Skip to main content

Thank you for visiting 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.

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


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.

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.


All prices are NET prices.

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.

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


  1. 1.

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

    CAS  Article  Google Scholar 

  2. 2.

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

    CAS  Article  Google Scholar 

  3. 3.

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

    CAS  Article  Google Scholar 

  4. 4.

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

    CAS  Article  Google Scholar 

  5. 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. 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).

    CAS  Article  Google Scholar 

  7. 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. 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).

    CAS  Article  Google Scholar 

  9. 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).

    CAS  Article  Google Scholar 

  10. 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).

    CAS  Article  Google Scholar 

  11. 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).

    CAS  Article  Google Scholar 

  12. 12.

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

    CAS  Article  Google Scholar 

  13. 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).

    CAS  Article  Google Scholar 

  14. 14.

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

    CAS  Article  Google Scholar 

  15. 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).

    CAS  Article  Google Scholar 

  16. 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).

    CAS  Article  Google Scholar 

  17. 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).

    CAS  Article  Google Scholar 

  18. 18.

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

    CAS  Article  Google Scholar 

  19. 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).

    CAS  Article  Google Scholar 

  20. 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. 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).

    CAS  Article  Google Scholar 

  22. 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).

    CAS  Article  Google Scholar 

  23. 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).

    CAS  Article  Google Scholar 

  24. 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).

    CAS  Article  Google Scholar 

  25. 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. 26.

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

    CAS  Article  Google Scholar 

  27. 27.

    Huang, S.-D. et al. LASP: Fast global potential energy surface exploration. WIREs Compt. Mol. Sci. (2019).

  28. 28.

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

    Article  Google Scholar 

  29. 29.

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

    CAS  Article  Google Scholar 

  30. 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. 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).

    CAS  Article  Google Scholar 

  32. 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).

    CAS  Article  Google Scholar 

Download references


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




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

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).

Download citation

Further reading


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