Investigation of the Photochemical Reactivity of Soot Particles Derived

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Investigation of the Photochemical Reactivity of Soot Particles Derived from Biofuels Towards NO. A Kinetic and Product Study. 2

Manolis N. Romanias, Philippe Dagaut, Yuri Bedjanian, Aurea Andrade-Eiroa, Roya Shahla, Karafas S Emmanouil, Vassileios C. Papadimitriou, and Apostolos Spyros J. Phys. Chem. A, Just Accepted Manuscript • DOI: 10.1021/jp511468t • Publication Date (Web): 16 Feb 2015 Downloaded from http://pubs.acs.org on February 18, 2015

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The Journal of Physical Chemistry

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Investigation of the Photochemical Reactivity of Soot Particles Derived from

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Biofuels Towards NO2. A Kinetic and Product Study.

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Manolis N. Romanías*, 1 Philippe Dagaut*, 1 Yuri Bedjanian, 1 Auréa Andrade-Eiroa, 1 Roya Shahla, 1 Karafas S. Emmanouil, 2 Vassileios C. Papadimitriou, 3 and Spyros Apostolos.2 1. Institute de Combustion, Aérothermique, Réactivité et Environnement (ICARE)CNRS, 1C Avenue de la Recherche Scientifique, 45071, Orléans, France. 2. NMR Laboratory, Department of Chemistry, University of Crete, Vassilika Vouton, 71003, Heraklion, Crete, Greece. 3. Laboratory of Photochemistry and Chemical Kinetics, Department of Chemistry,

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University of Crete, Vassilika Vouton, 71003, Heraklion, Crete, Greece.

Journal of Physical Chemistry A

*

Corresponding authors:

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Manolis N. Romanías, Tel.: +33 238255492, Fax: +33 238696004, e-mail address:

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[email protected]

36 37 38

Philippe Dagaut: Tel.: +33 238255466, Fax: +33 238696004, e-mail address: [email protected]

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Abstract

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In the current study, the heterogeneous reaction of NO2 with soot/bio-soot

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surfaces was investigated in the dark and under illumination relevant to the atmosphere

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conditions (JNO2 = 0.012 s-1). A flat-flame burner was used for preparation and collection

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of soot samples from premixed flames of liquid fuels. The biofuels were prepared by

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mixing

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(CH3(CH2)6COOCH3) (iii) anhydrous diethyl carbonate (C2H5O)2CO and 2,5 dimethyl

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furan (CH3)2C4H2O additive compounds in conventional kerosene fuel (JetA-1).

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Experiments were performed at 293 K using a low-pressure flow-tube reactor (P = 9

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Torr) coupled to a quadrupole mass spectrometer. The initial and steady-state uptake

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coefficients, γ0 and γss respectively, as well as the surface coverage, Ns, were measured

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under dry and humid conditions. Furthermore the branching ratios of the gas phase

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products NO (~80-100%) and HONO ( JetA-1/MOC JetA-1> JetA-1/DEC ≈ JetA-1/1-BNOL.

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Figure 5. γss of NO2 as a function of soot type under a) dry conditions (0.0032% RH)

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and b) 5% of RH. Experiments were performed at T = 293 K and 66 ppbv of NO2. Solid

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and open symbols denote results under dark and UV light irradiation conditions (JNO2 =

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0.012 s-1), respectively. Note that for JetA-1/1-BNOL sample under dry conditions,

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JetA-1/DEC and JetA-1/2,5-DMF under 5.5% of RH there is overlapping of the data

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points in the graph. The BET surface areas measured were used for γss calculations.

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A closer analysis of the results obtained for γ0 and those of γss reveals that the

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observable differences between the soot samples have been attenuated upon NO2

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processing of the soot surfaces. In particular, the initial uptake of NO2 on JetA-1/2,5-

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DMF particles was by a factor of 10 higher than on JetA-1/1-BNOL bio-soot, while for

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the steady state uptake a factor of 4.6 was obtained; similar attenuation was recorded for

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the other samples. The former results indicate that processing of the BC/BrC particles

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with NO2 lead to depletion of the most active surface sites existing on the freshly

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emitted soot samples.

