科研成果 by Year: 2013

Two polymers, r-PDI-diTh and i-PDI-diTh, were synthesized as acceptors applicable for solution-processed BHJ OSCs. By introducing a bulky, dove tailed side chain and thereby suppressing the p-p interactions between perylenediimide units in the backbones of acceptor polymers, more effective phase segregation of these acceptors with a donor polymer (P3HT) was realized. By employing the inverted device configuration to better match the vertical phase separation of donor-acceptor polymers produced by solution processing, undesirable polaron pair recombination was suppressed, and PCE up to 2.17% was achieved from the regio-regular acceptor r-PDI-diTh.

Classical Mach-number (M) scaling in compressible wall turbulence was suggested by van Driest (Van Driest E R. Turbulent boundary layers in compressible fluids. J Aerodynamics Science, 1951, 18(3): 145-160) and Huang et al. (Huang P G, Coleman G N, Bradshaw P. Compressible turbulent channel flows: DNS results and modeling. J Fluid Mech, 1995, 305: 185-218). Using a concept of velocity-vorticity correlation structure (VVCS), defined by high correlation regions in a field of two-point cross-correlation coefficient between a velocity and a vorticity component, we have discovered a limiting VVCS as the closest streamwise vortex structure to the wall, which provides a concrete Morkovin scaling summarizing all compressibility effects. Specifically, when the height and mean velocity of the limiting VVCS are used as the units for the length scale and the velocity, all geometrical measures in the spanwise and normal directions, as well as the mean velocity and fluctuation (r.m.s) profiles become M-independent. The results are validated by direct numerical simulations (DNS) of compressible channel flows with M up to 3. Furthermore, a quantitative model is found for the M-scaling in terms of the wall density, which is also validated by the DNS data. These findings yield a geometrical interpretation of the semi-local transformation (Huang et al., 1995), and a conclusion that the location and the thermodynamic properties associated with the limiting VVCS determine the M-effects on supersonic wall-bounded flows.

A large oxygenated organic uptake to aerosols was observed when exposing ambient urban air to inorganic acidic and non-acidic sulfate seed aerosol. For non-acidic seed aerosol the uptake was attributed to the direct dissolution of primary vehicle exhaust gases into the aqueous aerosol fraction, and was correlated to the initial seed sulphate mass. The uptake of primary oxygenated organic gases to aerosols in this study represents a significant amount of organic aerosol (OA) that may be considered primary when compared to that reported for primary organic aerosol (POA), but is considerably more oxygenated (O : C similar to 0.3) than traditional POA. Consequently, a fraction of measured ambient oxygenated OA, which correlates with secondary sulphate, may in fact be of a primary, rather than secondary source. These results represent a new source of oxygenated OA on neutral aerosol and imply that the uptake of primary organic gases will occur in the ambient atmosphere, under dilute conditions, and in the presence of pre-existing SO4 aerosols which contain water. Conversely, under acidic seed aerosol conditions, oligomer formation was observed with the uptake of organics being enhanced by a factor of three or more compared to neutral aerosols, and in less than 2 min, representing an additional source of SOA to the atmosphere. This resulted in a trajectory in Van Krevelen space towards higher O : C (slope similar to -1.5), despite a lack of continual gas-phase oxidation in this closed system. The results demonstrate that high molecular weight species will form on acidic aerosols at the ambient level and mixture of organic gases, but are otherwise unaffected by subsequent aerosol neutralization, and that aerosol acidity will affect the organic O : C via aerosolphase reactions. These two processes, forming oxygenated POA under neutral conditions and SOA under acidic conditions can contribute to the total ambient OA mass and the evolution of ambient aerosol O : C ratios. This may be important for properly representing organic aerosol O: C ratios in air quality and climate models.

The ozonolysis of alkenes is considered to be an important source of atmospheric peroxides, which serve as oxidants, reservoirs of HOx radicals, and components of secondary organic aerosols (SOAs). Recent laboratory investigations of this reaction identified hydrogen peroxide (H2O2) and hydroxymethyl hydroperoxide (HMHP) in ozonolysis of isoprene. Although larger hydroxyalkyl hydroperoxides (HAHPs) were also expected, their presence is not currently supported by experimental evidence. In the present study, we investigated the formation of peroxides in the gas phase ozonolysis of isoprene at various relative humidities on a time scale of tens of seconds, using a quartz flow tube reactor coupled with the online detection of peroxides. We detected a variety of conventional peroxides, including H2O2, HMHP, methyl hydroperoxide, bis-hydroxymethyl hydroperoxide, and ethyl hydroperoxide, and interestingly found three unknown peroxides. The molar yields of the conventional peroxides fell within the range of values provided in the literature. The three unknown peroxides had a combined molar yield of ~30% at 5% relative humidity (RH), which was comparable with that of the conventional peroxides. Unlike H2O2 and HMHP, the molar yields of these three unknown peroxides were inversely related to the RH. On the basis of experimental kinetic and box model analysis, we tentatively assigned these unknown peroxides to C2−C4 HAHPs, which are produced by the reactions of different Criegee intermediates with water. Our study provides experimental evidence for the formation of large HAHPs in the ozonolysis of isoprene (one of the alkenes). These large HAHPs have a sufficiently long lifetime, estimated as tens of minutes, which allows them to become involved in atmospheric chemical processes, e.g., SOA formation and radical recycling.