Article | Published:

Incorporating nitrogen atoms into cobalt nanosheets as a strategy to boost catalytic activity toward CO2 hydrogenation

Nature Energyvolume 2pages869876 (2017) | Download Citation


Hydrogenation of CO2 into fuels and useful chemicals could help to reduce reliance on fossil fuels. Although great progress has been made over the past decades to improve the activity of catalysts for CO2 hydrogenation, more efficient catalysts, especially those based on non-noble metals, are desired. Here we incorporate N atoms into Co nanosheets to boost the catalytic activity toward CO2 hydrogenation. For the hydrogenation of CO2, Co4N nanosheets exhibited a turnover frequency of 25.6 h−1 in a slurry reactor under 32 bar pressure at 150 °C, which was 64 times that of Co nanosheets. The activation energy for Co4N nanosheets was 43.3 kJ mol−1, less than half of that for Co nanosheets. Mechanistic studies revealed that Co4N nanosheets were reconstructed into Co4NH x , wherein the amido-hydrogen atoms directly interacted with the CO2 to form HCOO* intermediates. In addition, the adsorbed H2O* activated amido-hydrogen atoms via the interaction of hydrogen bonds.

Access optionsAccess options

Rent or Buy article

Get time limited or full article access on ReadCube.


All prices are NET prices.

Additional information

Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.


  1. 1.

    Behrens, M. et al. The active site of methanol synthesis over Cu/ZnO/Al2O3 industrial catalysts. Science 336, 893–897 (2012).

  2. 2.

    Chinchen, G. C., Denny, P. J., Parker, D. G., Spencer, M. S. & Whan, D. A. Mechanism of methanol synthesis from CO2/CO/H2 mixtures over copper/zinc oxide/alumina catalysts: use of 14C-labelled reactants. Appl. Catal. 30, 333–338 (1987).

  3. 3.

    Spencer, M. S. The role of zinc oxide in Cu/ZnO catalysts for methanol synthesis and the water-gas shift reaction. Top. Catal. 8, 259–266 (1999).

  4. 4.

    Kuld, S. et al. Quantifying the promotion of Cu catalysts by ZnO for methanol synthesis. Science 352, 969–974 (2016).

  5. 5.

    Preti, D., Resta, C., Squarcialupi, S. & Fachinetti, G. Carbon dioxide hydrogenation to formic acid by using a heterogeneous gold catalyst. Angew. Chem. Int. Ed. 50, 12551–12554 (2011).

  6. 6.

    Moret, S., Dyson, P. J. & Laurenczy, G. Direct synthesis of formic acid from carbon dioxide by hydrogenation in acidic media. Nat. Commun. 5, 4017 (2014).

  7. 7.

    Schneidewind, J., Adam, R., Baumann, W., Jackstell, R. & Beller, M. Low-temperature hydrogenation of carbon dioxide to methanol with a homogeneous cobalt catalyst. Angew. Chem. Int. Ed. 56, 1890–1893 (2017).

  8. 8.

    Rezayee, N. M., Huff, C. A. & Sanford, M. S. Tandem amine and ruthenium-catalyzed hydrogenation of CO2 to methanol. J. Am. Chem. Soc. 137, 1028–1031 (2015).

  9. 9.

    Khan, M. U. et al. Pt3Co octapods as superior catalysts of CO2 hydrogenation. Angew. Chem. Int. Ed. 55, 9548–9552 (2016).

  10. 10.

    Zhang, W. et al. Integration of quantum confinement and alloy effect to modulate electronic properties of RhW nanocrystals for improved catalytic performance toward CO2 hydrogenation. Nano. Lett. 17, 788–793 (2017).

  11. 11.

    Yang, X. et al. Low pressure CO2 hydrogenation to methanol over gold nanoparticles activated on a CeOx/TiO2 interface. J. Am. Chem. Soc. 137, 10104–10107 (2015).

  12. 12.

    Liao, F. et al. Electronic modulation of a copper/zinc oxide catalyst by a heterojunction for selective hydrogenation of carbon dioxide to methanol. Angew. Chem. Int. Ed. 51, 5832–5836 (2012).

  13. 13.

    Matsubu, J. C., Yang, V. N. & Christopher, P. Isolated metal active site concentration and stability control catalytic CO2 reduction selectivity. J. Am. Chem. Soc. 137, 3076–3084 (2015).

