Journal of Molecular Modeling

, 25:364 | Cite as

Theoretical study on simultaneous removal of SO2, NO, and Hg0 over graphene: competitive adsorption and adsorption type change

  • Xiaomin Zhao
  • Kai Li
  • Ping Ning
  • Chi Wang
  • Xin Sun
  • Yixing Ma
  • Xin SongEmail author
  • Lijuan JiaEmail author
  • Xingguang Hao
Original Paper


In this work, the influence of competitive adsorption and the change of charge transfer for simultaneous adsorption removal of SO2, NO, and Hg0 over graphene were investigated using density functional theory method. The results showed that all the adsorptive effect of SO2, NO, and Hg0 were caused by physical interaction. The adsorptive energy of SO2 was the highest, and the adsorptive energy of Hg0 was the lowest. SO2 could be preferentially adsorbed and removed. NO/SO2 and Hg0 had the mutual promotion effect for simultaneous adsorption over graphene surface. SO2 and NO had the mutual inhibition effect for simultaneous adsorption over graphene surface. Compared with single molecular adsorption, the adsorption type of bi-molecular adsorption did not change. However, the simultaneous adsorption changed the adsorption type of Hg0 + SO2 + NO to chemical adsorption due to the interaction among Hg0, SO2, and NO. As such, this study provides a theoretical insight for future application and development.

Graphical abstract

NO/SO2 and Hg0 had the mutual promotion effect for simultaneous adsorption. SO2 and NO had the mutual inhibition effect for simultaneous adsorption.


Density functional theory SO2 NO and Hg0 Graphene Competitive adsorption Adsorption type 


Funding information

This work was supported by National Natural Science Foundation of China (51568067, 21667015, 41807373 and 51708266), Applied Basic Research Fund Project of Yunnan Province (2016FB100), National Key R&D Program of China (2018YFC0213400) and the Analysis and Testing Foundation of Kunming University of Science and Technology.


