Thermal and photochemical oxidation of self-assembled monolayers on alumina particles exposed to nitrogen dioxide

Raff, Jonathan D.; Szanyi, János; Finlayson-Pitts, Barbara J.

doi:10.1039/c0cp01041c

Cited by 4 publications

(4 citation statements)

References 82 publications

(146 reference statements)

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“…Thus, it is possible that organic nitrates were formed during the nitration of methyl palmitate and subsequently decomposed. If so, the likely mechanism leading to RONO 2 would be H-abstraction by NO 3 radical (from thermal decomposition of N 2 O 5(aq) ) at the α-position relative to the carboxylic acid (or methyl ester) precursor, followed by secondary reactions involving O 2 and NO (Figure , R12). − This is similar to the mechanism proposed previously where RONO 2 groups were generated photochemically from OH-initiated H-abstraction of aliphatic −CH 2 – groups on a surface coated with self-assembled monolayers . The resulting organic nitrate at a secondary C would be susceptible to hydrolysis and could result in an alkene at the α,β position with respect to the carbonyl of the carboxylic acid according to (R12).…”

Section: Resultssupporting

confidence: 60%

“…71−73 This is similar to the mechanism proposed previously where RONO 2 groups were generated photochemically from OH-initiated Habstraction of aliphatic −CH 2 − groups on a surface coated with self-assembled monolayers. 74 The resulting organic nitrate at a secondary C would be susceptible to hydrolysis and could result in an alkene at the α,β position with respect to the carbonyl of the carboxylic acid according to (R12). The formation of alkenes is notable since it may help explain why there was no significant change in the DBE of SRFA following its reaction with HNO 3 .…”

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confidence: 99%

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Reaction of Organic Matter with Nitronium Ion as a Source of Organic Nitrate Esters in Proxies for Organic Aerosols

Hansen,

Dalton,

Abney

et al. 2023

ACS Earth Space Chem.

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Organic nitrate ester compounds (RONO2) are an important sink for nitrogen oxides (NO x ≡ NO + NO2) that impact ozone and organic aerosol formation in the lower atmosphere. While RONO2 formation from gas phase oxidation chemistry and heterogeneous reactions involving reactive uptake of NO3 into organic aerosols is well documented, in situ bulk-aqueous-phase production of RONO2 within organic aerosols has not been explored as extensively. Here, we provide evidence that RONO2 species are produced during aqueous phase reactions of nitronium (NO2 +) with humic and fulvic acids, which are used as surrogates for aerosol organic matter. X-ray photoelectron spectroscopy (XPS) and high-resolution mass spectrometry were used to characterize nitrogen functional groups and changes in bulk chemical composition during nitration reactions. Correlations between the organic N abundance in reacted humic and fulvic acids and functional group abundance measured by solid-state 13C NMR indicate that NO2 + targets the lipid fraction of the organic matter. Fourier transform infrared spectroscopy (FTIR) analysis of model lipid compounds shows that the reaction of NO2 + with terminal alcohols (ROH) and alkenes is a source of stable RONO2 compounds. Further, the low-pH environment of most nitrate aerosols is expected to enhance the total terminal ROH pool through acid-catalyzed ester hydrolysis within the lipid-like fraction of natural organic matter. Our findings demonstrate that multiphase oxidation of organic matter by NO2 +, along with air-particle partitioning of products from gas-phase chemistry, may be an important source of particle-phase organic nitrates.

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Section: Resultssupporting

confidence: 60%

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confidence: 99%

Reaction of Organic Matter with Nitronium Ion as a Source of Organic Nitrate Esters in Proxies for Organic Aerosols

Hansen,

Dalton,

Abney

et al. 2023

ACS Earth Space Chem.

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“…) and nitrate (NO 3 À ) ions. [22][23][24][25][26][27][28] Adsorbed water on oxide surfaces often has a significant effect on these heterogeneous reactions. [21][22][23]26,27,29,30 Enhanced surface uptake of NO 2 and HNO 3 has been reported on hydrated surfaces or in the presence of water vapor compared to dehydrated surfaces.…”

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confidence: 99%

“…[19][20][21] For example, mineral dust particles contain various oxides such as SiO 2 , Al 2 O 3 and Fe 2 O 3 , and the interactions of NO 2 and HNO 3 with these surfaces lead to the formation of various nitrogen containing surface species including nitrite (NO 2 À ) and nitrate (NO 3 À ) ions. [22][23][24][25][26][27][28] Adsorbed water on oxide surfaces often has a significant effect on these heterogeneous reactions. [21][22][23]26,27,29,30 Enhanced surface uptake of NO 2 and HNO 3 has been reported on hydrated surfaces or in the presence of water vapor compared to dehydrated surfaces.…”

Section: Introductionmentioning

confidence: 99%

Thermal and photochemical reactions of NO2 on chromium(iii) oxide surfaces at atmospheric pressure

Nishino

Finlayson-Pitts

2012

Phys. Chem. Chem. Phys.

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While many studies of heterogeneous chemistry on Cr 2 O 3 surfaces have focused on its catalytic activity, less is known about chemistry on this surface under atmospheric conditions. We report here studies of the thermal and photochemical reactions of NO 2 on Cr 2 O 3 at one atm in air. In order to follow surface species, the interaction of 16-120 ppm NO 2 with a 15 nm Cr 2 O 3 thin film deposited on a germanium crystal was monitored in a flow system using attenuated total reflectance (ATR) coupled to a Fourier transform infrared (FTIR) spectrometer. Gas phase products were monitored in the effluent of an B285 ppm NO 2 -air mixture that had passed over Cr 2 O 3 powder in a flow system. A chemiluminescence NO y analyzer, a photometric O 3 analyzer and a long-path FTIR spectrometer were used to probe the gaseous products. In the absence of added water vapor, NO 2 formed nitrate (NO 3 À ) ions coordinated to Cr 3+ . These surface coordinated NO 3 À were reversibly solvated by water under humid conditions. In both dry and humid cases, nitrate ions decreased during irradiation of the surface at 302 nm, and NO and NO 2 were generated in the gas phase. Under dry conditions, NO was the major gaseous product while NO 2 was the dominant species in the presence of water vapor. Heating of the surface after exposure to NO 2 led to the generation of both NO 2 and NO under dry conditions, but only NO 2 in the presence of water vapor. Elemental chromium incorporated into metal alloys such as stainless steel is readily oxidized in contact with ambient air, forming a chromium-rich metal oxide surface layer. The results of these studies suggest that active photo-and thermal chemistry will occur when boundary layer materials containing chromium(III) or chromium oxide such as stainless steel, roofs, automobile bumpers etc. are exposed to NO 2 under tropospheric conditions.

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Heterogeneous reactions of gaseous hydrogen peroxide on pristine and acidic gas-processed calcium carbonate particles: Effects of relative humidity and surface coverage of coating

Zhao

Chen

Shen

et al. 2013

Atmospheric Environment

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Thermal and photochemical oxidation of self-assembled monolayers on alumina particles exposed to nitrogen dioxide

Cited by 4 publications

References 82 publications

Reaction of Organic Matter with Nitronium Ion as a Source of Organic Nitrate Esters in Proxies for Organic Aerosols

Reaction of Organic Matter with Nitronium Ion as a Source of Organic Nitrate Esters in Proxies for Organic Aerosols

Thermal and photochemical reactions of NO2 on chromium(iii) oxide surfaces at atmospheric pressure

Heterogeneous reactions of gaseous hydrogen peroxide on pristine and acidic gas-processed calcium carbonate particles: Effects of relative humidity and surface coverage of coating

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