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Concerning the surface coverage of soot, Ns, it was found to be ~1013 molecule

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cm-2, in agreement with the literature,11, 12 independent on RH and irradiation conditions,

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(Figure 6 and Table 1). JetA-1/1-BNOL and JetA-1/DEC bio-soot surfaces displayed

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similar coverages, (2-3) × 1013 molecule cm-2, while the maximum Ns value was

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recorded on JetA-1/2,5-DMF surfaces, Ns ~ 8 × 1013 molecule cm-2. However, it should

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be noted that Ns values should be considered as lower limits since saturation of the

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surface (that would indicate the end of the reaction) was not achieved within the time

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scale of the experiment.

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Figure 6. Surface coverage of different types of soot upon their exposition to 66 ppbv of

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NO2 at 293 K for 45 min. Solid and open symbols corresponds to experiments under dry

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and humid conditions, 0.0032% and 5% RH respectively. The BET surface areas

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measured were used for Ns calculations.

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3.2.3 Product yield determination

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In addition to the kinetic measurements presented above, the yield of reaction

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products

formed

were

determined

according

to

the

following

expression:

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∆[product]/∆[ΝΟ2]. NO and HONO were the only gas phase products detected and their

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distribution is summarized in Figure 7. The formation of nitro containing surface

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products, (Nitro-PAHs, R-NO, R-NO2, RONO2, etc., R=alkyl group), should not be

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excluded, although their yield seems to be low, at least under the conditions of the

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present study. One should note that in our latest study,14 the formation of several

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nitroPAHs compounds was verified upon processing of kerosene BC/BrC particles with

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NO2.

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Under dry conditions, NO yields ranged from 80 to 100 % while HONO

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production was limited to < 5% for all soot surfaces, except JetA-1/1-BNOL bio-soot

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where it reached 10%, and JetA-1/2,5-DMF, where HONO was not produced. Similar

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results were obtained under humid conditions where NO was the major reaction product.

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However, HONO production was more pronounced in presence of H2O. Indeed, under

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dark conditions HONO yield increases up to 20% for pure kerosene and JetA-1/2,5-

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DMF soot surfaces, while it slightly increased for JetA-1/1-BNOL, >10%, ~5% for

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JetA-1/MOC and ~10% for JetA-1/DEC soot. This tendency could be expected since

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heterogeneous production of HONO is favoured on any humid surface that interacts

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with NO2.35,

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conditions. Note that similar behavior was observed in previous studies from our group

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where the interaction of NO2 with mineral oxide aerosols was studied.37, 38 Finally, the

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UV irradiation of soot surfaces caused a systematic increase of NO yields, probably due

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to photodegradation of surface nitro-containing products leading to NO production.

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Conversely, NO production rates were slightly lower under humid

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Figure 7. Product yield for NO (squares) and HONO (circles), under dark (solid

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symbols) and UV irradiation conditions (open symbols) upon exposition of soot surfaces

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to 66ppbv of NO2 at 293 K under a) dry conditions and b) 5% RH.

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3.3 Solid phase analysis of soot.

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One of the major tasks of the current study was the solid phase analysis of the soot

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surfaces. The objective was to correlate the chemical reactivity of soot towards NO2

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observed for each fuel, with the chemical composition and the existing functional groups

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on soot. To this end the analysis of solid soot surfaces was realized, with (i) Raman

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spectroscopy, (ii) NMR and (iii) HPLC for the determination of PAHs compounds on

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soot. 16 ACS Paragon Plus Environment

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3.3.1 Raman spectra

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The Raman spectra acquired for conventional and bio-kerosene soot samples are

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presented in Figure 8. For sake of clarity, obtained spectra are presented only in the

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wavelength range of interest, 900 and 1800 cm-1 where two broad bands appear, with

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peaks centered at 1330 cm-1 and 1585 cm-1 and correspond to Defective (D) and Graphitic

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(G) bands, respectively. In order to extract valuable information about the structure and

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the chemical composition of the soot films, the Raman spectra were deconvoluted.

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Different fitting methods have been proposed, using Gaussian, Lorentzian, or

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combination of those functions for peaks fitting..39-42 In addition, the number of the fitting

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components used is also critical. When using too many components for the same Raman

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peak, the residual might represent the original spectrum well but most of the produced

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peaks without any physical meaning. In the literature, up to 10 fitting peaks have been

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used to deconvolute Raman spectrum of carbon materials. 40, 43, 44

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The ratio of the intensities of the D and G bands, ID/IG has been used as an

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indicative parameter of the degree of disordering of the carbon material.45 High values of

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ID/IG indicate low graphitic-like structure of the material.45 The best deconvoluted fit was

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achieved using a Lorentzian function with two components. The JetA-1/MOC soot

