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:

Dynamic coordination of cations and catalytic selectivity on zinc–chromium oxide alloys during syngas conversion

Nature Catalysis volume 2, pages 671–677 (2019)Cite this article

Subjects

Abstract

Metal oxide alloys (for example AxByOz) exhibit dramatically different catalytic properties in response to small changes in composition (the A:B ratio). Here, we show that for the ternary zinc–chromium oxide (ZnCrO) catalysts the activity and selectivity during syngas (CO/H2) conversion strongly depend on the Zn:Cr ratio. By using a global neural network potential, stochastic surface walking global optimization and first principles validation, we constructed a thermodynamics phase diagram for Zn–Cr–O that reveals the presence of a small stable composition island, that is, Zn:Cr:O = 6:6:16 to 3:8:16, where the oxide alloy crystallizes into a spinel phase. By changing the Zn:Cr ratio from 1:2 to 1:1, the ability to form oxygen vacancies increases appreciably and extends from the surface to the subsurface, in agreement with previous experiments. This leads to the critical presence of a four-coordinated planar Cr2+ cation that markedly affects the syngas conversion activity and selectivity to methanol, as further proved by microkinetics simulations.

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

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

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

Fig. 1: Thermodynamics and structures of bulk ZnCrO at different compositions.
Fig. 2: Surface structures and phase diagram for ZnCr2O4 and Zn3Cr3O8 crystals under reaction conditions.
Fig. 3: Syngas conversion mechanisms and kinetics.
Fig. 4: Energetics and electronic structure analyses of CH3O adsorption.

Similar content being viewed by others

Data availability

All the data are available within the article (and Supplementary Information) and from the corresponding authors upon reasonable request.

Code availability

The software code for LASP and the NN potentials used within the article are available from the corresponding author upon request or on the website http://www.lasphub.com.

References

  1. Kung, H. H. Methanol synthesis. Catal. Rev. Sci. Eng. 22, 235–259 (1980).

    Article  CAS  Google Scholar 

  2. Molstad, M. C. & Dodge, B. F. Zinc oxide–chromium oxide catalysts for methanol synthesis. Ind. Eng. Chem. 27, 134–140 (1935).

    Article  CAS  Google Scholar 

  3. Jiao, F. et al. Selective conversion of syngas to light olefins. Science 351, 1065–1068 (2016).

    Article  CAS  Google Scholar 

  4. Waugh, K. Methanol synthesis. Catal. Today 15, 51–75 (1992).

    Article  CAS  Google Scholar 

  5. Dumitru, R. et al. Synthesis, characterization of nanosized ZnCr2O4 and its photocatalytic performance in the degradation of humic acid from drinking water. Catalysts 8, 210 (2018).

    Article  Google Scholar 

  6. Song, H. et al. Spinel-structured ZnCr2O4 with excess Zn is the active ZnO/Cr2O3 catalyst for high-temperature methanol synthesis. ACS Catal. 7, 7610–7622 (2017).

    Article  CAS  Google Scholar 

  7. Del Piero, G., Trifiro, F. & Vaccari, A. Non-stoichiometric Zn–Cr spinel as active phase in the catalytic synthesis of methanol. J. Chem. Soc. Chem. Commun. 00, 666–658 (1984).

    Google Scholar 

  8. Bertoldi, M., Fubini, B., Giamello, E., Trifirò, F. & Vaccari, A. Structure and reactivity of zinc–chromium mixed oxides. Part 1. The role of non-stoichiometry on bulk and surface properties. J. Chem. Soc. Faraday Trans. 84, 1405–1421 (1988).

    Article  CAS  Google Scholar 

  9. Errani, E., Trifiro, F., Vaccari, A., Richter, M. & Del Piero, G. Structure and reactivity of Zn–Cr mixed oxides. Role of non-stoichiometry in the catalytic synthesis of methanol. Catal. Lett. 3, 65–72 (1989).

    Article  CAS  Google Scholar 

  10. Bradford, M. C., Konduru, M. V. & Fuentes, D. X. Preparation, characterization and application of Cr2O3/ZnO catalysts for methanol synthesis. Fuel Process. Technol. 83, 11–25 (2003).

    Article  CAS  Google Scholar 

  11. Grimes, R. W., Binks, D. J. & Lidiard, A. The extent of zinc oxide solution in zinc chromate spinel. Phil. Mag. A 72, 651–668 (1995).

    Article  CAS  Google Scholar 

  12. Shang, C. & Liu, Z.-P. Stochastic surface walking method for structure prediction and pathway searching. J. Chem. Theory Comput. 9, 1838–1845 (2013).

    Article  CAS  Google Scholar 

  13. Zhang, X.-J., Shang, C. & Liu, Z.-P. From atoms to fullerene: stochastic surface walking solution for automated structure prediction of complex material. J. Chem. Theory Comput. 9, 3252–3260 (2013).

    Article  CAS  Google Scholar 

  14. Guan, S.-H., Zhang, X.-J. & Liu, Z.-P. Energy landscape of zirconia phase transitions. J. Am. Chem. Soc. 137, 8010–8013 (2015).

