Cooperation Between Active Metal and Basic Support in Ni-Based Catalyst for Low-Temperature CO2 Methanation

  • Yuan Ma
  • Jiao LiuEmail author
  • Mo Chu
  • Junrong Yue
  • Yanbin Cui
  • Guangwen Xu


The key challenge for CO2 methanation, an eight-electron process under kinetic limitation, relies on the design of non-noble metal catalysts so as to achieve high activity at low reaction temperatures. In this work, four Ni-based catalysts with different supports were prepared and tested for CO2 methanation at 250–550 °C in a fixed bed quartz reactor and further characterized to reveal the structure–function relationship. The Ni-based catalysts followed an activity order of Ni/CeO2 > Ni/Al2O3 > Ni/TiO2 > Ni/ZrO2, especially at temperatures lower than 350 °C. H2-TPR and TPD results indicated that the interaction between nickel and support was strong and the metallic nickel was well dispersed in the Ni/Al2O3 catalyst, while more amount of CO2 was adsorbed on the weak basic sites in the Ni/CeO2 catalyst. By establishing the correlation between the catalytic performance and the catalyst structure, it was found that the Ni nanoparticles and basic support serve as H2 and CO2 active centers respectively and cooperatively catalyze CO2 methanation, resulting in high low-temperature reaction activity.

Graphic Abstract

High CO2 conversion was achieved over Ni/CeO2 catalyst at 300 °C for its high H2 uptake on Ni nanoparticles and high CO2 adsorption capacity on the support with weak basic sites and cooperatively to catalyze CO2 methanation.


CO2 methanation Ni/CeO2 Catalyst Support Basic site TPD 



This work was supported by the Fund of State Key Laboratory of Multiphase Complex Systems (No. MPCS-2019-A-04) and International Science and Technology Cooperation Program of China (2018YFE010340).

Competing interest

There have no competing interest.