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sample was the only exception where a “D-side” band, SD, was observed at ~1200 cm-1,

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thus a 3 component Lorentzian function was employed to achieve the best fit. G band can

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stem from in two different origins.41, 46 The carbon stretch vibrations of benzene and in

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general condensed aromatic rings at ~1588 cm-1 and C=C sp2 stretching vibrations of

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olefinic or conjugated carbon chains.46 Regarding the origin of the D band, the presence

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of heavy aromatic compounds with large aromatic rings existing in soot (≥ 6) is

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considered as the major source.40,

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observed in all soot samples is due to a wide range of aromatic rings size.40 Therefore, an

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increased ID/IG ratio can be attributed to the formation of aromatic compounds having 6

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or more fused benzene rings and provide information about the aromatic/olefinic ratio of

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the soot sample (the higher the ID/IG, the higher the aromatic/olefinic ratio). The presence

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of the SD peak after Raman deconvolution of JetA-1/MOC sample is attributed to sp2 and

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sp3 structures. Compounds such as aryl-alkyl ethers, and methyl carbon dangling to

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aromatics rings contributes to these wavenumbers and are considered as the major source

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of this band.40, 41, 48

47, 48

In addition, the wide range of the D bands



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Figure 8. Raman spectra of soot/bio-soot samples studied (λ= 780 nm, focused area =10

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µm2, resolution, R= 2 cm-1). The spectra were focus for presentation purposes. 18 ACS Paragon Plus Environment

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The values of the ID/IG ratios obtained for reference JetA-1 and bio soot samples

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are presented in Table 1. JetA-1/2,5-DMF appears with the maximum ID/IG value

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followed by pure kerosene, JetA-1/MOC, JetA-1/1-BNOL and JetA-1/DEC soot surfaces,

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1.45, 1.41, 1.28, 1.23 and 1.11 respectively. One can note that samples with high

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chemical reactivity appear with the maximum values of ID/IG ratio. This is an indication

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that the heavy aromatic fraction of soot can possibly influence BC/BrC particles

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reactivity. However, it should be mentioned that the absolute concentrations of both the

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aromatic and the aliphatic fractions should be determined.

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3.3.2 NMR analysis

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The 1H NMR spectra of the chloroform soluble fraction of the soot samples and

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the type of chemical groups associated with each signal are presented in Figure S3. One

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can note that the soot spectra have similar features, which can be explained by the

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presence of kerosene as the major (80% vol) component in all fuels. Table 2 summarizes

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the soot characterization data obtained by 1H NMR and reports the proton density of

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several types of structural units of soot, the CH2/CH3 ratio and the aromatic/aliphatic ratio

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for the apolar fraction of pure and bio-soot samples.

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The region δ=0.5 – 2.0 corresponds to aliphatic methyl (-CH3) and methylene (-

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CH2-) soot protons, and the presence of large signals in this region indicates the high

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amount of alkanes in pure and bio soot samples. The relative ratio of CH2/CH3 groups

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can be used to assess the amount of carbon branching in the soot samples. Except from

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the JetA-1/MOC soot (2.6) the other soot samples were found to have very similar

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branching ratios (3.3±0.1), indistinguishable from the value of the pure kerosene soot

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(3.4). This indicates that branching is not substantially affected by the additive compound

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used to prepare the bio soot. The high values of branching ratio suggest the existence of

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alkanes with large and straight chains.

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The signals in the region between δ 2.0 – 2.8 of the NMR spectra represent the

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presence of methyl and ethyl-substituted aromatic compounds. As can been seen in Table

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2 these compounds are present in higher amounts in the butanol and the dimethyl furan

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soot, compared to pure kerosene soot, while smaller amounts are observed for the JetA-

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1/MOC and JetA-1/DEC soot samples. Figure S3 shows that the combustion of all fuels

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leads to the production of R-CH (R is nitrogen or an oxygen atom) protons in the region δ

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2.8 – 4.6 in which the nitrogen atom is chemically connected to aromatic rings.

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According to Table 2 the JetA-1/1-BNOL soot contains the largest amount of these 19 ACS Paragon Plus Environment


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compounds, followed by the JetA-1/2,5-DMF and JetA-1/DEC soots that contain similar

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amounts to JetA-1, and the JetA-1/MOC soot which appears to contain the smallest

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amount of N-CH compounds. In the region δ 4.6 – 6.2 all the spectra exhibit peaks

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indicating the presence of very small amounts of vinyl C=CH protons. The low signal in

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this region indicates the small amount of olefins present in the apolar extracts of all

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samples.

