Mechanisms of Hydration Reactions of Typical Small α-dicarbonyls at the Interfaces of Ammonium-bearing Particles

Ma Ruize; Wang Jiaxin; Li Wenjian; Shi Qiuju; Ji Yuemeng

doi:10.12052/gdutxb.250076

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Mechanisms of Hydration Reactions of Typical Small α-dicarbonyls at the Interfaces of Ammonium-bearing Particles

更新时间：2026-05-27

- Mechanisms of Hydration Reactions of Typical Small α-dicarbonyls at the Interfaces of Ammonium-bearing Particles
- Vol. 42, Issue 5, Pages: 31-38(2025)
- 作者机构：
  
  1. 广东工业大学环境科学与工程学院,广东,广州,510006
  2. 广东工业大学环境催化与污染控制广州重点实验室,广东,广州,510006
  3. 广东工业大学城市群环境安全与绿色发展教育部重点实验室,广东,广州,510006
- 作者简介：
- 基金信息：
- DOI：10.12052/gdutxb.250076
  CLC： X513
- Published：2025
- 稿件说明：
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马睿泽, 王甲新, 李文健, 等. 典型小分子量α-二羰基化合物在含铵颗粒物界面的水合反应机理[J]. 广东工业大学学报, 2025, 42(5): 31–38.

Ma Ruize, Wang Jiaxin, Li Wenjian, et al. Mechanisms of Hydration Reactions of Typical Small α-dicarbonyls at the Interfaces of Ammonium-bearing Particles[J]. 2025, 42(5): 31-38.
马睿泽, 王甲新, 李文健, 等. 典型小分子量α-二羰基化合物在含铵颗粒物界面的水合反应机理[J]. 广东工业大学学报, 2025, 42(5): 31–38. DOI： 10.12052/gdutxb.250076

Ma Ruize, Wang Jiaxin, Li Wenjian, et al. Mechanisms of Hydration Reactions of Typical Small α-dicarbonyls at the Interfaces of Ammonium-bearing Particles[J]. 2025, 42(5): 31-38. DOI： 10.12052/gdutxb.250076.

摘要

小分子量α-二羰基化合物(Small α-dicarbonyls，SαDs) 作为二次有机气溶胶(Secondary Organic Aerosol，SOA) 的重要前体物，其界面化学过程被认为是SOA的重要生成途径。然而，SαDs在复杂颗粒物界面上的化学反应及其对SOA的贡献机制还不清晰。因此，本文采用玻恩−奥本海默分子动力学模拟研究了乙二醛(Glyoxal，GL) 和甲基乙二醛(Methylglyoxal，MG) 两种典型SαDs在氯化铵(NH

Cl) 和硫酸铵[(NH

)

]

颗粒物界面上的水合反应机制。结果表明，GL和MG的醛基基团在NH

Cl和(NH

)

颗粒物界面上的水合反应均经历了(I) 水分子中的氢转移形成阳离子中间体、(II) 水分子中羟基攻击醛基碳原子形成过渡态(Transition State，TS) 以及(III) 水团簇间的氢转移形成醛基−二醇3个步骤。

${\mathrm{SO}}_4^{2-} $

img text_id='Z-20250616102831' class='formula-img' style='display:none;' src='250076_Z-20250616102831.jpg'>

的存在对GL和MG的界面水合反应起促进作用。然而，MG的酮基基团在NH

Cl和(NH

)

颗粒物界面上的水合反应包括(I) TS的形成和(II) 酮基−二醇的形成2个步骤，反应分别由1个及7个水分子介导。过量水分子的参与导致MG酮基基团在(NH

)

颗粒物界面上的水合反应比在NH

Cl颗粒物界面上更难发生。GL和MG在含铵颗粒物界面生成的二醇产物有进入溶液内部参与液相低聚反应的潜势，从而促进SOA的形成。研究结果揭示了不同含铵颗粒物界面组分对GL和MG界面水合反应机理的影响，这为理解

SαDs在复杂气溶胶颗粒物中的界面化学过程及其如何影响SOA的形成提供了理论依据。

Abstract

Small α-dicarbonyls (SαDs)

as the important precursors of secondary organic aerosol (SOA)

significantly contribute to SOA formation through their interfacial chemical processes. However

the reaction mechanisms of SαDs at the interfaces and their roles in the formation of SOA remain uncertain. Hence

Born-Oppenheimer molecular dynamics simulation was performed to investigate the interfacial hydration reaction mechanisms of typical SαDs

including glyoxal (GL) and methylglyoxal (MG)

at the interfaces of ammonium chloride (NH

Cl) and ammonium sulfate [(NH

)

]

particles. The results show that the hydration reactions of the aldehyde groups of GL and MG at both interfaces proceed via three steps: (I) hydrogen transfer of the interfacial water molecule leading to the formation of the cationic intermediates

(II) the attack of the aldehyde carbon atom by the hydroxyl group of the interfacial water molecule forming the transition states (TS)

and (III) subsequent aldehyde-diol formation. Sulfate ion (

${\mathrm{SO}}_4^{2-} $

img text_id='Z-20250616091541' class='formula-img' style='display:none;' src='250076_Z-20250616091541.jpg'>

) promotes the interfacial hydration reactions of the aldehyde groups of GL and MG. However

two steps

i.e.

(I) TS formation and (II) ketone-diol formation exist for the hydration reaction of the ketone group of MG. The process is mediated by one and seven water molecules

respectively. Excess water molecules hinder the hydration reaction of the ketone group of MG at the interface of (NH

)

particle. The diol products generated by the hydration reactions of GL and MG at the interfaces have the potential to come into the droplet interior and subsequently engage into oligomerization

reactions

thereby contributing to the formation of SOA. The results provide an insight into the interfacial chemistry of GL and MG in different particles and their influence on the SOA formation.

关键词

Keywords

references

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