246 research outputs found

    Time-resolved Microwave Conductivity. Part 2.-Quantum-sized TiO_2 and the Effect of Adsorbates and Light Intensity on Charge-carrier Dynamics

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    Charge-carrier recombination dynamics after a pulsed laser excitation are investigated by time-resolved microwave conductivity (TRMC) for quantum-sized (Q-) TiO_2 and P25, a bulk-phase TiO_2. Adsorbed scavengers such as HNO_3, HC, HCIO_4, isopropyl alcohol, trans-decalin, tetranitromethane, and methyl viologen dichloride result in different charge-carrier recombination dynamics for Q-TiO_2 and P25. The differences include a current doubling with isopropyl alcohol for which electron injection into Q-TiO_2 is much slower than into P25 and relaxation of the selection rules of an indirect-bandgap semiconductor due to size quantization. However, the faster interfacial charge transfer predicted for Q-TiO_2 due to a 0. 2 eV gain in redox overpotentials is not observed. The effect of light intensity is also investigated. Above a critical injection level, fast recombination channels are opened, which may be a major factor resulting in the dependence of the steady-state photolysis quantum yields on l^(–1/2). The fast recombination channels are opened at lower injection levels for P25 than for Q-TiO_2, and a model incorporating the heterogeneity of surface-hole traps is presented

    Time-resolved Microwave Conductivity. Part 1.—TiO_2 Photoreactivity and Size Quantization

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    Charge-carrier recombination dynamics after laser excitation are investigated by time-resolved microwave conductivity (TRMC) measurements of quantum-sized (Q-) TiO_2, Fe^(III)-doped Q-TiO_2, ZnO and CdS, and several commercial bulk-sized TiO2 samples. After pulsed laser excitation of charge carriers, holes that escape recombination react with sorbed trans-decalin within ns while the measured conductivity signal is due to conduction-band electrons remaining in the semiconductor lattice. The charge-carrier recombination lifetime and the interfacial electron-transfer rate constant that are derived from the TRMC measurements correlate with the CW photo-oxidation quantum efficiency obtained for aqueous chloroform in the presence of TiO_2. The quantum efficiencies are 0. 4 % for Q-TiO_2, 1. 6 % for Degussa P25, and 2. 0 % for Fe^(III)-doped Q-TiO_2. The lower quantum efficiencies for Q-TiO_2 are consistent with the relative interfacial electron-transfer rates observed by TRMC for Q-TiO_2 and Degussa P25. The increased quantum efficiencies of Fe^(III)-doped Q-TiO_2 and the observed TRMC decays are consistent with a mechanism involving fast trapping of valence-band holes as Fe^(IV) and inhibition of charge-order recombination

    Hygroscopic Behavior of NaCl-Bearing Natural Aerosol Particles Using Environmental Transmission Electron Microscopy

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    We used conventional and environmental transmission electron microscopes to determine morphology, composition, and water uptake of individual natural inorganic aerosol particles collected from industrial pollution plumes and from clean and polluted marine environments. Five particle types are described in detail. They range from relatively insoluble mineral grains to internally mixed particles containing NaCl with other soluble or relatively insoluble material. We studied the hygroscopic behavior of these particles from 0 to 100% relative humidity (RH). Relatively insoluble materials do not take up water over the experimental RH range. Single crystals of NaCl from both natural and laboratory sources have a well-defined deliquescence point of approximately 76% RH at 291 K. NaCl-bearing aggregate particles appear to deliquesce between 74 and 76% RH (same RH within error) when NaCl is internally mixed with relatively insoluble phases, but the particles deliquesce at lower RH when aggregated with other soluble phases such as NaNO3. For all NaCl-bearing particles studied, hygroscopic growth is pronounced above 76% RH, and water uptake by the particles is dominated by the soluble phase. Furthermore, the soluble phase initiating deliquescence controls the locus of further hygroscopic growth of the aggregate particle. Our results demonstrate that composition and mixing state affect water uptake of natural aerosol particles. Furthermore, internally mixed particles are confirmed to deliquesce at lower RH values than predicted from the individual components

    Hygroscopic Behavior and Liquid-Layer Composition of Aerosol Particles Generated from Natural and Artificial Seawater

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    Sea-salt aerosol (SSA) particles affect the Earth\u27s radiative balance and moderate heterogeneous chemistry in the marine boundary layer. Using conventional and environmental transmission electron microscopes (ETEM), we investigated the hygroscopic growth and liquid-layer compositions of particles generated from three types of aqueous salt solutions: sodium chloride, laboratory-synthesized seawater (S-SSA particles), and natural seawater (N-SSA particles). Three levels of morphological change were observed with the ETEM as the laboratory-generated particles were exposed to increasing relative humidity (RH). The first level, onset of observable morphological changes, occurred on average at 70, 48, and 35% RH for the NaCl, S-SSA, and N-SSA particles, respectively. The second level, rounding, occurred at 74, 66, and 57% RH for NaCl, S-SSA, and N-SSA particles, respectively. The third level, complete deliquescence, occurred at 75% RH for all particles. Collected ambient SSA particles were also examined. With the exception of deliquescence, they did not exhibit the same hygroscopic characteristics as the NaCl particles. The ambient particles, however, behaved most similarly to the synthesized and natural SSA particles, although the onset of morphological change was slightly higher for the S-SSA particles. We used energy-dispersive X-ray spectrometry to study the composition of the liquid layer formed on the S-SSA and N-SSA particles. The layer was enriched in Mg, S, and O relative to the solid particle core. An important implication of these results is that MgSO4-enriched solutions on the surface of SSA particles may be the solvents of many heterogeneous reactions

    Hygroscopic behavior of aerosol particles from biomass fires using environmental transmission electron microscopy

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    Abstract We used both a conventional transmission electron microscope and an environmental transmission electron microscope (ETEM) to determine morphology, composition, and water uptake of 80 individual aerosol particles collected from the young smoke of flaming and smoldering fires during SAFARI-2000, a comprehensive air quality campaign in southern Africa. Six representative carbonaceous particle types are described, including soot, tar balls, and heterogeneously internally mixed particles containing C with S-, K-, Mg-or Narich inorganic phases. The hygroscopic behavior of these particles over the range 0-100% relative humidity (RH) was studied in detail. Soot and tar balls did not take up water, whereas the mixed organic-inorganic particles took up water between 55 and 100% RH, the exact value depending on the composition of their water-soluble phases. The inorganic phase appeared to determine the hygroscopic properties of all mixed organic-inorganic particles. Thus, incorporation of inorganic plant material or reactions with inorganic atmospheric components can dramatically alter the hygroscopic properties of carbonaceous particles in smoke plumes. The fraction of these mixed organic-inorganic particles plausibly increases with time, which will modulate the effects of smoke on radiative budgets
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