  1. 1.
    Yang S, Wang D, Liu H, Liu C, Xie X, Xu Z, Liu Z (2019) Highly stable activated carbon composite material to selectively capture gas-phase elemental mercury from smelting flue gas: copper polysulfide modification. Chem. Eng. J. 358:1235–1242CrossRefGoogle Scholar
  2. 2.
    Quan Z, Huang W, Liao Y, Liu W, Xu H, Yan N, Qu Z (2019) Study on the regenerable sulfur-resistant sorbent for mercury removal from nonferrous metal smelting flue gas. Fuel 241:451–458CrossRefGoogle Scholar
  3. 3.
    Liu W, Xu H, Liao Y, Quan Z, Li S, Zhao S, Qu Z, Yan N (2019) Recyclable CuS sorbent with large mercury adsorption capacity in the presence of SO2 from non-ferrous metal smelting flue gas. Fuel 235:847–854CrossRefGoogle Scholar
  4. 4.
    Sun Y, Ren S, Hou Y, Zhang K, Wu W (2018) Absorption of nitric oxide in simulated flue gas by a metallic functional ionic liquid. Fuel Process. Technol. 178:7–12CrossRefGoogle Scholar
  5. 5.
    Díaz-de-Mera Y, Aranda A, Martínez E, Rodríguez AA, Rodríguez D, Rodríguez A (2017) Formation of secondary aerosols from the ozonolysis of styrene: effect of SO2 and H2O. Atmos. Environ. 171:25–31CrossRefGoogle Scholar
  6. 6.
    Nava Núñez MY, Martínez-de la Cruz A (2018) Nitric oxide removal by action of ZnO photocatalyst hydrothermally synthesized in presence of EDTA. Mat Sci Semicon Proc 81:94–101CrossRefGoogle Scholar
  7. 7.
    He F, Deng X, Chen M (2017) Nitric oxide removal by combined urea and FeIIEDTA reaction systems. Chemosphere 168:623–629CrossRefGoogle Scholar
  8. 8.
    Zhou J, Cao L, Wang Q, Tariq M, Xue Y, Zhou Z, Sun W, Yang J (2019) Enhanced Hg0 removal via α-MnO2 anchored to MIL-96(Al). Appl. Surf. Sci. 483:252–259CrossRefGoogle Scholar
  9. 9.
    Liu Z, Adewuyi YG, Shi S, Chen H, Li Y, Liu D, Liu Y (2019) Removal of gaseous Hg0 using novel seaweed biomass-based activated carbon. Chem. Eng. J. 366:41–49CrossRefGoogle Scholar
  10. 10.
    Yu X, Hao J, Xi Z, Liu T, Lin Y, Xu B (2019) Investigation of low concentration SO2 adsorption performance on different amine-modified Merrifield resins. Atmos Pollut Res 10:404–411CrossRefGoogle Scholar
  11. 11.
    Chinh ND, Hien TT, Do Van L, Hieu NM, Quang ND, Lee SM, Kim C, Kim D (2019) Adsorption/desorption kinetics of nitric oxide on zinc oxide nano film sensor enhanced by light irradiation and gold-nanoparticles decoration. Sensors Actuat B 281:262–272CrossRefGoogle Scholar
  12. 12.
    Luo J, Niu Q, Jin M, Cao Y, Ye L, Du R (2019) Study on the effects of oxygen-containing functional groups on Hg0 adsorption in simulated flue gas by XAFS and XPS analysis. J. Hazard. Mater. 376:21–28CrossRefGoogle Scholar
  13. 13.
    Yang Y, Xu W, Wang J, Zhu T (2019) New insight into simultaneous removal of NO and Hg0 on CeO2-modified V2O5/TiO2 catalyst: a new modification strategy. Fuel 249:178–187CrossRefGoogle Scholar
  14. 14.
    Fang Z, Yu X, Tu ST (2019) Catalytic oxidation of NO on activated carbons. Energy Procedia 158:2366–2371CrossRefGoogle Scholar
  15. 15.
    Qing M, Su S, Wang L, Liu L, Xu K, He L, Jun X, Hu S, Wang Y, Xiang J (2019) Getting insight into the oxidation of SO2 to SO3 over V2O5-WO3/TiO2 catalysts: reaction mechanism and effects of NO and NH3. Chem. Eng. J. 361:1215–1224CrossRefGoogle Scholar
  16. 16.
    Yang Y, Liu J, Liu F, Wang Z, Ding J, Huang H (2019) Reaction mechanism for NH3-SCR of NOx over CuMn2O4 catalyst. Chem. Eng. J. 361:578–587CrossRefGoogle Scholar
  17. 17.
    Chen L, Wang X, Cong Q, Ma H, Li S, Li W (2019) Design of a hierarchical Fe-ZSM-5@CeO2 catalyst and the enhanced performances for the selective catalytic reduction of NO with NH3. Chem. Eng. J. 369:957–967CrossRefGoogle Scholar
  18. 18.
    Kwon DW, Kim J, Ha HP (2019) Establishment of surface/bulk-like species functionalization by controlling the sulfation temperature of Sb/V/Ce/Ti for NH3-SCR. Appl. Surf. Sci. 481:1503–1514CrossRefGoogle Scholar
  19. 19.
    Liu Y, Liu Z, Wang Y, Yin Y, Pan J, Zhang J, Wang Q (2018) Simultaneous absorption of SO2 and NO from flue gas using ultrasound/Fe2+/heat coactivated persulfate system. J. Hazard. Mater. 342:326–334CrossRefGoogle Scholar
  20. 20.
    Wu Q, Sun C, Wang H, Wang T, Wang Y, Wu Z (2018) The role and mechanism of triethanolamine in simultaneous absorption of NOx and SO2 by magnesia slurry combined with ozone gas-phase oxidation. Chem. Eng. J. 341:157–163CrossRefGoogle Scholar
  21. 21.
    Hao R, Mao Y, Mao X, Wang Z, Gong Y, Zhang Z, Zhao Y (2019) Cooperative removal of SO2 and NO by using a method of UV-heat/H2O2 oxidation combined with NH4OH-(NH4)2SO3 dual-area absorption. Chem. Eng. J. 365:282–290CrossRefGoogle Scholar
  22. 22.