    Article  CAS  Google Scholar 

  15. Zhu, S.-C., Xie, S.-H. & Liu, Z.-P. Nature of rutile nuclei in anatase-to-rutile phase transition. J. Am. Chem. Soc. 137, 11532–11539 (2015).

    Article  CAS  Google Scholar 

  16. Li, Y.-F., Zhu, S.-C. & Liu, Z.-P. Reaction network of layer-to-tunnel transition of MnO2. J. Am. Chem. Soc. 138, 5371–5379 (2016).

    Article  CAS  Google Scholar 

  17. Huang, S.-D., Shang, C., Zhang, X.-J. & Liu, Z.-P. Material discovery by combining stochastic surface walking global optimization with a neural network. Chem. Sci. 8, 6327–6337 (2017).

    Article  CAS  Google Scholar 

  18. Behler, J. Representing potential energy surfaces by high-dimensional neural network potentials. J. Phys. Condens. Matter 26, 183001–1830024 (2014).

    Article  CAS  Google Scholar 

  19. Ma, S., Huang, S.-D., Fang, Y.-H. & Liu, Z.-P. TiH hydride formed on amorphous black titania: unprecedented active species for photocatalytic hydrogen evolution. ACS Catal. 8, 9711–9721 (2018).

    Article  CAS  Google Scholar 

  20. Cheng, K. et al. Direct and highly selective conversion of synthesis gas into lower olefins: design of a bifunctional catalyst combining methanol synthesis and carbon–carbon coupling. Angew. Chem. Int. Ed. 128, 4803–4806 (2016).

    Article  Google Scholar 

  21. Riva, A., Trifirò, F., Vaccari, A. & Mintchev, L. Structure and reactivity of zinc–chromium mixed oxides. Part 2. Study of the surface reactivity by temperature-programmed desorption of methanol. J. Chem. Soc. Faraday Trans. 84, 1423–1435 (1988).

    Article  CAS  Google Scholar 

  22. Giamello, E., Fubini, B., Bertoldi, M. & Vaccari, A. Structure and reactivity of zinc–chromium mixed oxides. Part 3. The surface interaction with carbon monoxide. J. Chem. Soc. Faraday Trans. 85, 237–249 (1989).

    Article  CAS  Google Scholar 

  23. Tan, L. et al. Iso-butanol direct synthesis from syngas over the alkali metals modified Cr/ZnO catalysts. Appl. Catal. A 505, 141–149 (2015).

    Article  CAS  Google Scholar 

  24. Tian, S. et al. The role of potassium promoter in isobutanol synthesis over Zn–Cr based catalysts. Catal. Sci. Technol. 6, 4105–4115 (2016).

    Article  CAS  Google Scholar 

  25. Wang, J. et al. A highly selective and stable ZnO–ZrO2 solid solution catalyst for CO2 hydrogenation to methanol. Sci. Adv. 3, e1701290 (2017).

    Article  Google Scholar 

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

    Article  CAS  Google Scholar 

  27. Huang, S.-D. et al. LASP: Fast global potential energy surface exploration. WIREs Compt. Mol. Sci. https://doi.org/10.1002/wcms.1415 (2019).

  28. Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).

    Article  Google Scholar 

  29. Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758–1775 (1999).

    Article  CAS  Google Scholar 

  30. Yaresko, A. Electronic band structure and exchange coupling constants in ACr2X4 spinels (A = Zn, Cd, Hg; X = O, S, Se). Phys. Rev. B 77, 115106 (2008).

    Article  Google Scholar 

  31. Zhang, X.-J., Shang, C. & Liu, Z.-P. Double-ended surface walking method for pathway building and transition state location of complex reactions. J. Chem. Theory Comput. 9, 5745–5753 (2013).

    Article  CAS  Google Scholar 

  32. Zhang, X.-J. & Liu, Z.-P. Variable-cell double-ended surface walking method for fast transition state location of solid phase transitions. J. Chem. Theory Comput. 11, 4885–4894 (2015).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the National Key Research and Development Program of China (2018YFA0208600) and the National Science Foundation of China (21573149, 21533001 and 91745201).

Author information

Authors and Affiliations

  1. Collaborative Innovation Centre of Chemistry for Energy Material, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Key Laboratory of Computational Physical Science, Department of Chemistry, Fudan University, Shanghai, China

    Sicong Ma, Si-Da Huang & Zhi-Pan Liu

Authors
  1. Sicong Ma
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Si-Da Huang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Zhi-Pan Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

Z.-P.L. conceived the project and contributed to the design of the calculations and analyses of the data. S.M. carried out most of the calculations and wrote the draft of the paper. S.-D.H. wrote the neural network code and contributed to the analyses of the data. All the authors discussed the results and commented on the manuscripts.

Corresponding author

Correspondence to Zhi-Pan Liu.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

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

Supplementary information

Supplementary Information

Supplementary Methods, Supplementary Figs. 1–9, Supplementary Tables 1–9, Supplementary References.

Supplementary Data Set

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Ma, S., Huang, SD. & Liu, ZP. Dynamic coordination of cations and catalytic selectivity on zinc–chromium oxide alloys during syngas conversion. Nat Catal 2, 671–677 (2019). https://doi.org/10.1038/s41929-019-0293-8

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41929-019-0293-8

This article is cited by

Search

Advanced 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