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A major feature of the spectra of all soot samples is the large amount of signal in

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the aromatic region δ 6.5 – 9.4 indicating that the majority of protons in soot have a large

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aromatic character, with 55-69% of the total protons appearing in this region. It should

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also be noted that the presence of peaks with chemical shift 9.5 < δ < 8.0 in the NMR

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spectra of the soot samples indicates that a significant amount of PAHs is present in the

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soot samples. Finally the peaks with chemical shifts δ 9.5 – 10.8 indicate that the

499

combustion of all fuels leads to the production of aldehydes.

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3.3.3 HPLC analysis

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The fresh collected soot samples were analysed with a HPLC chromatograph

503

coupled with a UV/Visible photodiode array detector prior to their exposure to NO2. The

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objective of this series of experiments was to analyze the PAHs content of the soot

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samples and find relations between measured concentration of classes of compounds and

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the observed reactivity of the samples towards NO2. Seven different classes of PAHs

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were separated and more than 200 hundred compounds were identified. The presentation

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of a detailed list of PAHs compounds identified is a subject of ongoing publications from

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our lab and was beyond the scope of the present study. We only present the results that

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are correlated with the observed chemical reactivity of soot with NO2. The HPLC

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analysis showed that the relative abundance of nitro-PAHs pre-existing on soot (prior to

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its exposure to NO2) is the key factor influencing the chemical reactivity. In particular, in

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Figure 9 the concentrations of the 10 Nitro-PAHs compounds identified are displayed.

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JetA-1/1-BNOL (~5800 ng/mg soot) and JetA-1/DEC (~4000 ng/mg soot) were the soot

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samples with the highest nitro-PAHs concentrations, followed by Jet A1 (~1800 ng/mg

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soot). Regarding the JetA-1/MOC and JetA-1/2,5-DMF samples, their nitro-PAHs

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contents are significantly lower, 400 ng and 169 ng per mg of soot, respectively. The

518

former observation clearly demonstrates that soot samples containing high concentrations

519

of nitro-PAHs prior to their reaction with NO2 have the lower reactivity towards NO2.


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Although this trend looks like “quite logical” it has never been reported in the past and

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could be a quite useful prediction factor for soot reactivity with NOx.

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Figure 9. Concentrations of nitro-PAHs detected in soot samples prior to their exposure to

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NO2.

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4. Summary and Conclusions. In the framework of this study, the chemical reactivity of soot/bio-soot particles

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towards NO2 has been studied and the chemical composition of the soot samples

530

produced were analysed using Raman spectroscopy, NMR and HPLC. Furthermore, the

531

BET surface areas were measured and the pore size distributions of the freshly produced

532

BC/BrC particles have been determined employing NLDFT. To the best of our

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knowledge, this is the first experimental study where the reactivity, under relevant

534

atmospheric conditions, and the physicochemical properties of soot particles has been

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investigated together.

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The results showed that the additive compounds used to dope the kerosene fuel

537

influenced the physicochemical properties and reactivity of the corresponding bio-soot

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showed that the combustion of JetA-1/2,5-DMF and JetA-1/DEC biofuels produced soot

540

particles with the highest and lowest surface area and pore volume, respectively (Figures

541

2, S1 and Table 1). Conversely, no significant differences have been observed between

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the other Br/BrC particles.

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The degradation of NO2 over the soot particles was found to depend on the

544

substrate BC/BrC sample. Using JetA-1 as reference fuel, JetA-1/2,5-DMF and JetA-

545

1/MOC appeared to be more reactive while for JetA-1/1-BNOL and JetA-1/DEC NO2

546

reactivity was significantly decreased. These differences were observed at the maximum

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extent within the first minutes of the NO2-soot interaction, where γ0 was measured, and

548

were attenuated upon processing of soot particles for longer time, γss. This attenuation

549

was attributed to the depletion of the most reactive surface sites of soot within the first

550

minutes of the interaction. UV illumination of the surface didn’t accelerate the uptake

551

process at least to an extent that could be clearly measured and not be attributed to

552

experimental uncertainties. Regarding the products, NO was measured to be the major

553

one, ranging from 80% to 100%, while HONO production was limited to significantly

554

lower limits (

Investigation of the Photochemical Reactivity of Soot Particles Derived

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