Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Article
  • Published:

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

Abstract

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.

This is a preview of subscription content, access via your institution

Access options

Rent or buy this article

Prices vary by article type

from$1.95

to$39.95

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: Structural characterization of Co4N nanosheets.
Fig. 2: Catalytic performance of Co4N in the hydrogenation of CO2.
Fig. 3: The formation of Co4NH x from Co4N under H2 atmosphere.
Fig. 4: Mechanistic studies of the catalytic activity of Co4N nanosheets in CO2 hydrogenation.

Similar content being viewed by others

References

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

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

    Article  Google Scholar 

  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. 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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

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

  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).

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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. 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).

    Article  Google Scholar 

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

Download references

Acknowledgements

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

Authors and Affiliations

Authors

Contributions

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.

Corresponding author

Correspondence to Jie Zeng.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Additional information

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

Electronic supplementary material

Supplementary Information

Supplementary Figures 1–28, Supplementary Tables 1 and 2

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Wang, L., Zhang, W., Zheng, X. et al. Incorporating nitrogen atoms into cobalt nanosheets as a strategy to boost catalytic activity toward CO2 hydrogenation. Nat Energy 2, 869–876 (2017). https://doi.org/10.1038/s41560-017-0015-x

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41560-017-0015-x

This article is cited by

Search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing