大气颗粒物表面的非均相反应过程，既会影响气态污染物的源汇平衡，也会改变颗粒物的微观组成和性质(吸湿性和消光性质等)，在灰霾形成过程中具有重要作用。然而，在大气复合污染条件下，颗粒物表面的非均相反应过程中是否存在新的机制并不清楚。因此，亟待开展多种污染物在大气非均相反应过程中的相互影响及复合效应的研究，揭示复合污染条件下二次粒子的生成机制，为阐明我国大气复合污染成因提供科学依据。
1. 大气非均相反应中复合效应的研究进展
1.1. 首次发现了共存的NOx可以极大地促进SO2和亚硫酸盐向硫酸盐的转化，揭示了NO2和矿质氧化物共同催化活化分子氧，并促进硫酸盐的形成(JPCA, 2008, 112, 6630; PCCP, 2012, 14(5), 1668; PCCP, 2013, 15, 19196);
1.2. 进一步证实了SO2可以极大促进NO2在MgO表面转化为HONO，该过程可能是大气中HONO的潜在来源(EST, 2017, 51, 3767);
1.3. 系统研究了SO2和NH3在矿质氧化物表面非均相反应过程中的相互促进作用机制，揭示了这一过程是大气中硫酸盐和铵盐形成的重要途径(PCCP, 2016, 18 (2), 956; JPCA 2018, 122 (30), 6311; ESNano, 2019, 6, 2749 (HOT Article)；AE, 2019, 208: 133);
1.4. 液相反应中共存NH3促进SO2溶解，离子强度改变NO2氧化SO2的速率常数，进而加速硫酸盐形成（EP, 2019, 252, 236);
1.5. 北京地区冬季强霾期间的监测数据分析结果表明，成霾期间共存矿质颗粒物和高浓度NOx是促进SO2转化为硫酸盐的关键因素。复合污染条件下，SO2的环境容量下降，导致硫酸盐快速增长致霾(SR, 2014(4): 04172；EP, 2018, 233, 662)。
2. 颗粒物吸湿性及吸湿过程中的复合效应研究进展
2.1. 建立了基于压力平衡法的水蒸气吸附仪(JPCA, 2010, 114, 4232)和吸湿性差分电迁移率分析仪HTDMA(ACS Earth and Space Chemistry, 2019, 3(7), 1216)，结合原位红外光谱和拉曼光谱等手段，研究了非均相反应对颗粒物吸湿性的促进作用及其机制(PCCP, 2012, 14 (23), 8403; JES, 2010, 22 (4), 555; 2012, 24(1), 62);
2.2. 揭示了多相过程中的复合效应改变大气中硫酸盐的赋存形式，是大气中二次石膏形成的关键机制(PCCP, 2013, 15, 19196);
2.3. 发现了有机-无机混合颗粒物吸湿过程中存在液相反应，阐明了弱酸置换强酸的内在机制 (EST, 2013, 47(18), 10381; AE, 2012, 50, 97; 2013, 69, 281; 2019, 200, 34)。
3. 黑碳表面的非均相过程研究进展
3.1. 在不同燃氧比条件下制备了甲苯、正己烷和癸烷燃烧的黑碳样品。基于组成和吸湿性表征，发现正己烷和癸烷黑碳的亲水性随燃氧比减小而增大，平均粒径 和有机碳含量随燃氧比减小而降低，黑碳的聚集形态不受燃氧比影响。基于红外 光谱和拉曼光谱的分析，发现亲水性官能团主要位于黑碳结构中的石墨层边缘和 表面石墨层。(JPCA, 2012, 116, 4129)
3.2. 利用原位拉曼光谱研究 O3 与黑碳的非均相反应，发现O3老化导致黑碳微晶有序度降低，无序碳和无定型碳为臭氧化反应活性位点。 O3老化使得黒碳表面含氧官能团含量升高，光照可以进一步增强O3对黒碳的老化。(PCCP, 2010, 12, 10896; JPC, 2012, 137, 084507; PCCP, 2016, 18, 24401)
3.3. 发现 NO2 摄取系数和 HONO 产率随燃氧比减小而减小，有机碳(OC) 是 NO2 老化过程中的主要活性组分。光照可以进一步增强老化作用，并证明黒碳表面含氮物种的光解是大气中HONO的一个重要来源。(EST, 2013, 47, 3174; AE, 2013, 64, 270)
3.4. 发现可见光可激发分子 O2 与黑碳的非均相化学反应，导致黑碳表面生成各种含氧官能团，有机碳(OC)是参与老化反应的主要活性组分。(PNAS, 2012, 109, 21250)
3.5. 发现黒碳可以催化O2氧化SO2向硫酸盐的转化，并通过理论计算揭示了其催化反应机理。分子O2可以在黒碳表面的醚键位点(C-O-C)常温下裂解为环氧基，环氧基进而实现对SO2的直接氧化。 (AE, 2016, 142, 383; PCCP, 2016, 18, 31691; AE, 2017, 152, 465; ACS Catal, 2018, 8, 3825)
相关论文:
53) Biwu Chu, Yali Wang, Weiwei Yang, Jinzhu Ma, Qingxin Ma*, Peng Zhang, Yongchun Liu, Hong He, “Effects of NO2 and C3H6 on the heterogeneous oxidation of SO2 on TiO2 in the presence or absence of UV-Vis irradiation.” Atmos. Chem. Phys., 19, (2019) 14777-14790.
