高等学校化学学报 ›› 2012, Vol. 33 ›› Issue (10): 2295-2302.doi: 10.7503/cjcu20120024

• 物理化学 • 上一篇    下一篇

黑碳颗粒物表面SO2的非均相臭氧氧化

宋寒, 尚静, 朱彤, 赵黎, 叶俊辉   

  1. 北京大学环境科学与工程学院, 环境模拟与污染控制国家重点实验室, 北京 100871
  • 收稿日期:2012-01-06 出版日期:2012-10-10 发布日期:2012-09-12
  • 通讯作者: 尚 静, 女, 博士, 副教授, 主要从事大气化学研究. E-mail: shangjing@pku.edu.cn; 朱 彤, 男, 博士, 教授, 主要从事大气化学和环境健康研究. E-mail: tzhu@pku.edu.cn E-mail:shangjing@pku.edu.cn;tzhu@pku.edu.cn
  • 基金资助:

    国家自然科学基金(批准号: 20637020, 20407002); 国家科技部"八六三"计划项目(批准号: 2008AA062503)和环境模拟与污染控制国家重点联合实验室(北京大学)专项基金资助.

Heterogeneous Oxidation of SO2 by Ozone on the Surface of Black Carbon Particles

SONG Han, SHANG Jing, ZHU Tong, ZHAO Li, YE Jun-Hui   

  1. State Key Joint Laboratory of Environmental Simulation and Pollution Control, College of Environmental Sciences and Engineering, Peking University, Beijing 100871, China
  • Received:2012-01-06 Online:2012-10-10 Published:2012-09-12
  • Contact: Shang Jing E-mail:shangjing@pku.edu.cn;tzhu@pku.edu.cn

摘要:

采用漫反射红外傅里叶变换光谱(DRIFTS)结合离子色谱(IC)、 X射线光电子能谱(XPS)研究了常温常压下SO2与O3在黑碳颗粒物(以Printex U为代表, 简称UBC)表面的非均相反应. 研究发现, 在O3和水气存在的情况下, 体系的反应产物主要是SO42-, 反应在一定时间内持续进行. UBC可提供反应活性位点, 促进SO2在其表面的臭氧氧化. O3是关键的氧化剂, 能显著提高SO2非均相氧化生成SO42-的速率. 水气的存在有利于表面活性位点再生, 使反应持续发生. 当SO2和O3的浓度为1014~1015 molecule/cm3、 相对湿度为40%时, SO2在UBC(1: 400, 以NaCl为稀释剂稀释400倍)表面非均相反应生成SO42-的稳态摄取系数(γBET)为1~6×10-6, SO42-的生成速率为1014~1015 ion·s-1·g-1.

关键词: 黑碳, 硫酸根, 臭氧, 非均相反应, 稳态摄取系数

Abstract:

Black carbon (BC) produced by incomplete combustion processes is an important aerosol species. The heterogeneous reactions of gaseous pollutants (such as SO2, O3 and NOx) on the surface of BC particles are of significance because these reactions can change the particles' morphology, chemical composition, hygroscopicity and optical properties, and thus alter their climate or health effect, as well as these reactions can influence environmental chemical cycling. In this study, the heterogeneous oxidation of SO2 by O3 on the surface of black carbon(using Printex U as the model particles, denoted as UBC) was investigated by the method of Diffuse Reflectance Infrared Fourier Transform Spectroscopy(DRIFTS). The surface product was monitored, and confirmed by Ion Chromatographic (IC) and X-ray photoelectron spectroscopy (XPS) techniques. It was found that the main product of SO2 heterogeneous reaction on the surface of UBC or diluted UBC [with one part of UBC diluted in 399 parts of infrared transparent NaCl powder, denoted as UBC(1:400)] was sulfate and the oxidation reaction rate could be greatly enhanced by O3. The simultaneous presence of ozone and water vapor are necessary for the sulfate formation and the reaction rate can sustain for 3 h. UBC particles supply reactive surface sites(SS) which react with O3 to produce oxygen atom(SSO), promoting the heterogeneous oxidation of SO2 to SO42-. O3 is the dominating oxidant, and water vapor makes for SS regeneration. In the condition of 1014-1015 molecule/cm3 SO2+1014-1015 molecule/cm3 O3+40%RH, the steady state uptake coefficient of SO2 on UBC(1:400) was (1-6)×10-6 using BET surface area as the effective reaction area. The reaction order of O3 was found to be 0.5. The sulfate formation rate on the surface of UBC(1:400) particles was calculated up to 1014-1015 ion·s-1·g-1, indicating that this kind of heterogeneous reaction may play an important role in altering the physicochemical properties of BC particles in the highly air-polluted weather conditions.

Key words: Black carbon, Sulfate, Ozone, Heterogeneous reaction, Steady state uptake coefficient

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