Heterogeneous chemistry and reaction dynamics of the atmospheric oxidants, O₃, NO₃, and OH, on organic surfaces

Abstract

Heterogeneous chemistry of the most important atmospheric oxidants, O 3 , NO 3 , and OH, plays a central role in regulating atmospheric gas concentrations, processing aerosols, and aging materials. Recent experimental and computational studies have begun to reveal the detailed reaction mechanisms and kinetics for gas-phase O 3 , NO 3 , and OH when they impinge on organic surfaces. Through new research approaches that merge the fields of traditional surface science with atmospheric chemistry, researchers are developing an understanding for how surface structure and functionality affect interfacial chemistry with this class of highly oxidizing pollutants. Together with future research initiatives, these studies will provide a more complete description of atmospheric chemistry and help others more accurately predict the properties of aerosols, the environmental impact of interfacial oxidation, and the concentrations of tropospheric gases.

Atmospheric chemistry of bioaerosols: heterogeneous and multiphase reactions with atmospheric oxidants and other trace gases

“…112 Additionally, the interaction of ozone with organic aerosols, especially those containing unsaturated bonds, has been extensively studied. 55,113–117 …”

“…Aerosols evolve away from their native states as they undergo heterogeneous and multiphase reactions that modify gas and particle phases, 50–55 affecting both atmospheric composition and air quality. 50 Tremendous progress has been made in the fundamental understanding of heterogeneous chemical reactions involving primary aerosols such as mineral dust 56,57 and sea-spray aerosol.…”

Photocatalytic Oxygenation Reactions Using Water and Dioxygen

“…[47] Ethylbenzene was also hydroxylated to yield 1-phenylethanol using [47] The oxygen source in the oxygenatedp roducts was confirmed by using 18 Oi sotopic labeling to be H 2 O. [58] The photocatalytic oxygenation is started by photoinduced ET from [Ru(bpy) 3 [58] The quantum yield for the formationo fp-styrene oxide sulfonate in thep hotocatalytic oxygenation of p-styrene sulfonate with [(TMPS)Mn III (OH)] increased with increasing [Co III (NH 3 ) 5 Cl] 2 + concentration to reach ac onstantv alue close to 50 %, which corresponds to the maximum value for the one-photon one-electronprocess in Scheme 2. [35][36][37][38][39][40][41][42][43][44][45][46][47] [Ru(bpy) 3 ] 3 + was used as ao neelectron oxidant to produce high-valent metal-oxo complexes, but it can be replaced by much milder oxidants such as [Co III (NH 3 ) 5 Cl] 2 + under photoirradiation.…”

“…[1][2][3][4][5][6][7][8][9][10][11][12][13][14] Amongo xidants used in oxidation reactions, dioxygen (O 2 )i s the greenest, since the product of O 2 reduction is water or hydrogen peroxide. [1][2][3][4][5][6][7][8][9][10][11][12][13][14] Amongo xidants used in oxidation reactions, dioxygen (O 2 )i s the greenest, since the product of O 2 reduction is water or hydrogen peroxide.…”

“…[35][36][37][38][39][40][41][42][43][44][45][46][47] [Ru(bpy) 3 ] 3 + was used as ao neelectron oxidant to produce high-valent metal-oxo complexes, but it can be replaced by much milder oxidants such as [Co III (NH 3 ) 5 Cl] 2 + under photoirradiation. [60,61] The iron(III) complex of biuret-modified tetraamidomacrocyclic ligand (bTAML) also acts as an oxygenation catalyst in the photocatalytic hydroxylation and epoxidation of alkanes and alkenes, respectively, by using [Ru II (bpy) 3 5 Cl] 2 + as aw eak electron acceptor,a nd H 2 Oa sa n oxygen source (Scheme 4). [58] The photocatalytic oxygenation is started by photoinduced ET from [Ru(bpy) 3 [58] The quantum yield for the formationo fp-styrene oxide sulfonate in thep hotocatalytic oxygenation of p-styrene sulfonate with [(TMPS)Mn III (OH)] increased with increasing [Co III (NH 3 ) 5 Cl] 2 + concentration to reach ac onstantv alue close to 50 %, which corresponds to the maximum value for the one-photon one-electronprocess in Scheme 2.…”