52) Shuping Zhang, Jia Xing*, Golam Sarwar, Yanli Ge, Hong He, Fengkui Duan, Yan Zhao, Kebin He, Lidan Zhu, Biwu Chu*, “Parameterization of heterogeneous reaction of SO2 to sulfate on dust with coexistence of NH3 and NO2 under different humidity conditions”, Atmos. Environ., 208, (2019) 133-140.
51) Qingxin Ma, Cheng Zhong, Chang Liu, Jun Liu, Jinzhu Ma, Lingyan Wu, Hong He*, “A comprehensive study about the hygroscopic behavior of mixtures of oxalic acid and nitrate salts: Implication for the occurrence of atmospheric metal oxalate complex”, ACS Earth. Space Chem., 3, (2019) 1216-1225.
50) Qingxin Ma*, Ling Wang, Biwu Chu, Jinzhu Ma, Hong He*, “Contrary role of H2O and O2 in the kinetics of heterogeneous photochemical reactions of SO2 on TiO2”, J. Phys. Chem. A., 123, (2019) 1311-1318.
49) Qingxin Ma, Chang Liu, Jinzhu Ma, Biwu Chu, Hong He*, “A laboratory study on the hygroscopic behavior of H2C2O4-containing mixed particles”, Atmos. Environ., 200, (2019) 34-39.
48) Tianzeng Chen, Biwu Chu*, Yanli Ge, Shuping Zhang, Qingxin Ma, Hong He, Shao-Meng Li, “Enhancement of aqueous sulfate formation by the coexistence of NO2/NH3 under high ionic strengths in aerosol water”, Environ. Pollut., 252, (2019), 236-244.
47) 王铃，马庆鑫*，贺泓，“光照对SO2在矿质氧化物表面非均相反应的影响”，环境科学，38 (3), (2018) 1-2.
46) Weiwei Yang, Qinxin Ma*, Yongchun Liu, Jinzhu Ma, Biwu Chu, Ling Wang, Hong He, “Role of NH3 in the heterogeneous formation of secondary inorganic aerosols on mineral oxides”, J. Phys. Chem. A, 122, (2018) 6311-6320.
45) Guangzhi He, Jinzhu Ma,Hong He*, “Role of carbonaceous aerosols in catalyzing sulfate formation”, ACS. Catal., 8, (2018) 3825-3832.
44) Jinzhu Ma, Biwu Chu, Jun Liu, Yongchun Liu, Hongxing Zhang,Hong He*, “NOX promotion of SO2 conversion to sulfate: An important mechanism for the occurrence of heavy haze during winter in Beijing”, Environ. Pollut., 233, (2018) 662-669.
43) Chang Liu, Qingxin Ma,Hong He*, Guangzhi He, Jinzhu Ma, Yongchun Liu, Ying Wu, “Structure-activity relationship of surface hydroxyl groups during NO2 adsorption and transformation on TiO2 nanoparticles”, Environ. Sci. Nano., 4, (2017) 2388-2394.
42) Qingxin Ma*, Tao Wang*, Chang Liu, Hong He, Zhe Wang, Weihan Wang, Yutong Liang, “SO2 initiates the efficient conversion of NO2 to HONO on MgO surface”, Environ. Sci. Technol., 51, (2017) 3767-3775.
41) Weiwei Yang, Jianghao Zhang, Qingxin Ma*, Yan Zhao, Yongchun Liu, Hong He*, “Heterogeneous reaction of SO2 on manganese oxides: the effect of crystal structure and relative humidity”, Sci. Rep., 7, (2017) 4550.
40) Chong Han, Yongchun Liu, Hong He*, “Heterogeneous reaction of NO2 with soot at different relative humidity”, Environ. Sci. Pollut. Res., 24, (2017) 21248-21255.
39) Yan Zhao, Yongchun Liu*, Jinzhu Ma, Qingxin Ma, Hong He*, “Heterogeneous reaction of SO2 with soot: the roles of relative humidity and combustion conditions in sulfuric acid formation”, Atmos. Environ., 152, (2017) 465-476.
