and equilibrium constants for surface reactions and CO adsorption show that both parameters increase as the coordination of exposed Pt atoms decreases in Pt(201) cluster surfaces; such compensation dampens but does not eliminate coordination and cluster size effects on measured rate constants. The structural features and intrinsic non-uniformity of cluster surfaces weaken when CO forms saturated monolayers on such surfaces, apparently because surfaces and adsorbates restructure to balance CO surface binding and CO-CO interaction energies.

Oxidation of nitric oxide (NO) for subsequent efficient reduction in selective catalytic reduction or lean NO(x) trap devices continues to be a challenge in diesel engines because of the low efficiency and high cost of the currently used platinum (Pt)-based catalysts. We show that mixed-phase oxide materials based on Mn-mullite (Sm, Gd)Mn(2)O(5) are an efficient substitute for the current commercial Pt-based catalysts. Under laboratory-simulated diesel exhaust conditions, this mixed-phase oxide material was superior to Pt in terms of cost, thermal durability, and catalytic activity for NO oxidation. This oxide material is active at temperatures as low as 120°C with conversion maxima of ~45% higher than that achieved with Pt. Density functional theory and diffuse reflectance infrared Fourier transform spectroscopy provide insights into the NO-to-NO(2) reaction mechanism on catalytically active Mn-Mn sites via the intermediate nitrate species.

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We evaluated a nonthermal plasma jet for a respective use to prevent infections from bacteria and yeasts. The plasma jet is generated from the flow of ambient air with 8 slm through a microhollow cathode discharge assembly that is operated with a direct current of 30 mA. With these parameters, the temperature in the jet reaches 43 • C at 10 mm from the discharge. Agar plates that were inoculated with Staphylococcus aureus, Pseudomonas aeruginosa, Acinetobacter baumannii, and Candida kefyr were treated at this distance, moving the plates through the jet in a meander that covered a 2 cm by 2 cm area. Different exposure times were realized by changing the speed of the movement and adjusting the distance between consecutive passes. S. aureus was most responsive to the exposure with a reduction in the number of colony forming units of 5.5 log steps in 40 s. All other microorganisms show a more gradual inactivation with exposure times. For all bacteria, a clearing of the treated area is achieved in about 2.5-3.5 min, corresponding to log-reduction factors of 5.5-6.5. Complete inactivation of the yeast requires about 7 min. Both S. aureus and C. kefyr show considerable inactivation also outside the immediate treatment area, while P. aeruginosa and A. baumannii do not. We conclude that differences in the morphologies of the membrane structures are responsible for the diverging results, together with a targeted response to different agents provided with the plasma jet. For the gram negative bacteria, we hold short-lived agents, acting across a short range, responsible, while for the other microorganisms, longer lived species seem more important. Our measurements show that neither heat, ultraviolet radiation, nor the generation of ozone can be responsible for the observed results. The most prominent long lived reaction product found is nitric oxide, which, by itself or through induced chemical reactions, might affect cell viability.

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The combined application of TiO 2 photocatalyst and pulsed high-voltage electrical discharge process for the degradation of organic pollutant parachlorophenol (4-CP) in aqueous solution was tentatively investigated. The optimum conditions for 4-CP removal were applied voltage at 14 kV, electrode distance at 2 cm, pH at 6.5 (close to neutral solution), TiO 2 concentration at 50 mg/L, gas source O 2 at 100 L/h, and hybrid corona-streamer discharge mode. Introduced TiO 2 into pulsed discharge plasma process under such optimum condition, the rate constant of 4-CP degradation (k cp ) was greatly promoted, from 1.56 · 10 )3 to 2.81 · 10 )3 s )1 , and energy efficiency for 4-CP removal was greatly enhanced by approximately one time, and it was attributed to more amounts of chemically active species (e.g., ozone and hydrogen peroxide, especially hydroxyl radicals) produced in pulsed discharge plasma process in combination with TiO 2 photocatalyst.