  14. 14.

    Iablokov, V. et al. Size-controlled model co nanoparticle catalysts for CO2 hydrogenation: synthesis, characterization, and catalytic reactions. Nano Lett. 12, 3091–3096 (2012).

  15. 15.

    Calaza, F. et al. Carbon dioxide activation and reaction induced by electron transfer at an oxide-metal interface. Angew. Chem. Int. Ed. 54, 12484–12487 (2015).

  16. 16.

    He, Z. et al. Water-enhanced synthesis of higher alcohols from CO2 hydrogenation over a Pt/Co3O4 catalyst under milder conditions. Angew. Chem. Int. Ed. 55, 737–741 (2016).

  17. 17.

    Liu, C. et al. Carbon dioxide conversion to methanol over size-selected Cu4 clusters at low pressures. J. Am. Chem. Soc. 137, 8676–8679 (2015).

  18. 18.

    Wang, F. et al. Active site dependent reaction mechanism over Ru/CeO2 catalyst toward CO2 methanation. J. Am. Chem. Soc. 138, 6298–6305 (2016).

  19. 19.

    Matsubu, J. C. et al. Adsorbate-mediated strong metal-support interactions in oxide-supported Rh catalysts. Nat. Chem. 9, 120–127 (2017).

  20. 20.

    Li, C. S. et al. High-performance hybrid oxide catalyst of manganese and cobalt for low-pressure methanol synthesis. Nat. Commun. 6, 6538 (2015).

  21. 21.

    Graciani, J. et al. Highly active copper-ceria and copper-ceria-titania catalysts for methanol synthesis from CO2. Science 345, 546–550 (2014).

  22. 22.

    Li, Y., Chan, S. H. & Sun, Q. Heterogeneous catalytic conversion of CO2: a comprehensive theoretical review. Nanoscale 7, 8663–8683 (2015).

  23. 23.

    Studt, F. et al. Discovery of a Ni-Ga Catalyst for carbon dioxide reduction to methanol. Nat. Chem. 6, 320–324 (2014).

  24. 24.

    Nam, K. M. et al. Single-crystalline hollow face-centered-cubic cobalt nanoparticles from solid face-centered-cubic cobalt oxide nanoparticles. Angew. Chem. Int. Ed. 47, 9504–9508 (2008).

  25. 25.

    Oda, K., Yoshio, T. & Oda, K. Preparation of Co-N films by RF-sputtering. J. Mater. Sci. 22, 2729–2733 (1987).

  26. 26.

    Pozzo, M. & Alfe, D. Hydrogen dissociation and diffusion on transition metal (=Ti, Zr, V, Fe, Ru, Co, Rh, Ni, Pd, Cu, Ag)-doped Mg(0001) surfaces. Int. J. Hydrogen Energy 34, 1922–1930 (2009).

  27. 27.

    Gomez, T., Florez, E., Rodriguez, J. A. & Illas, F. Reactivity of transition metals (Pd, Pt, Cu, Ag, Au) toward molecular hydrogen dissociation: extended surfaces versus particles supported on TiC(001) or small is not always better and large is not always bad. J. Phys. Chem. C 115, 11666–11672 (2011).

  28. 28.

    Rodriguez, J. A. et al. Hydrogenation of CO2 to methanol: importance of metal-oxide and metal-carbide interfaces in the activation of CO2.ACS Catal. 5, 6696–6706 (2015).

  29. 29.

    Bai, S. et al. Highly active and selective hydrogenation of CO2 to ethanol by ordered Pd-Cu nanoparticles. J. Am. Chem. Soc. 139, 6827–6830 (2017).

  30. 30.

    Rasko, J., Kecskes, T. & Kiss, J. Adsorption and reaction of formaldehyde on TiO2-supported Rh catalysts studied by FTIR and mass spectrometry. J. Catal. 226, 183–191 (2004).

  31. 31.

    Sun, S. et al. Photocatalytic oxidation of gaseous formaldehyde on TiO2: an in-situ DRIFTS study. Catal. Lett. 137, 239–246 (2010).

  32. 32.

    Huang, Q. W., Zeng, D. W., Li, H. Y. & Xie, C. S. room temperature formaldehyde sensors with enhanced performance, fast response and recovery based on zinc oxide quantum dots/graphene nanocomposites. Nanoscale 4, 5651–5658 (2012).

