Citation: XU Zi-yang, YUE Shuang, WANG Chun-bo, SUN Bo-zhao, LI Hang-xing. Reaction mechanism of heterogeneous reduction of NO₂ on carbonaceous surface[J]. Journal of Fuel Chemistry and Technology, ;2020, 48(10): 1236-1247. shu

Reaction mechanism of heterogeneous reduction of NO₂ on carbonaceous surface

School of Energy, Power Engineering and Mechanical Engineering, North China Electric Power University, Baoding 071003, China

Corresponding author: XU Zi-yang, 923126537@qq.com
Received Date: 11 August 2020
Revised Date: 26 September 2020

Fund Project: The National Natural Science Foundation of China 51976059The project was supported by the National Natural Science Foundation of China (51976059)

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Based on the quantum chemical density functional theory(DFT), the mechanism of heterogeneous reduction of NO₂ on carbonaceous surface was studied. For zigzag and armchair carbonaceous surfaces, M06-2X method and 6-311G(d) basis set were used to optimize the geometry configuration and energy of all stagnation points under different reaction paths, and the reaction paths were analyzed and compared from thermodynamics and kinetics. The role of CO in the heterogeneous reduction of NO₂ was deeply investigated, and the effects of carbon surface and reaction temperature on the heterogeneous reaction were also investigated. The results show that the heterogeneous reduction process of NO₂ on the carbon surface can be divided into two stages: the reduction stage of NO₂ and the desorption stage of carbon oxide. By comparing the reactions without CO molecules, it can be seen that the CO molecules involved in the reaction can reduce the reaction energy barrier of each stage and accelerate the reaction rate of each stage. In the presence of CO molecule, the reaction energy barrier at the reduction stage of NO₂ is reduced, which promotes the heterogeneous reaction process of NO₂ reduction to NO. CO molecules participating in the reaction can combine with the residual oxygen atoms on the surface to form and release CO₂ molecules, which reduces the reaction energy barrier in the release stage of carbon oxides, thus promoting the overall reduction reaction. In addition, the energy barrier of NO₂ heterogeneous reduction reaction on zigzag surface is lower and the reaction rate is faster than that on armchair surface, which indicates that the heterogeneous reduction reaction of NO₂ is easier on Zigzag carbonaceous surface. Finally, the reaction kinetics analysis shows that the reaction rate of each stage increases with the increase of temperature, which indicates that increasing temperature can promote the heterogeneous reduction of NO₂ on the carbonaceous surface.
- NO₂,
- CO,
- carbonaceous surface,
- heterogeneous reduction,
- density functional theory,
- reaction kinetics
1. [1]
  ZHANG Xiu-xia, LV Xiao-xue, WU Hui-xi, XIE Miao, LIN Ri-yi, ZHOU Zhi-jun. Microscopic mechanism for effect of sodium on NO heterogeneous reduction by char[J]. J Fuel Chem Technol, 2020,48(6):663-673.
2. [2]
  TAN Guan-xi, CHI Yao-ling, LI Shuang, YI Yu-feng, JIN Guang-zhou. Study on the performance of Mn-Zr composite oxide for CO reduction of NO[J]. J Fuel Chem Technol, 2019,47(10):1258-1264.
3. [3]
  TAYLOR K. nitric oxide catalysis in automotive exhaust systems[J]. Catal Rev, 1993,4(35):457-481.
4. [4]
  WANG C, WANG P, DU Y, CHE D. Experimental study on effects of combustion atmosphere and coal char on NO₂ reduction under oxy-fuel condition[J]. J Energy Ins, 2019,92(4):1023-1033. doi: 10.1016/j.joei.2018.07.004
5. [5]
  XIN Jing. Mechanism and experimental study of nitrogen conversion in coal char-NO reaction process[D]. Beijing: North China Electric Power University, 2015.
