Blue, green and yellow carbon dots derived from pyrogenic carbon: Structure and fluorescence behaviour

Fluorescence lifetimes and quantum yields featuring polycyclic aromatic hydrocarbons (PAHs) and other organics constituting pyrogenic carbon particulate matter (PM) are seldom measured. In this work, PM sampled in a fuel-rich ethylene flame was firstly separated in organic carbon (OC), soluble in dichloromethane, and refractory organic carbon (ROC), soluble in N-methyl pyrrolidinone, and then analyzed by size exclusion chromatography (SEC) coupled with online UV and fluorescence detection, and by offline fluorescence spectroscopy and mass spectrometry. It was found that three classes of differently light emitting carbon dots (CDs) could be bottom-up synthesized in the same flame system by selecting appropriately the residence time. Actually, OC presented blue fluorescence regardless the residence time, whereas ROC sampled at low and high residence time emitted fluorescence in the green (green CDs) and in the yellow (yellow CDs) region, respectively. The SEC molecular weight of all CDs presented similar trimodal distributions, centered around 300, 1000 and 10,000 u. For the first time fluorescence lifetimes and quantum yields of pyrogenic CD fractions were measured as additional parameters useful for discriminating the fluorescent components and inferring their structural properties, with the support of mass spectrometry. The different spectroscopic features of CDs could be associated to different compositional characteristics as the polydispersity of molecular components featuring blue CDs, opposed to the oligomer-like nature of green and yellow CDs. Pyrogenic CDs showed different fluorescence emission ranges, quantum yield and lifetimes, appealing for their possible applications in the fields of imaging, electronics and sensors

PAHs and fullerenes as structural and compositional motifs tracing and distinguishing organic carbon from soot

Examining the features distinguishing organic carbon from soot is crucial for understanding the source, the effect on the environment and their respective role in aerosol chemistry and soot formation. Beside to the obvious PAH picking-out in the low-mass mode (C number 40) of organic carbon, separated by carbon particulate matter extraction from young and mature soot thermophoretically sampled in premixed flames, was done by laser-desorption-time-of-flight mass spectrometry, exploiting the laser power increase. The perusal of organic carbon mass spectra through mathematical tools in comparison to aromatic and alkyl-substituted PAH-laden samples and the persistence of high-mass mode at high laser power led to exclude the contribution of dimers and alkyl-bridged PAHs attributing the second mode to both fully-benzenoid and cyclopenta-PAHs. Profound differences between mass spectra of organic carbon and soot were noticed as neither molecules nor radicals of PAHs could be drawn out from soot, even at high laser power, and only small radicals and carbon clusters like fullerenes were observed, especially for young soot. These inferences evidenced the importance of analysing separately organic carbon and soot especially if insights into soot particles nucleation are to be obtained. In the case of benzene flame, already at the inception, soot consists of strongly tangled aromatic motifs crosslinked each other, presumably deriving from reactive coagulation/clustering of relatively small aromatic hydrocarbons/radicals early formed. In methane and ethylene flames, coalesced liquid-like material composed of soot and PAHs is formed and transformed later on undergoing some carbonization and molecular growth, respectively

Optical Properties of Organic Carbon and Soot Produced in an Inverse Diffusion Flame

The carbonaceous matter (soot plus organic carbon) sampled downstream of an ethylene inverse diffusion flame (IDF) was chemically and spectroscopically analyzed in detail. In particular, the H/C ratio, the UV-Visible absorption coefficient and Raman parameters were measured and found to be representative of a highly disordered sp2 -rich carbon as the early soot sampled in a premixed flame. In contrast, the optical band gap was found to be relatively low (0.7eV), closer to the optical band gap of graphite than to that of medium-sized polycyclic aromatic hydrocarbons (\u3e2eV) which are widely considered to be soot precursors and are mostly contained in the organic carbon. The significance of the optical band gap as signature of different structural levels (nano-, micro- and macro-structure) of sp2 -rich aromatic disordered carbons was critically analyzed in reference to their molecular weight/size distribution. The relevance of the optical band analysis to the study of the soot formation mechanism was also highlighted

Effect of Fuel/Air Ratio and Aromaticity on the Molecular Weight Distribution of Soot in Premixed n-Heptane Flames

Soot growth from inception to mass-loading is studied in a wide range of molecular weights (MW) from 105 to 1010u by means of size exclusion chromatography (SEC) coupled with on-line UV-visible spectroscopy. The evolution of MW distributions of soot is also numerically predicted by using a detailed kinetic model coupled with a discrete-sectional approach for the modeling of the gas-to-particle process. Two premixed flames burning n-heptane in slightly-sooting and heavily-sooting conditions are studied. The effect of aromatic addition to the fuel is studied by adding n-propylbenzene (10% by volume) to n-heptane in the heavily-sooting condition. A progressive reduction of the MW distribution from multimodal to unimodal is observed along the flames testifying the occurrence of particle growth and agglomeration. These processes occur earlier in the aromatic-doped n-heptane flame due to the overriding role of benzene on soot formation which results in bigger young soot particles. Modeled MW distributions are in reasonable agreement with experimental data although the model predicts a slower coagulation process particularly in the slightly-sooting n-heptane flame. Given the good agreement between model predictions and experiments, the model is used to explore the role of fuel chemistry on MW distributions. Two flames of n-heptane and n-heptane/n-propylbenzene in heavily-sooting conditions with the same temperature profile and inert dilution are modeled. The formation of larger soot particles is still evident in the n-heptane/n-propylbenzene flame with respect to the n-heptane flame in the same operating conditions of temperature and dilution. In addition the model predicts a larger formation of molecular particles in the flame containing n-propylbenzene and shows that soot inception occurs in correspondence of their maximum formation thus indicating the importance of molecular growth in soot inception

Effect of Fuel/Air Ratio and Aromaticity on Sooting Behavior of Premixed Heptane Flames

Oxidation and pyrolysis products were sampled and quantified along the axis of premixed laminar flames burning n-heptane in slightly sooting (C/O=0.7) and heavily sooting conditions (C/O=0.8) by means of gas chromatographic analysis. Total particulate was extracted with dichloromethane (DCM) in order to separate condensed species (CS) including polycyclic aromatic hydrocarbons from soot. The effect of aromatic addition (10 vol % of n-propylbenzene) to n-heptane fuel in heavily sooting conditions on the distribution of light hydrocarbons was also studied. Detailed modeling extended to the formation of high-molecular-weight species and soot was performed to verify the effect of the C/O ratio and of the fuel aromatic content on soot formation. The C/O ratio was found to affect benzene formation which in turn caused an increase of condensed species and soot formation rates. The fuel aromaticity was found to shift soot inception upstream in the flame increasing soot in the oxidation region of the flame. However, aromaticity was not found to influence the ultimate soot loading because of the reduced soot growth rate due to the slightly lower temperature and lower acetylene formation in the aromatic-doped flame. The model was used to explore the effect of larger amounts of aromatics on soot formation. Increased benzene and condensed species, including polycyclic aromatic hydrocarbons, are obtained from the addition of more aromatics (>10%) to n-heptane resulting in higher ultimate soot loading, confirming the direct relation between gas-phase aromatics and final soot loading