  33. 33.

    Toth, M. et al. Hydrogenation of carbon dioxide on Rh, Au and Au-Rh bimetallic clusters supported on titanate nanotubes, nanowires and TiO2. Top. Catal. 55, 747–756 (2012).

  34. 34.

    Yang, R. Q., Fu, Y. L., Zhang, Y. & Tsubaki, N. In situ DRIFT study of low-temperature methanol synthesis mechanism on Cu/ZnO catalysts from co2-containing syngas using ethanol promoter. J. Catal. 228, 23–35 (2004).

  35. 35.

    Korhonen, S. T., Banares, M. A., Fierro, J. L. G. & Krause, A. O. I. Adsorption of methanol as a probe for surface characteristics of zirconia-, alumina-, and zirconia/alumina-supported chromia catalysts. Catal. Today 126, 235–247 (2007).

  36. 36.

    Kahler, K., Holz, M. C., Rohe, M., Strunk, J. & Muhler, M. Probing the reactivity of ZnO and Au/ZnO nanoparticles by methanol adsorption: a TPD and DRIFTS study. ChemPhysChem 11, 2521–2529 (2010).

  37. 37.

    Jacobs, G. & Davis, B. H. In situ DRIFTS investigation of the steam reforming of methanol over Pt/ceria. Appl. Catal. A-Gen. 285, 43–49 (2005).

  38. 38.

    Lin, S. D., Cheng, H. K. & Hsiao, T. C. In situ DRIFTS study on the methanol oxidation by lattice oxygen over Cu/ZnO catalyst. J. Mol. Catal. A-Chem. 342, 35–40 (2011).

  39. 39.

    Flores-Escamilla, G. A. & Fierro-Gonzalez, J. C. Participation of linear methoxy species bonded to Ti4+ sites in the methanol carbonylation catalyzed by TiO2-supported rhodium: an infrared investigation. J. Mol. Catal. A-Chem. 359, 49–56 (2012).

Download references


This work was supported by the Collaborative Innovation Center of Suzhou Nano Science and Technology, MOST of China (2014CB932700), NSFC (21573206 and 51371164), Key Research Program of Frontier Sciences of the CAS (QYZDB-SSW-SLH017), Anhui Provincial Key Scientific and Technological Project (1704a0902013), and Fundamental Research Funds for the Central Universities.

Author information

Author notes

  1. Liangbing Wang, Wenbo Zhang and Xusheng Zheng contributed equally to this work.


  1. Hefei National Laboratory for Physical Sciences at the Microscale, Key Laboratory of Strongly-Coupled Quantum Matter Physics of Chinese Academy of Sciences, National Synchrotron Radiation Laboratory, Department of Chemical Physics, University of Science and Technology of China, Hefei, Anhui, 230026, China

    • Liangbing Wang
    • , Wenbo Zhang
    • , Xusheng Zheng
    • , Yizhen Chen
    • , Wenlong Wu
    • , Jianxiang Qiu
    • , Xiangchen Zhao
    • , Xiao Zhao
    • , Yizhou Dai
    •  & Jie Zeng


  1. Search for Liangbing Wang in:

  2. Search for Wenbo Zhang in:

  3. Search for Xusheng Zheng in:

  4. Search for Yizhen Chen in:

  5. Search for Wenlong Wu in:

  6. Search for Jianxiang Qiu in:

  7. Search for Xiangchen Zhao in:

  8. Search for Xiao Zhao in:

  9. Search for Yizhou Dai in:

  10. Search for Jie Zeng in:


L.W., W.Z. and X. Zheng equally contributed to this work. L.W. and J.Z. designed the studies and wrote the paper. L.W., W.Z., and Y.C. synthesized catalysts. L.W., W.Z., W.W. and J.Q. performed catalytic tests. L.W., Xiangchen Zhao, Xiao Zhao and Y.D. conducted in situ DRIFT, XRD, solid-state D-NMR and isotope measurements. L.W. and Xus.Z. conducted quasi in situ XPS measurements. All authors discussed the results and commented on the manuscript.

Competing interests

The authors declare no competing financial interests.

Corresponding author

Correspondence to Jie Zeng.

Electronic supplementary material

  1. Supplementary Information

    Supplementary Figures 1–28, Supplementary Tables 1 and 2

About this article

Publication history