38) Guangzhi He, Hong He*, “DFT studies on the heterogeneous oxidation of SO2 by oxygen functional groups on grapheme”, Phys. Chem. Chem. Phys., 18, (2016) 31691-31697.
37) Yan Zhao, Qingxin Ma, Yongchun Liu, Hong He*, “Influence of sulfur in fuel on the properties of diffusion flame soot”, Atmos. Environ., 142, (2016) 383-392.
36) Chong Han, Yongchun Liu, Hong He*, “The photoenhanced aging process of soot by the heterogeneous ozonization reaction”, Phys. Chem. Chem. Phys., 18, (2016) 24401-24407.
34) Biwu Chu, Tengyu Liu, Xiao Zhang, Yongchun Liu, Qingxin Ma, Jinzhu Ma, Hong He*, Xinming Wang, Junhua Li, Jiming Hao, “Secondary aerosol formation and oxidation capacity in photooxidation in the presence of Al2O3 seed particles and SO2”, Sci. China-Chem., 58 (9), (2015) 1426-1434.
33) 马庆鑫，马金珠，楚碧武，刘永春，赖承钺，贺泓*，“矿质和黑碳颗粒物表面大气非均相反应研究进展”, 科学通报，60(2)，(2015)122-136.
32) Yongchun Liu, Chong Han, Jinzhu Ma, Xiaolei Bao, Hong He*, “Influence of relative humidity on heterogeneous kinetics of NO2 on kaolin and hematite”, Phys. Chem. Chem. Phys., 17, (2015) 19424-19431.
31) Chengyue Lai, Yongchun Liu*, Jinzhu Ma, Qingxin Ma, Biwu Chu, and Hong He*, “Heterogeneous kinetics of cis-pinonic acid with hydroxyl radical under different environmental conditions”, J. Phys. Chem. A, 119, (2015) 6583-6593.
30) Chengyue Lai, Yongchun Liu*, Jinzhu Ma, Qingxin Ma, Hong He*, “Laboratory study on OH-initiated degradation kinetics of dehydroabietic acid”, Phys. Chem. Chem. Phys., 17, (2015) 10953-10962.
29) Chengyue Lai, Yongchun Liu*, Jinzhu Ma, Qingxin Ma, Hong He*, “Degradation kinetics of levoglucosan initiated by hydroxyl radical under different environmental conditions”, Atmos. Environ., 91, (2014) 32-39.
28) Biwu Chu, Kun Wang, Hideto Takekawa, Junhua Li, Wei Zhou, Jingkun Jiang, Qingxin Ma, Hong He, Jinming Hao*, “Hygroscopicity of particles generated from photooxidation of α-pinene under different oxidation conditions in the presence of sulfate seed aerosols”, J. Environ. Sci., 26, (2014) 129-139.
27) Hong He*, Yuesi Wang*, Qingxin Ma, Jinzhu Ma, Biwu Chu, Dongsheng Ji, Guiqian Tang, Chang Liu, Hongxing Zhang, Jiming Hao, “Mineral dust and NOx promote the conversion of SO2 to sulfate in heavy pollution days”, Sci. Rep., 4, (2014) 04172.
26) Qingxin Ma, Hong He*, Yongchun Liu, Chang Liu, Vicki H. Grassian, “Heterogeneous and multiphase formation pathways of gypsum in the atmosphere”, Phys. Chem. Chem. Phys., 15, (2013) 19196-19204.
25) Qingxin Ma, Jinzhu Ma, Chang Liu, Chengyue Lai, Hong He*, “Laboratory study on the hygroscopicbehavior of external and internal C2−C4 dicarboxylic Acid−NaCl mixtures”, Environ. Sci. Technol., 47, (2013) 10381-10388.
24) Qingxin Ma, Hong He*, Chang Liu, “Hygroscopic properties of oxalic acid and atmospherically relevant oxalates”, Atmos. Environ., 69, (2013) 281-288.
23) Chong Han, Yongchun Liu, Hong He*, “Role of Organic Carbon in Heterogeneous Reaction of NO2 with Soot”, Environ. Sci. Technol., 47, (2013) 3174-3181.
22) Jinzhu Ma, Yongchun Liu, Chong Han, Qingxin Ma, Chang Liu, Hong He*, “Review of heterogeneous photochemical reactions of NOy on aerosol – A possible daytime source of nitrous acid (HONO) in the atmosphere”, J. Environ. Sci., 25, (2013) 326-334.
21) Jinzhu Ma, Yongchun Liu, Qingxin Ma, Chang Liu, Hong He*，“Heterogeneous photochemical reaction of ozone with anthracene adsorbed on mineral dust”, Atmos. Environ., 72, (2013) 165-170.
