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At least 883 records · Page 49

Statistical characteristics of cloud variability. Part 1: Retrieved cloud liquid water path at three ARM sites: Observed cloud variability at ARM sites

Statistical characteristics of cloud variability are examined for their dependence on averaging scales and best representation of probability density function with the decade-long retrieval products of cloud liquid water path (LWP) from the tropical western Pacific (TWP), Southern Great Plains (SGP), and North Slope of Alaska (NSA) sites of the Department of Energy’s Atmospheric Radiation Measurement Program. The statistical moments of LWP show some seasonal variation at the SGP and NSA sites but not much at the TWP site. It is found that the standard deviation, relative dispersion (the ratio of the standard deviation to the mean), and skewness all quickly increase with the averaging window size when the window size is small and become more or less flat when the window size exceeds 12 h. On average, the cloud LWP at the TWP site has the largest values of standard deviation, relative dispersion, and skewness, whereas the NSA site exhibits the least. Correlation analysis shows that there is a positive correlation between the mean LWP and the standard deviation. The skewness is found to be closely related to the relative dispersion with a correlation coefficient of 0.6. The comparison further shows that the log normal, Weibull, and gamma distributions reasonably explain the observed relationship between skewness and relative dispersion over a wide range of scales.

54 ENVIRONMENTAL SCIENCES↗

Seven years of aerosol scattering hygroscopic growth measurements from SGP: Factors influencing water uptake: Aerosol Scattering Hygroscopic Growth

Long-term measurements of changes in the aerosol scattering coefficient hygroscopic growth at the U.S. Department of Energy Southern Great Plains site provide information on the seasonal as well as size and chemical dependence of aerosol hygroscopic growth. Annual average sub 10 um fRH values (the ratio of aerosol scattering at 85%/40% RH) were 1.75 and 1.87 for the gamma and kappa fit algorithms, respectively. The study found higher growth rates in the winter and spring seasons that correlated with high aerosol nitrate mass fraction. FRH, exhibited strong, but differing correlations with the scattering Ångström exponent and backscatter fraction, two optical size-dependent parameters. The aerosol organic fraction had a strong influence, with fRH decreasing with increases in the organic mass fraction and absorption Ångström exponent and increasing with the aerosol single scatter albedo. Uncertainty analysis if the fit algorithms revealed high uncertainty at low scattering coefficients and slight increases in uncertainty at high RH and fit parameters values.

Jefferson, A.↗

Multiscale model based design of an energy–intensified novel adsorptive reactor process for the water gas shift reaction

In this work, an adsorptive reactor (AR) process is considered that can energetically intensify the water gas shift reaction (WGSR). To best understand AR process behavior, a multiscale, dynamic, process model is developed. This multiscale model enables the quantification of catalyst and adsorbent effectiveness factors within the reactor environment, obliviating the commonly employed assumption that these factors are constant. Simulations of the AR's alternating adsorption-reaction/desorption operation, using the proposed model, illustrate rapid convergence to a long-term periodic solution. The obtained simulation results quantify the influence of key operating conditions and design parameters (e.g., reactor temperature/pressure, W cat /F CO , W ad /F CO , F H2O /F CO ratios, and pellet size) on the AR's behavior. Finally, they also demonstrate, for pellet diameters used at the industrial scale, significant temporal and axial variation of the catalyst/adsorbent pellet effectiveness factors. Finally, the energetic intensification benefits of the proposed AR process over conventional WGSR packed-bed reactors are quantified.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Sugar Blowing-Induced Porous Cobalt Phosphide/Nitrogen-Doped Carbon Nanostructures with Enhanced Electrochemical Oxidation Performance toward Water and Other Small Molecules

Finely controlled synthesis of high active and robust nonprecious metal catalysts with excellent catalytic efficiency in oxygen evolution reaction (OER) is extremely vital for making the water splitting process more energy-efficient and economical. Among these noble metal-free catalysts, transition-metal-based nanomaterials are considered as one of the most promising OER catalysts due to their relatively low-cost intrinsic activities, high abundance and diversity in terms of structure and morphology. In this work, we reported a facile sugar-blowing technique and low-temperature phosphorization to generate 3D self-supported metal involved carbon nanostructures, which termed as Co2P@Co/nitrogen-doped carbon (Co2P@Co/N-C). By capitalizing on the 3D porous nanostructures with high surface area, generously dispersed active sites, the intimate interaction between active sites and 3D N-doped carbon, the resultant Co2P@Co/N-C exhibited satisfying OER performance superior to CoO@Co/N-C, delivering 10 mA cm-2 at overpotential of 0.32 V. It is noting that in contrast to the substantial current density loss of RuO2, Co2P@Co/N-C showed much enhanced catalytic activity during the stability test and the 1.8-fold increase in current density was observed after stability test. Furthermore, the obtained Co2P@Co/N-C can also be served as an excellent nonprecious metal catalyst for methanol and glucose electrooxidation in alkaline media, further extending their potential applications.

Environmental Molecular Sciences Laboratory↗

Striving toward noble-metal-free photocatalytic water splitting: The hydrogenated-graphene-TiO 2 prototype

Graphane, graphone and hydrogenated graphene (HG) have been extensively studied in recent years due to their interesting properties and potential use in commercial and industrial applications. The present study reports investigation of hydrogenated graphene/TiO 2-x (HGT) nanocomposites as photocatalysts for H 2 and O 2 production from water without the assistance of a noble metal co-catalyst. By combination of several techniques, the morphologies, bulk/atomic structure and electronic properties of all the powders were exhaustively interrogated. Hydrogenation treatment efficiently reduces TiO 2 nanoparticles, while the graphene oxide sheets undergo the topotactic transformation from a graphene-like structure to a mixture of graphitic and turbostratic carbon (amorphous/disordered) upon altering the calcination atmosphere from a mildly reducing to a H 2 -abundant environment. Remarkably, the hydrogenated graphene-TiO 2-x composite that results upon H 2 -rich reduction exhibits the highest photocatalytic H 2 evolution performance equivalent to low loading of Pt (~0.12 wt%), whereas the addition of HG suppresses the O 2 production. As a result, we propose that such an enhancement can be attributed to a combination of factors including the introduction of oxygen vacancies and Ti 3+ states, retarding the recombination of charge carriers and thus, facilitating the charge transfer from TiO 2 -x to the carbonaceous sheet.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

5-Methoxyquinoline Photobasicity Is Mediated by Water Oxidation

A mechanism explaining the photobasicity of 5-methoxyquinoline (5-MeOQ) is proposed on the basis of nonadiabatic molecular dynamics simulations using time-dependent hybrid density functional theory (TDDFT) and fewest switches surface hopping (SH) and analysis of existing ultrafast spectroscopy experiments. According to the TDDFT-SH simulations, the rate-determining step is hole transfer from photoexcited 5-MeOQ to adjacent water molecules within ~5 ps followed by rapid electron-coupled proton transfer and deactivation to the ground state. This fast redox-catalyzed proton transfer mechanism is consistent with simple thermodynamic arguments, correlated wavefunction calculations, and recent isotope substitution time-resolved fluorescence experiments. Although energetically feasible, direct protonation of 5-MeOQ in the S 1 state appears to be too slow to contribute significantly to 5-MeOQ photobasicity in aqueous solution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