Photoactivation of Chlorine and Its Catalytic Role in the Formation of Sulfate Aerosols

Yiqun Cao; Jiarong Liu; Qingxin Ma; Chunyan Zhang; Peng Zhang; Tianzeng Chen; Yonghong Wang; Biwu Chu; Xiuhui Zhang; Joseph S. Francisco; Hong He

doi:10.1021/jacs.3c10840

Photoactivation of Chlorine and Its Catalytic Role in the Formation of Sulfate Aerosols

Yiqun Cao
, Jiarong Liu
, Qingxin Ma^*
, Chunyan Zhang
, Peng Zhang
, Tianzeng Chen
, Yonghong Wang
, Biwu Chu
, Xiuhui Zhang
, Joseph S. Francisco^*
, Hong He^*

^*Corresponding author for this work

CAS - Research Center for Eco-Environmental Sciences
University of Chinese Academy of Sciences
Beijing Institute of Technology
Chinese Academy of Sciences
Department of Mathematics, University of Pennsylvania

Research output: Contribution to journal › Article › peer-review

39 Citations (Scopus)

Abstract

We present a novel mechanism for the formation of photocatalytic oxidants in deliquescent NaCl particles, which can greatly promote the multiphase photo-oxidation of SO₂ to produce sulfate. The photoexcitation of the [Cl^--H₃O⁺-O₂] complex leads to the generation of Cl and OH radicals, which is the key reason for enhancing aqueous-phase oxidation and accelerating SO₂ oxidation. The mass normalization rate of sulfate production from the multiphase photoreaction of SO₂ on NaCl droplets could be estimated to be 0.80 × 10^-4 μg·h^-1 at 72% RH and 1.33 × 10^-4 μg·h^-1 at 81% RH, which is equivalent to the known O₃ liquid-phase oxidation mechanism. Our findings highlight the significance of multiphase photo-oxidation of SO₂ on NaCl particles as a non-negligible source of sulfate in coastal areas. Furthermore, this study underscores the importance of Cl^- photochemistry in the atmosphere.

Original language	English
Pages (from-to)	1467-1475
Number of pages	9
Journal	Journal of the American Chemical Society
Volume	146
Issue number	2
DOIs	https://doi.org/10.1021/jacs.3c10840
Publication status	Published - 17 Jan 2024
Externally published	Yes

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title = "Photoactivation of Chlorine and Its Catalytic Role in the Formation of Sulfate Aerosols",

abstract = "We present a novel mechanism for the formation of photocatalytic oxidants in deliquescent NaCl particles, which can greatly promote the multiphase photo-oxidation of SO2 to produce sulfate. The photoexcitation of the [Cl--H3O+-O2] complex leads to the generation of Cl and OH radicals, which is the key reason for enhancing aqueous-phase oxidation and accelerating SO2 oxidation. The mass normalization rate of sulfate production from the multiphase photoreaction of SO2 on NaCl droplets could be estimated to be 0.80 × 10-4 μg·h-1 at 72\% RH and 1.33 × 10-4 μg·h-1 at 81\% RH, which is equivalent to the known O3 liquid-phase oxidation mechanism. Our findings highlight the significance of multiphase photo-oxidation of SO2 on NaCl particles as a non-negligible source of sulfate in coastal areas. Furthermore, this study underscores the importance of Cl- photochemistry in the atmosphere.",

author = "Yiqun Cao and Jiarong Liu and Qingxin Ma and Chunyan Zhang and Peng Zhang and Tianzeng Chen and Yonghong Wang and Biwu Chu and Xiuhui Zhang and Francisco, \{Joseph S.\} and Hong He",

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year = "2024",

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doi = "10.1021/jacs.3c10840",

language = "English",

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T1 - Photoactivation of Chlorine and Its Catalytic Role in the Formation of Sulfate Aerosols

AU - Cao, Yiqun

AU - Liu, Jiarong

AU - Ma, Qingxin

AU - Zhang, Chunyan

AU - Zhang, Peng

AU - Chen, Tianzeng

AU - Wang, Yonghong

AU - Chu, Biwu

AU - Zhang, Xiuhui

AU - Francisco, Joseph S.

AU - He, Hong

PY - 2024/1/17

Y1 - 2024/1/17

N2 - We present a novel mechanism for the formation of photocatalytic oxidants in deliquescent NaCl particles, which can greatly promote the multiphase photo-oxidation of SO2 to produce sulfate. The photoexcitation of the [Cl--H3O+-O2] complex leads to the generation of Cl and OH radicals, which is the key reason for enhancing aqueous-phase oxidation and accelerating SO2 oxidation. The mass normalization rate of sulfate production from the multiphase photoreaction of SO2 on NaCl droplets could be estimated to be 0.80 × 10-4 μg·h-1 at 72% RH and 1.33 × 10-4 μg·h-1 at 81% RH, which is equivalent to the known O3 liquid-phase oxidation mechanism. Our findings highlight the significance of multiphase photo-oxidation of SO2 on NaCl particles as a non-negligible source of sulfate in coastal areas. Furthermore, this study underscores the importance of Cl- photochemistry in the atmosphere.

AB - We present a novel mechanism for the formation of photocatalytic oxidants in deliquescent NaCl particles, which can greatly promote the multiphase photo-oxidation of SO2 to produce sulfate. The photoexcitation of the [Cl--H3O+-O2] complex leads to the generation of Cl and OH radicals, which is the key reason for enhancing aqueous-phase oxidation and accelerating SO2 oxidation. The mass normalization rate of sulfate production from the multiphase photoreaction of SO2 on NaCl droplets could be estimated to be 0.80 × 10-4 μg·h-1 at 72% RH and 1.33 × 10-4 μg·h-1 at 81% RH, which is equivalent to the known O3 liquid-phase oxidation mechanism. Our findings highlight the significance of multiphase photo-oxidation of SO2 on NaCl particles as a non-negligible source of sulfate in coastal areas. Furthermore, this study underscores the importance of Cl- photochemistry in the atmosphere.

UR - https://www.scopus.com/pages/publications/85182011297

U2 - 10.1021/jacs.3c10840

DO - 10.1021/jacs.3c10840

M3 - Article

C2 - 38186050

AN - SCOPUS:85182011297

SN - 0002-7863

VL - 146

SP - 1467

EP - 1475

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 2

ER -

Photoactivation of Chlorine and Its Catalytic Role in the Formation of Sulfate Aerosols

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