6. [6]
  LI Jing-ji, YANG Xin-hua, YANG Hai-rui, LV Jun-fu. Experimental and model study on the formation of coke type NO_x in bubble bed[J]. J China Coal Soc, 2016,41(6):1546-1553.
7. [7]
  WANG C A, DU Y, CHE D. Study on N₂O reduction with synthetic coal char and high concentration CO during oxy-fuel combustion[J]. Proc Combust Inst, 2015,35(2):2323-2330. doi: 10.1016/j.proci.2014.07.018
8. [8]
  ZHANG Xiu-xia, ZHOU Zhi-jun, ZHOU Jun-hu, JIANG Shu-dong, LIU Jian-zhong, CEN Ke-fa. Density Functional Theory study on the mechanism of heterogeneous formation and decomposition of N₂O on coke surface[J]. J Fuel Chem Technol, 2011,39(11):806-811.
9. [9]
  ARENILLAS A, ARIAS B, RUBIERA F, PIS J J, LÓPEZ R, CAMPOMANES P, PEVIDA C, MENÉNDEZ M I. Heterogeneous reaction mechanisms of the reduction of nitric oxide on carbon surfaces:A theoretical analysis[J]. Theor Chem Acc, 2010,127(1/2):95-108.
10. [10]
  PEVIDA C, ARENILLAS A, RUBIERA F, PIS J J. Synthetic coal chars for the elucidation of NO heterogeneous reduction mechanisms[J]. Fuel, 2007,86(1/2):41-49.
11. [11]
  YING Zhi, ZHENG Xiao-yuan, CUI Guo-min. Study on combustion performance of pulverized coal based on O₂/CO₂ atmosphere[J]. Chin J Power Eng, 2019,39(1):7-12.
12. [12]
  DEGRAEUWE B, THUNIS P, CLAPPIER A, WEISS M, LEFEBVRE W, JANSSEN S, VRANCKX S. Impact of passenger car NO_x emissions and NO₂ fractions on urban NO₂ pollution-Scenario analysis for the city of Antwerp, Belgium[J]. Atmos Environ, 2016,126:218-224. doi: 10.1016/j.atmosenv.2015.11.042
13. [13]
  OUYANG Zi-qu, ZHU Jian-guo, LV Qing-gang. Experimental study on combustion and NO_x emission of pulverized anthracite coal preheated by a circulating fluidized bed[J]. Proc CSEE, 2014(11):1748-1754.
14. [14]
  GARCÍA-GARCÍA A, ILLÁN-GÓMEZ M J, LINARES-SOLANO A, SALINAS-MARTÍNEZ DE LECEA C. NO_x Reduction by potassium-containing coal briquettes.effect of NO₂ concentration[J]. Energy Fuels, 1999,13(2):499-505. doi: 10.1021/ef980165h
15. [15]
  SADAOKA Y, JONES T A, REVELL G S, G PEL W. Effects of morphology on NO₂ detection in air at room temperature with phthalocyanine thin films[J]. J Mater Sci, 1990,25(12):5257-5268. doi: 10.1007/BF00580159
16. [16]
  ZHU X, ZHANG L, ZHANG M, MA C. Effect of N-doping on NO₂ adsorption and reduction over activated carbon:An experimental and computational study[J]. Fuel, 2019,258116109. doi: 10.1016/j.fuel.2019.116109
17. [17]
  JEGUIRIM M, TSCHAMBER V, BRILHAC J F, EHRBURGER P. Interaction mechanism of NO₂ with carbon black:effect of surface oxygen complexes[J]. J Anal Appl Pyrolysis, 2004,72(1):171-181. doi: 10.1016/j.jaap.2004.03.008
18. [18]
  MUCKENHUBER H, GROTHE H. The heterogeneous reaction between soot and NO₂ at elevated temperature[J]. Carbon, 2006,44(3):546-559. doi: 10.1016/j.carbon.2005.08.003
19. [19]
  WANG Chun-bo, YUE Shuang, XU Xu-bin, LI Yi-peng. NO_x emission characteristics of coal coke under constant temperature combustion in O₂/CO₂ atmosphere[J]. J China Coal Soc, 2018,43(1):257-264.
20. [20]
  WANG Bi, SU Sheng, SUN Lu-shi, HU Song, FEI Hua, LU Teng-fei, XIANG Jun. Study on the effect of CO on NO reduction in coal coke under O₂/CO₂ atmosphere[J]. J Eng Thermo, 2012,33(2):336-338.
21. [21]
  WEI Shuai, YAN Guo-chao, ZHANG Zhi-qiang, LIU Meng-song, ZHANG Yuan-fang. Analysis of molecular structure characteristics of Jincheng Anthracite[J]. J China Coal Soc, 2018,43(2):555-562.
22. [22]
  ZOU Chan, WANG Chun-bo, XING Jia-ying. Reaction mechanism of arsenic and nitrous oxides during coal combustion[J]. J Fuel Chem Technol, 2019,47(2):138-143.
23. [23]
  SINGLA P, SINGHAL S, GOEL N. Theoretical study on adsorption and dissociation of NO₂ molecules on BNNT surface[J]. Appl Surf Sci, 2013,283:881-887. doi: 10.1016/j.apsusc.2013.07.038
