The effects of acetaldehyde, glyoxal and acetic acid on the heterogeneous reaction of nitrogen dioxide on gamma-alumina.
The effects of acetaldehyde, glyoxal and acetic acid on the heterogeneous reaction of nitrogen dioxide on gamma-alumina.
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DOI：
10.1039/c5cp05632b
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发表时间：
2016-03
期刊：
影响因子：
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通讯作者：
Zhenyu Sun;Lingdong Kong;Xiaoxia Ding;Chengtian Du;Xi Zhao;Jianmin Chen;Hongbo Fu;Xin Yang;T. Cheng
中科院分区：
文献类型：
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作者：
Zhenyu Sun;Lingdong Kong;Xiaoxia Ding;Chengtian Du;Xi Zhao;Jianmin Chen;Hongbo Fu;Xin Yang;T. Cheng
氮氧化物在氧化铝表面的非均相反应导致形成吸附的亚硝酸盐和硝酸盐。然而，很少有人知道其他物种对这些多相反应及其产物的影响。在这项研究中，漫反射红外光谱（DRIFTS）被用来分析在298 K的预吸附的有机物种（乙醛，乙二醛和乙酸）的存在下，在氧化铝颗粒表面的NO2的非均相反应的过程中，揭示这些有机物种对吸附的亚硝酸盐和硝酸盐的形成的影响。结果表明，有机物（乙醛、乙二醛和乙酸）在γ-Al 2 O3上的预吸附对硝酸盐的生成有不同程度的抑制作用。在相同实验条件下，乙酸预吸附对NO2生成的抑制作用远强于乙醛和乙二醛预吸附，表明乙酸对NO2非均相反应的影响不同于乙醛和乙二醛。表面亚硝酸盐形成并被鉴定为中间产物。对于有和无乙醛和乙二醛预吸附的NO2在γ-Al 2 O3表面上的非均相反应，随着反应的进行，NO2首先生成，然后逐渐消失;而对于有乙酸预吸附的反应，NO2是除硝酸盐外的最终主要产物。这表明乙酸的预吸附会促进亚硝酸盐的形成，而其他物质的预吸附不会改变亚硝酸盐的形成趋势。提出了乙醛、乙二醛和乙酸预吸附对γ-Al 2 O3非均相转化NO2的可能影响机制，并讨论了这些结果的大气意义。
Heterogeneous reactions of nitrogen oxides on the surface of aluminium oxide result in the formation of adsorbed nitrite and nitrate. However, little is known about the effects of other species on these heterogeneous reactions and their products. In this study, diffuse reflectance infrared spectroscopy (DRIFTS) was used to analyze the process of the heterogeneous reaction of NO2 on the surface of aluminium oxide particles in the presence of pre-adsorbed organic species (acetaldehyde, glyoxal and acetic acid) at 298 K and reveal the influence of these organic species on the formation of adsorbed nitrite and nitrate. It was found that the pre-adsorption of organic species (acetaldehyde, glyoxal and acetic acid) on γ-Al2O3 could suppress the formation of nitrate to different extents. Under the same experimental conditions, the suppression of the formation of nitrate by the pre-adsorption of acetic acid is much stronger than that by pre-adsorption of acetaldehyde and glyoxal, indicating that the influence of acetic acid on the heterogeneous reaction of NO2 is different from that of acetaldehyde and glyoxal. Surface nitrite is formed and identified to be an intermediate product. For the heterogeneous reaction of NO2 on the surface of γ-Al2O3 with and without the pre-adsorption of acetaldehyde and glyoxal, it is firstly formed and then gradually disappears as the reaction proceeds, but for the reaction with the pre-adsorption of acetic acid, it is the final main product besides nitrate. This indicates that the pre-adsorption of acetic acid would promote the formation of nitrite, while the others would not change the trend of the formation of nitrite. The possible influence mechanisms of the pre-adsorption of acetaldehyde, glyoxal and acetic acid on the heterogeneous conversion of NO2 on γ-Al2O3 are proposed and atmospheric implications based on these results are discussed.