微液滴表面驱动和加速质子控制,大小依赖的硝酸盐光解

IF 15.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Xiaowu Zhang, Qishen Huang*, Yu-Xin Liu, Jiayi Yin, Shu-Feng Pang, Pai Liu*, Yun-Hong Zhang* and Maofa Ge*, 
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引用次数: 0

摘要

颗粒硝酸盐光解再生大气中的活性氧化氮(HONO和NOx),影响对流层臭氧、大气氧化能力和颗粒物质形成。然而,报道的硝酸盐光解速率在数量级上有所不同,并且质子和空气-水界面在加速溶解的气溶胶(即微滴)中硝酸盐光解的作用仍不清楚。利用共聚焦拉曼光谱和气溶胶光镊测量了微液滴中硝酸盐的光解速率系数(j),其范围为5.28 × 10-8 ~ 9.07 × 10-6 s-1,取决于pH值(3.2 ~ 7.4)和半径(3.7 μm ~ 6.0 mm)。j在质子充足条件下保持与pH无关(pH <;6.5),但在质子缺乏条件下随着pH的增加而降低(pH >;6.5),解决了以往研究的差异。此外,我们确定了一个临界点半径(r* = 706 μm),在此半径以下,j与液滴半径成反比,在此半径以上,j在水体积值(6.73±2.12 × 10-8 s-1)处趋于稳定。这些发现表明,硝酸盐光解作用主要发生在空气-水界面的微滴中。由于大气气溶胶的pH值和半径通常低于这些临界点(pH* = 6.5, r* = 706 μm),表面驱动的尺寸依赖性光解作用可能解释了大气颗粒物硝酸盐光解速率的变化。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Microdroplet Surface Drives and Accelerates Proton-Controlled, Size-Dependent Nitrate Photolysis

Microdroplet Surface Drives and Accelerates Proton-Controlled, Size-Dependent Nitrate Photolysis

Particulate nitrate photolysis regenerates reactive oxidized nitrogen species (HONO and NOx) in the atmosphere, influencing tropospheric ozone, atmospheric oxidation capacity, and particulate matter formation. However, reported nitrate photolysis rates vary by orders of magnitude, and the roles of protons and the air–water interface in accelerating nitrate photolysis in deliquesced aerosols (i.e., microdroplets) remain unclear. Using confocal Raman spectroscopy and aerosol optical tweezer, we measured nitrate photolysis rate coefficients (j) in microdroplets, ranging from 5.28 × 10–8 to 9.07 × 10–6 s–1, depending on pH (3.2–7.4) and radius (3.7 μm to 6.0 mm). j remained pH-independent under proton-sufficient conditions (pH < 6.5) but decreased with increasing pH under proton-deficient conditions (pH > 6.5), resolving discrepancies in previous studies. Moreover, we identified a tipping-point radius (r* = 706 μm), below which j scales inversely with the droplet radius and above which j plateaus at the aqueous bulk value (6.73 ± 2.12 × 10–8 s–1). These findings demonstrate that nitrate photolysis occurs predominantly at the air–water interface in microdroplets. With the atmospheric aerosol pH and radii typically below these tipping points (pH* = 6.5, r* = 706 μm), the surface-driven size-dependent photolysis likely explains the variations in atmospheric particulate nitrate photolysis rates.

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来源期刊
CiteScore
24.40
自引率
6.00%
发文量
2398
审稿时长
1.6 months
期刊介绍: The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.
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