    Wang H, You C (2018) Photocatalytic oxidation of SO2 on TiO2 and the catalyst deactivation: a kinetic study. Chem. Eng. J. 350:268–277CrossRefGoogle Scholar
  23. 23.
    Wang H, You C, Tan Z (2018) Enhanced photocatalytic oxidation of SO2 on TiO2 surface by Na2CO3 modification. Chem. Eng. J. 350:89–99CrossRefGoogle Scholar
  24. 24.
    Zhang AC, Zhang ZH, Shi JM, Chen GY, Zhou CS, Sun LS (2015) Effect of preparation methods on the performance of MnOx-TiO2 adsorbents for Hg0 removal and SO2 resistance. J. Fuel Chem. Technol. 43:1258–1266CrossRefGoogle Scholar
  25. 25.
    Gao L, Li C, Li S, Zhang W, Du X, Huang L, Zhu Y, Zhai Y, Zeng G (2019) Superior performance and resistance to SO2 and H2O over CoOx-modified MnOx/biomass activated carbons for simultaneous Hg0 and NO removal. Chem. Eng. J. 371:781–795CrossRefGoogle Scholar
  26. 26.
    Chiu CH, Kuo TH, Chang TC, Lin SF, Lin HP, Hsi HC (2017) Multipollutant removal of Hg0/SO2/NO from simulated coal-combustion flue gases using metal oxide/mesoporous SiO2 composites. Int. J. Coal Geol. 170:60–68CrossRefGoogle Scholar
  27. 27.
    Li B, Ma C (2018) Study on the mechanism of SO2 removal by activated carbon. Energy Procedia 153:471–477CrossRefGoogle Scholar
  28. 28.
    Wang Z, Jin H, Wang K, Xie Y, Ning J, Tu Y, Chen Y, Liu H, Zeng H (2019) A two-step method for the integrated removal of HCl, SO2 and NO at low temperature using viscose-based activated carbon fibers modified by nitric acid. Fuel 239:272–281CrossRefGoogle Scholar
  29. 29.
    Delley B (1990) An all-electron numerical method for solving the local density functional for polyatomic molecules. J. Chem. Phys. 92:508–517CrossRefGoogle Scholar
  30. 30.
    Song X, Ning P, Li K, Sun X, Wang C, Sun L (2018) Hydrogen transfer effect and reaction mechanism for catalytic hydrolysis of HCN in ionic liquids: a density functional theory study. Chem. Eng. J. 348:630–636CrossRefGoogle Scholar
  31. 31.
    Song X, Ning P, Wang C, Li K, Tang L, Sun X (2017) Catalytic hydrolysis of COS over CeO2 (110) surface: a density functional theory study. Appl. Surf. Sci. 414:345–352CrossRefGoogle Scholar
  32. 32.
    Perdew JP, Burke K, Ernzerhof M (1996) Generalized gradient approximation made simple. Phys. Rev. Lett. 77:3865–3868CrossRefGoogle Scholar
  33. 33.
    Delley B (2000) From molecules to solids with the DMol3 approach. J. Chem. Phys. 113:7756–7764CrossRefGoogle Scholar
  34. 34.
    Song X, Wang C, Gasem KAM, Li K, Sun X, Ning P, Gong W, Wang T, Fan M, Sun L (2019) New insight into the reaction mechanism of carbon disulfide hydrolysis and the impact of H2S with density functional modeling. New J. Chem. 43:2347–2352CrossRefGoogle Scholar
  35. 35.
    Li K, Song X, Zhu T, Wang C, Sun X, Ning P, Tang L (2018) Mechanistic and kinetic study on the catalytic hydrolysis of COS in small clusters of sulfuric acid. Environ. Pollut. 232:615–623CrossRefGoogle Scholar
  36. 36.
    Song X, Sun L, Ning P, Wang C, Sun X, Li K, Fan M (2019) Catalytic synthesis of non-carbon fuel NH3 from easily available N2 and H2O over FeO(100) surface: study of reaction mechanism using the density functional theory. New J. Chem. 43:10066–10072CrossRefGoogle Scholar
  37. 37.
    Song X, Sun L, Guo H, Li K, Sun X, Wang C, Ning P (2019) Experimental and theoretical studies on the influence of carrier gas for COS catalytic hydrolysis over MgAlCe composite oxides. ACS Omega 4:7122–7127CrossRefGoogle Scholar
  38. 38.
    Ning P, Song X, Li K, Wang C, Tang L, Sun X (2017) Catalytic hydrolysis of carbonyl sulphide and carbon disulphide over Fe2O3 cluster: competitive adsorption and reaction mechanism. Sci. Rep. 7:14452CrossRefGoogle Scholar
  39. 39.
    Cottrell TL (1958) The strengths of chemical bondssecond edn. Butterworths Scientific Publications, LondonGoogle Scholar
  40. 40.
    U.S. Dept. of Commerce (1970) National standard reference data series. National Bureau of Standards, WashingtonGoogle Scholar
  41. 41.
    Abbasi A, Sardroodi JJ (2019) Adsorption of O3, SO2 and SO3 gas molecules on MoS2 monolayers: a computational investigation. Appl. Surf. Sci. 469:781–791Google Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Faculty of Environmental Science and EngineeringKunming University of Science and TechnologyKunmingChina
  2. 2.National-Regional Engineering Center for Recovery of Waste Gases from, Metallurgical and Chemical IndustriesKunming University of Science and TechnologyKunmingPeople’s Republic of China
  3. 3.Faculty of Chemical EngineeringKunming University of Science and TechnologyKunmingChina
  4. 4.School of Chemistry and EnvironmentYunnan Minzu UniversityKunmingChina

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