  1. 1.
    Zhen W, Gao F, Tian B et al (2017) Enhancing activity for carbon dioxide methanation by encapsulating (111) facet Ni particle in metal–organic frameworks at low temperature. J Catal 348:200–211. CrossRefGoogle Scholar
  2. 2.
    Younas M, Loong Kong L, Bashir MJK et al (2016) Recent advancements, fundamental challenges, and opportunities in catalytic methanation of CO2. Energy Fuel 30:8815–8831. CrossRefGoogle Scholar
  3. 3.
    Li W, Zhang A, Jiang X et al (2017) Low temperature CO2 methanation: ZIF-67-derived co-based porous carbon catalysts with controlled crystal morphology and size. ACS Sustain Chem Eng 5:7824–7831. CrossRefGoogle Scholar
  4. 4.
    Danaci S, Protasova L, Lefevere J et al (2016) Efficient CO2 methanation over Ni/Al2O3 coated structured catalysts. Catal Today 273:234–243. CrossRefGoogle Scholar
  5. 5.
    Muroyama H, Tsuda Y, Asakoshi T et al (2016) Carbon dioxide methanation over Ni catalysts supported on various metal oxides. J Catal 343:178–184. CrossRefGoogle Scholar
  6. 6.
    Beuls A, Swalus C, Jacquemin M et al (2012) Methanation of CO2: further insight into the mechanism over Rh/γ-Al2O3 catalyst. Appl Catal B Environ 113–114:2–10. CrossRefGoogle Scholar
  7. 7.
    Lin Q, Liu XY, Jiang Y et al (2014) Crystal phase effects on the structure and performance of ruthenium nanoparticles for CO2 hydrogenation. Catal Sci Technol 4:2058–2063. CrossRefGoogle Scholar
  8. 8.
    Karelovic A, Ruiz P (2012) CO2 hydrogenation at low temperature over Rh/γ-Al2O3 catalysts: effect of the metal particle size on catalytic performances and reaction mechanism. Appl Catal B Environ 113–114:237–249. CrossRefGoogle Scholar
  9. 9.
    Mutz B, Sprenger P, Wang W et al (2018) Operando Raman spectroscopy on CO2 methanation over alumina-supported Ni, Ni3Fe and NiRh0.1 catalysts: role of carbon formation as possible deactivation pathway. Appl Catal A Gen 556:160–171. CrossRefGoogle Scholar
  10. 10.
    Xu L, Lian X, Chen M et al (2018) CO2 methanation over Co Ni bimetal-doped ordered mesoporous Al2O3 catalysts with enhanced low-temperature activities. Int J Hydrog Energy 43:17172–17184. CrossRefGoogle Scholar
  11. 11.
    Pan Q, Peng J, Sun T et al (2014) Insight into the reaction route of CO2 methanation: promotion effect of medium basic sites. Catal Commun 45:74–78. CrossRefGoogle Scholar
  12. 12.
    Ma S, Tan Y, Han Y (2011) Methanation of syngas over coral reef-like Ni/Al2O3 catalysts. J Nat Gas Chem 20:435–440. CrossRefGoogle Scholar
  13. 13.
    Jia X, Zhang X, Rui N et al (2019) Structural effect of Ni/ZrO2 catalyst on CO2 methanation with enhanced activity. Appl Catal B Environ 244:159–169. CrossRefGoogle Scholar
  14. 14.
    Tada S, Shimizu T, Kameyama H et al (2012) Ni/CeO2 catalysts with high CO2 methanation activity and high CH4 selectivity at low temperatures. Int J Hydrog Energy 37:527–5531. CrossRefGoogle Scholar
  15. 15.
    Liu J, Li C, Wang F et al (2013) Enhanced low-temperature activity of CO2 methanation over highly-dispersed Ni/TiO2 catalyst. Catal Sci Technol 3:2627–2633. CrossRefGoogle Scholar
  16. 16.
    He L, Lin Q, Liu Y et al (2014) Unique catalysis of Ni-Al hydrotalcite derived catalyst in CO2 methanation: cooperative effect between Ni nanoparticles and a basic support. Energy Chem 23:587–592. CrossRefGoogle Scholar
  17. 17.
    Vogt C, Groeneveld E, Kamsma G et al (2018) Unravelling structure sensitivity in CO2 hydrogenation over nickel. Nat Catal 1:127–134. CrossRefGoogle Scholar
  18. 18.
    Aldana PAU, Ocampo F, Kobl K et al (2013) Catalytic CO2 valorization into CH4 on Ni-based ceria-zirconia. Reaction mechanism by operando IR spectroscopy. Catal Today 215:201–207. CrossRefGoogle Scholar
  19. 19.
    Lin J, Ma C, Wang Q et al (2019) Enhanced low-temperature performance of CO2 methanation over mesoporous Ni/Al2O3-ZrO2 catalysts. Appl Catal B Environ 243:262–272. CrossRefGoogle Scholar
  20. 20.
    Song F, Zhong Q, Yu Y et al (2017) Obtaining well-dispersed Ni/Al2O3 catalyst for CO2 methanation with a microwave-assisted method. Int J Hydrog Energy 42:4174–4183. CrossRefGoogle Scholar
  21. 21.
    Quindimil A, De-La-Torre U, Pereda-Ayo B et al (2018) Ni catalysts with La as promoter supported over Y- and BETA- zeolites for CO2 methanation. Appl Catal B Environ 238:393–403. CrossRefGoogle Scholar
  22. 22.
    Park J-N, McFarland EW (2009) A highly dispersed Pd–Mg/SiO2 catalyst active for methanation of CO2. J Catal 266:92–97. CrossRefGoogle Scholar