24. [24]
  SHENG C. Char structure characterised by Raman spectroscopy and its correlations with combustion reactivity[J]. Fuel, 2007,86(15):2316-2324. doi: 10.1016/j.fuel.2007.01.029
25. [25]
  ENOKI T, FUJⅡ S, TAKAI K. Zigzag and armchair edges in graphene[J]. Carbon, 2012,50(9):3141-3145. doi: 10.1016/j.carbon.2011.10.004
26. [26]
  GIRITÇÖ , MEYER J C, ERNI R, ROSSELL M D, KISIELOWSKI C, YANG L, PARK C, CROMMIE M F, COHEN M L, LOUIE S G, ZETTL A. Graphene at the edge:Stability and dynamics[J]. Science, 2009,323(5922):1705-1708. doi: 10.1126/science.1166999
27. [27]
  JIAO A, ZHANG H, LIU J, JIANG X. Quantum chemical and kinetics calculations for the NO reduction with char(N):Influence of the carbon monoxide[J]. Combust Flame, 2018,196:377-385. doi: 10.1016/j.combustflame.2018.06.029
28. [28]
  YU Yue-xi, GAO Zheng-yang, JI Peng, LI Fang-yong, YANG Wei-jie. Reaction mechanism of heterogeneous reduction of N₂O from coal coke[J]. CIESC J, 2017,68(1):369-374.
29. [29]
  CHEN N, YANG R T. Ab initio molecular orbital calculation on graphite:Selection of molecular system and model chemistry[J]. Carbon, 1998,36(7):1061-1070.
30. [30]
  YANG F H, YANG R T. Ab initio molecular orbital study of adsorption of atomic hydrogen on graphite:Insight into hydrogen storage in carbon nanotubes[J]. Carbon, 2002,40(3):437-444. doi: 10.1016/S0008-6223(01)00199-3
31. [31]
  GAO Z, YANG W, DING X, DING Y, YAN W. Theoretical research on heterogeneous reduction of N₂O by char[J]. App Thermal Eng, 2017,126:28-36. doi: 10.1016/j.applthermaleng.2017.07.166
32. [32]
  JIAO A, ZHANG H, LIU J, SHEN J, JIANG X. The role of CO played in the nitric oxide heterogeneous reduction:A quantum chemistry study[J]. Energy, 2017,141:1538-1546. doi: 10.1016/j.energy.2017.11.115
33. [33]
  ZHAO Y, TRUHLAR D G. The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements:Two new functionals and systematic testing of four M06 functionals and 12 other functionals[J]. Theor Chem Acc, 2008,119(5/6)525.
34. [34]
  ZHAO Y, TRUHLAR D G. A Prototype for graphene material simulation:Structures and interaction potentials of coronene dimers[J]. J Phys Chem C, 2008,112(11):4061-4067. doi: 10.1021/jp710918f
35. [35]
  GAO Zheng-yang, YANG Wei-jie, YAN Wei-ping. Reaction mechanism of coal coke catalyzing HCN reduction[J]. J Fuel Chem Technol, 2017,45(9):1043-1048.
36. [36]
  J F M, W T G, B S H, E S G, A R M, et al. Revision A.03[CP]. Wallingford CT: Gaussian, Inc., 2016.
37. [37]
  ZHANG H, LIU J, SHEN J, JIANG X. Thermodynamic and kinetic evaluation of the reaction between NO (nitric oxide) and char(N) (char bound nitrogen) in coal combustion[J]. Energy, 2015,82:312-321. doi: 10.1016/j.energy.2015.01.040
38. [38]
  XU Zi-yang, YUE Shuang, WANG Chun-bo, LIU Rui-qi. Study on the reaction mechanism of NO reduction with CO catalyzed by char[J]. J Fuel Chem Technol, 2020,48(3):266-274.
39. [39]
  ZHONG Jun, GAO Zheng-yang, DING Yi, YU Yue-xi, YANG Wei-jie. Heterogeneous reduction of N₂O reaction on Zigzag coal char surface[J]. J China Coal Soc, 2017,42(11):3028-3034.
40. [40]
  CHEN P, GU M, CHEN G, LIU F, LIN Y. DFT study on the reaction mechanism of N₂O reduction with CO catalyzed by char[J]. Fuel, 2019,254115666. doi: 10.1016/j.fuel.2019.115666
41. [41]
  WANG Peng-qian, WANG Chang-an, DU Yong-bo, ZHANG Long-fei, CHE De-fu. Experimental study on NO₂ reduction characteristics under O₂/CO₂ combustion conditions[J]. J Xi'an Jiaotong Univ, 2017,51(5):16-22.
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Reaction mechanism of heterogeneous reduction of NO2 on carbonaceous surface

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Reaction mechanism of heterogeneous reduction of NO₂ on carbonaceous surface