Resolving the Formation Mechanism of HONO via Ammonia-Promoted Photosensitized Conversion of Monomeric NO2 on Urban Glass Surfaces

Liu, Jiangping1,2,3,4,5; Li, Bai6; Deng, Huifan1,2,3,4,7; Yang, Yan8,9,10; Song, Wei1,2,3,4; Wang, Xinming1,2,3,4; Luo, Yongming5,11; Francisco, Joseph S.12; Li, Lei6; Gligorovski, Sasho1,2,3,4

2023-05-01

10.1021/jacs.3c02067

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   影响因子和分区

0002-7863

1520-5126

Understanding the formation processesof nitrous acid (HONO) iscrucial due to its role as a primary source of hydroxyl radicals (OH)in the urban atmosphere and its involvement in haze events. In thisstudy, we propose a new pathway for HONO formation via the UVA-light-promotedphotosensitized conversion of nitrogen dioxide (NO2) inthe presence of ammonia (NH3) and polycyclic aromatic hydrocarbons(PAHs, common compounds in urban grime). This new mechanism differsfrom the traditional mechanism, as it does not require the formationof the NO2 dimer. Instead, the enhanced electronic interactionbetween the UVA-light excited triplet state of PAHs and NO2-H2O/NO2-NH3-H2O significantly reduces the energy barrier and facilitatesthe exothermic formation of HONO from monomeric NO2. Furthermore,the performed experiments confirmed our theoretical findings and revealedthat the synergistic effect from light-excited PAHs and NH3 boosts the HONO formation with determined HONO fluxes of 3.6 x10(10) molecules cm(-2) s(-1) at 60% relative humidity (RH) higher than any previously reportedHONO fluxes. Intriguingly, light-induced NO2 to HONO conversionyield on authentic urban grime in presence of NH3 is unprecedented130% at 60% RH due to the role of NH3 acting as a hydrogencarrier, facilitating the transfer of hydrogen from H(2)Oto NO2. These results show that NH3-assistedUVA-light-induced NO2 to HONO conversion on urban surfacescan be a dominant source of HONO in the metropolitan area.

SCI ; EI

英语

NI论文

通讯

Ministry of Science and Technology of China[2022YFC-3701102] ; National Natural Science Foundation of China["42177087","41977187","42207127"] ; Chinese Academy of Science, International Cooperation Grant[132744KYSB-20190007] ; State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry["SKLOG2020-5","KTZ_17101"] ; Guangdong Foundation for Program of Science and Technology Research[2017B0303-14057] ; Guangdong Provincial Department of Education Innovation Team Program[2021KCXTD012] ; National Key Ramp;D Program of China[2021YFC-1808903] ; Key-Area Research and Development Program of Guangdong Province[2019B11-0207002] ; Science and Technology Planning Project of Guangdong Province["20010610-5876892","19080711-5560881"]

Chemistry

Chemistry, Multidisciplinary

WOS:001014287900001

AMER CHEMICAL SOC

20232314180792

Dimers ; Excited states ; Hydrogen ; Nitrogen oxides ; Polycyclic aromatic hydrocarbons

Chemical Products Generally:804 ; Organic Compounds:804.1 ; Inorganic Compounds:804.2 ; Organic Polymers:815.1.1 ; Atomic and Molecular Physics:931.3 ; Quantum Theory; Quantum Mechanics:931.4

Web of Science

1.Chinese Acad Sci, Guangzhou Inst Geochem, State Key Lab Organ Geochem, Guangzhou 510640, Peoples R China
2.Chinese Acad Sci, Guangzhou Inst Geochem, Guangdong Prov Key Lab Environm Protect & Resourc, Guangzhou 510640, Peoples R China
3.Chinese Acad Sci, Guangzhou Inst Geochem, Guangdong Hong Kong Macao Joint Lab Environm Poll, Hong Kong 510640, Peoples R China
4.Chinese Acad Sci, Ctr Excellence Deep Earth Sci, Guangzhou 510640, Peoples R China
5.Kunming Univ Sci & Technol, Fac Environm Sci & Engn, Kunming 650500, Peoples R China
6.Southern Univ Sci & Technol, Dept Mat Sci & Engn, Shenzhen 518055, Peoples R China
7.Univ Chinese Acad Sci, Beijing 100049, Peoples R China
8.Guangdong Univ Technol, Sch Environm Sci & Engn, Guangzhou 510006, Peoples R China
9.Rongjiang Lab, Jieyang Branch, Chem & Chem Engn Guangdong Lab, Jieyang 515200, Peoples R China
10.GDUT, Synergy Innovat Inst, Shantou 515041, Peoples R China
11.Kunming Univ Sci & Technol, Fac Chem Engn, Kunming 650500, Peoples R China
12.Univ Penn, Dept Chem, Philadelphia, PA 19104 USA

Liu, Jiangping,Li, Bai,Deng, Huifan,et al. Resolving the Formation Mechanism of HONO via Ammonia-Promoted Photosensitized Conversion of Monomeric NO2 on Urban Glass Surfaces[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2023,145(21):11488-11493.

Liu, Jiangping.,Li, Bai.,Deng, Huifan.,Yang, Yan.,Song, Wei.,...&Gligorovski, Sasho.(2023).Resolving the Formation Mechanism of HONO via Ammonia-Promoted Photosensitized Conversion of Monomeric NO2 on Urban Glass Surfaces.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,145(21),11488-11493.

Liu, Jiangping,et al."Resolving the Formation Mechanism of HONO via Ammonia-Promoted Photosensitized Conversion of Monomeric NO2 on Urban Glass Surfaces".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 145.21(2023):11488-11493.