  23. 23.
    Crespo-Quesada M, Yarulin A, Jin M et al (2011) Structure sensitivity of alkynol hydrogenation on shape- and size-controlled palladium nanocrystals: which sites are most active and selective? J Am Chem Soc 133:12787–12794. CrossRefPubMedGoogle Scholar
  24. 24.
    Hansen TW, Wagner JB, Hansen PL et al (2001) Atomic-resolution in situ transmission electron microscopy of a promoter of a heterogeneous catalyst. Science 294:1508–1510. CrossRefPubMedGoogle Scholar
  25. 25.
    Andersson MP, Abild-Pedersen F, Remediakis IN et al (2008) Structure sensitivity of the methanation reaction: H2-induced CO dissociation on nickel surfaces. J Catal 55:6–19. CrossRefGoogle Scholar
  26. 26.
    Wu HC, Chang YC, Wu JH et al (2015) Methanation of CO2 and reverse water gas shift reactions on Ni/SiO2 catalysts: the influence of particle size on selectivity and reaction pathway. Catal Sci Technol 5:4154–4163. CrossRefGoogle Scholar
  27. 27.
    Beierlein D, Schirrmeister S, Traa Y et al (2018) Experimental approach for identifying hotspots in lab-scale fixed-bed reactors exemplified by the Sabatier reaction. React Kinet Mech Catal 125:157–170. CrossRefGoogle Scholar
  28. 28.
    Vita A, Italiano C, Pino L et al (2018) Activity and stability of powder and monolith-coated Ni/GDC catalysts for CO2 methanation. Appl Catal B Environ 226:384–395. CrossRefGoogle Scholar
  29. 29.
    Stangeland K, Kalai DY, Li H et al (2018) Active and stable Ni based catalysts and processes for biogas upgrading: the effect of temperature and initial methane concentration on CO2 methanation. Appl Energy 227:206–212. CrossRefGoogle Scholar
  30. 30.
    Damyanova S, Bueno JMC (2003) Effect of CeO2 loading on the surface and catalytic behaviors of CeO2-Al2O3-supported Pt catalysts. Appl Catal A Gen 253:135–150. CrossRefGoogle Scholar
  31. 31.
    Du X, Zhang D, Shi L et al (2012) Morphology dependence of catalytic properties of Ni/CeO2 nanostructures for carbon dioxide reforming of methane. Phys Chem C 116:10009–10016. CrossRefGoogle Scholar
  32. 32.
    Zhang Z, Wei T, Chen G et al (2019) Understanding correlation of the interaction between nickel and alumina with the catalytic behaviors in steam reforming and methanation. Fuel 250:176–193. CrossRefGoogle Scholar
  33. 33.
    Cao HX, Zhang J, Ren XK et al (2017) Enhanced CO methanation over Ni-based catalyst using a support with 3D-mesopores. Korean J Chem Eng 34:2374–2382. CrossRefGoogle Scholar
  34. 34.
    Chen S, Miao C, Luo Y et al (2018) Study of catalytic hydrodeoxygenation performance of Ni catalysts: effects of prepared method. Renew Energy 115:1109–1117. CrossRefGoogle Scholar
  35. 35.
    Li H, Ren J, Qin X et al (2015) Ni/SBA-15 catalysts for CO methanation: effects of V, Ce, and Zr promoters. RSC Adv 5:96504–96517. CrossRefGoogle Scholar
  36. 36.
    Vrijburg W, van Helden J, van Hoof A et al (2019) Tunable colloidal Ni nanoparticles confined and redistributed in mesoporous silica for CO2 methanation. Catal Sci Technol 9:2578–2591. CrossRefGoogle Scholar
  37. 37.
    Liu J, Bing W, Xue X et al (2016) Alkaline-assisted Ni nanocatalysts with largely enhanced low-temperature activity toward CO2 methanation. Catal Sci Technol 6:3976–3983. CrossRefGoogle Scholar
  38. 38.
    Lee S, Lee Y, Moon D et al (2019) Reaction mechanism and catalytic impact of Ni/CeO2−x catalyst for low-temperature CO2 methanation. Ind Eng Chem Res 58:8656–8662. CrossRefGoogle Scholar
  39. 39.
    Schweke D, Zalkind S, Attia S et al (2018) The interaction of CO2 with CeO2 powder explored by correlating adsorption and thermal desorption analyses. J Phys Chem C 122:9947–9957. CrossRefGoogle Scholar
  40. 40.
    Zhou G, Liu H, Cui K et al (2017) Methanation of carbon dioxide over Ni/CeO2 catalysts: effects of support CeO2 structure. Int J Hydrog Energy 42:16108–16117CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  • Yuan Ma
    • 1
  • Jiao Liu
    • 2
    Email author
  • Mo Chu
    • 1
  • Junrong Yue
    • 2
  • Yanbin Cui
    • 2
  • Guangwen Xu
    • 3
  1. 1.School of Chemical and Environmental EngineeringChina University of Mining & Technology (Beijing)BeijingChina
  2. 2.State Key Laboratory of Multi-phase Complex Systems, Institute of Process EngineeringChinese Academy of SciencesBeijingChina
  3. 3.Institute of Industrial Chemistry and Energy TechnologyShenyang University of Chemical TechnologyShenyangChina

Personalised recommendations