20) Chong Han, Yongchun Liu*, Hong He*, “Heterogeneous photochemical aging of soot by NO2 under simulated sunlight”, Atmos. Environ., 64, (2013) 270-276.
19) Chong Han, Yongchun Liu*, Jinzhu Ma, Hong He*, “Key role of organic carbon in the sunlight enhanced atmospheric aging of soot by O2”, Proc. Nat. Acad. Sci. USA., 109(52), (2012) 21250-21255.
18) Yongchun Liu, Qingxin Ma, Hong He*, “Heterogeneous Uptake of Amines by Citric Acid and Humic Acid”, Environ. Sci. Technol., 46, (2012) 11112-11118.
17) Chong Han, Yongchun Liu*, Jinzhu Ma, Hong He*, “Effect of soot microstructure on its ozonization reactivity”, J. Chem. Phys., 137, (2012) 084507.
16) Yongchun Liu, Chong Han, Chang Liu, Jinzhu Ma, Qingxin Ma, Hong He*, “Differences in the reactivity of ammonium salts with methylamine”, Atmos. Chem. Phys., 12, (2012) 4855-4865.
15) Qingxin Ma, Yongchun Liu, Chang Liu, Hong He*, “Heterogeneous reaction of acetic acid on MgO, a-Al2O3, and CaCO3 and the effect on the hygroscopic behaviour of these particles”, Phys. Chem. Chem. Phys., 14, (2012) 8403-8409.
14）Chong Han, Yongchun Liu*, Chang Liu, Jinzhu Ma, Hong He*, “Influence of combustion conditions on hydrophilic properties and microstructure of flame soot”, J. Phys. Chem. A, 116, (2012) 4129-4136.
13) Qingxin Ma, Yongchu Liu, Chang Liu, Jinzhu Ma, Hong He*, “A case study of Asian dust storm particles: Chemical composition, reactivity to SO2 and hygroscopic properties”, J. Environ. Sci, 24, (2012) 62-71.
12) Qingxin Ma, Hong He*, “Synergistic effect in the humidifying process of atmospheric relevant calcium nitrate, calcite and oxalic acid mixtures”, Atmos. Environ., 50, (2012) 97-102.
11) Chang Liu, Qingxin Ma, Yongchun Liu, Jinzhu Ma, Hong He*, “Synergistic reaction between SO2 and NO2 on mineral oxides: a potential formation pathway of sulfate aerosol. Phys. Chem. Chem. Phys., 14, (2012) 1668-1676.
10) 马金珠、刘永春、马庆鑫、刘畅、贺泓*, “大气非均相反应及其环境效应”, 环境化学, 30, (2011) 97-119.
9) Jinzhu Ma, Yongchun Liu, Hong He*, “Heterogeneous reactions between NO2 and anthracene adsorbed on SiO2 and MgO ”, Atmos. Environ., 45, (2011) 917-924.
8) Jinzhu Ma, Yongchun Liu, Hong He*, “Degradation kinetics of anthracene by ozone on mineral oxides”, Atmos. Environ., 44, (2010) 4446-4453.
7) Yongchun Liu, Chang Liu, Jinzhu Ma, Qingxin Ma, Hong He*, “Structural and hygroscopic changes of soot during heterogeneous reaction with O3”, Phys. Chem. Chem. Phys., 12, (2010) 10896-10903.
6) Qingxin Ma, Yongchun Liu, Chang Liu, Jinzhu Ma, Hong He*, “A comprehensive characterisation of Asian dust storm particles: chemical composition, reactivity to SO2, and hygroscopic property”, Atmos. Chem. Phys. Discuss., 10, (2010) 8899-8925.
5) Qingxin Ma, Hong He*，Yongchun Liu, “In situ DRIFTS study of hygroscopic behavior of mineral aerosol ”, J. Environ. Sci., 22, (2010) 555-560.
4)Qingxin Ma, Yongchun Liu, Hong He*, “The utilization of physisorption analyzer for studying the hygroscopic properties of atmospheric relevant particles”, J. Phys. Chem. A, 114, (2010) 4232-4237.
3) Yongchun Liu, Qingxin Ma, Hong He*, “Comparative study of the effect of water on the heterogeneous reactions of carbonyl sulfide on the surface of α-Al2O3 and MgO” , Atmos. Chem. Phys., 9, (2009) 6273-6286.
2) 贺泓*, 刘永春，曲久辉, “环境微界面过程的原位和在线研究方法”, 环境科学学报,29, (2009) 11-20.
1) Qingxin Ma, Yingchun Liu, Hong He*, “Synergistic effect between NO2 and SO2 in their adsorption and reaction on γ-Alumina”, J. Phys. Chem. A, 112, (2008) 6630-6635.
