Unravelling structure sensitivity in CO2 hydrogenation over nickel


Continuous efforts in the field of materials science have allowed us to generate smaller and smaller metal nanoparticles, creating new opportunities to understand catalytic properties that depend on the metal particle size. Structure sensitivity is the phenomenon where not all surface atoms in a supported metal catalyst have the same activity. Understanding structure sensitivity can assist in the rational design of catalysts, allowing control over mechanisms, activity and selectivity, and thus even the viability of a catalytic reaction. Here, using a unique set of well-defined silica-supported Ni nanoclusters (1–7 nm) and advanced characterization methods, we prove how structure sensitivity influences the mechanism of catalytic CO2 reduction, the nature of which has been long debated. These findings bring fundamental new understanding of CO2 hydrogenation over Ni and allow us to control both activity and selectivity, which can be a means for CO2 emission abatement through its valorization as a low- or even negative-cost feedstock on a low-cost transition-metal catalyst.

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Fig. 1: Mechanisms of catalytic CO2 hydrogenation.
Fig. 2: Particle size–activity relationships.
Fig. 3: Combined operando FT-IR and catalyst activity measurements.
Fig. 4: Q-XAS of five Ni/SiO2 catalysts with different mean Ni particle sizes.

Change history

  • 05 February 2018

    In the version of this Article originally published online, in Fig. 2b, the y axis unit incorrectly included superscript –1 on Ni; it should have been just Ni. In the PDF only, in Fig. 2d–f, the label ‘Particle size (nm)’ was missing from the x axes. All of these corrections have now been made.


  1. 1.

    Adoption of the Paris Agreement FCCC/CP/2015/L.9/Rev.1 (UNFCCC, 2015).

  2. 2.

    McGlade, C. & Ekins, P. The geographical distribution of fossil fuels unused when limiting global warming to 2 °C. Nature 517, 187–190 (2015).

    CAS  Article  Google Scholar 

  3. 3.

    Ertl, G., Knözinger, H. & Weitkamp, J. (eds) Handbook of Heterogeneous Catalysis (Wiley VCH, Weinheim, 1997).

    Google Scholar 

  4. 4.

    Ertl, G. Reactions at surfaces: From atoms to complexity (Nobel lecture). Angew. Chem. Int. Ed. 47, 3524–3535 (2008).

    CAS  Article  Google Scholar 

  5. 5.

    Somorjai, G. A. & Li, Y. Introduction to Surface Chemistry and Catalysis (John Wiley & Sons, New York, 2010).

    Google Scholar 

  6. 6.

    Senderens, J.-B. & Sabatier, P. Nouvelles synthèses du méthane. Compt. Rend. 82, 514–516 (1902).

    Google Scholar 

  7. 7.

    Sabatier, P. & Senderens, J.-B. Hydrogénation directe des oxydes du carbone en présence de divers métaux divisés. Compt. Rend. 134, 689–691 (1903).

    Google Scholar 

  8. 8.

    Armstrong, R. C. et al. The frontiers of energy. Nat. Energy 1, 15020 (2016).

    Article  Google Scholar 

  9. 9.

    Hull, J. F. et al. Reversible hydrogen storage using CO2 and a proton-switchable iridium catalyst in aqueous media under mild temperatures and pressures. Nat. Chem. 4, 383–388 (2012).

    CAS  Article  Google Scholar 

  10. 10.

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

    CAS  Article  Google Scholar 

  11. 11.

    Schuchmann, K. & Muller, V. Direct and reversible hydrogenation of CO2 to formate by a bacterial carbon dioxide reductase. Science 342, 1382–1386 (2013).

  12. 12.

    Rostrup-Nielsen, J. R., Pedersen, K. & Sehested, J. High temperature methanation - sintering and structure sensitivity. Appl. Catal. A 330, 134–138 (2007).

    CAS  Article  Google Scholar 

  13. 13.

    Silaghi, M., Comas-Vives, A. & Copéret, C. CO2 activation on Ni/γ−Al2O3 catalysts by first-principles calculations: from ideal surfaces to supported nanoparticles. ACS Catal. 6, 4501–4505 (2016).

    CAS  Article  Google Scholar 

  14. 14.

    Kopyscinski, J., Schildhauer, T. J. & Biollaz, S. M. A. Production of synthetic natural gas (SNG) from coal and dry biomass—a technology review from 1950 to 2009. Fuel 89, 1763–1783 (2010).

    CAS  Article  Google Scholar 

  15. 15.

    Yan, Z., Ding, R., Song, L. & Qian, L. Mechanistic study of carbon dioxide reforming with methane over supported nickel catalysts. Energy Fuels 12, 1114–1120 (1998).

    CAS  Article  Google Scholar 

  16. 16.

    Lewis, N. S. & Nocera, D. G. Powering the planet: chemical challenges in solar energy utilization. Proc. Natl Acad. Sci. USA 104, 15729–15735 (2007).

    Article  Google Scholar 

  17. 17.

    Steinfeld, A. Solar thermochemical production of hydrogen—a review. Sol. Energy 78, 603–615 (2005).

    CAS  Article  Google Scholar 

  18. 18.

    Centi, G. & Perathoner, S. Opportunities and prospects in the chemical recycling of carbon dioxide to fuels. Catal. Today 148, 191–205 (2009).

    CAS  Article  Google Scholar 

  19. 19.

    Tada, S., Shimizu, T., Kameyama, H., Haneda, T. & Kikuchi, R. Ni/CeO2 catalysts with high CO2 methanation activity and high CH4 selectivity at low temperatures. Int. J. Hydrog. Energy 37, 5527–5531 (2012).

    CAS  Article  Google Scholar 

  20. 20.

    Schlögl, R. The revolution continues: Energiewende 2.0. Angew. Chem. Int. Ed. 54, 4436–4439 (2015).

    Article  Google Scholar 

  21. 21.

    van Santen, R. A. Complementary structure sensitive and insensitive catalytic relationships. Acc. Chem. Res. 42, 57–66 (2009).

    Article  Google Scholar 

  22. 22.

    van Hardeveld, R. & van Montfoort, A. The influence of crystallite size on the adsorption of molecular nitrogen on nickel, palladium and platinum. Surf. Sci. 4, 396–430 (1966).

    Article  Google Scholar 

  23. 23.

    Bezemer, G. L. et al. Cobalt particle size effects in the Fischer−Tropsch reaction studied with carbon nanofiber supported catalysts. J. Am. Chem. Soc. 128, 3956–3964 (2006).

    CAS  Article  Google Scholar 

  24. 24.

    Ren, J. et al. Insights into the mechanisms of CO2 methanation on Ni(111) surfaces by density functional theory. Appl. Surf. Sci. 351, 504–516 (2015).

    CAS  Article  Google Scholar 

  25. 25.

    den Breejen, J. P. et al. On the origin of the cobalt particle size effects in Fischer–Tropsch catalysis. J. Am. Chem. Soc. 131, 7197–7203 (2009).

    Article  Google Scholar 

  26. 26.

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

    CAS  Article  Google Scholar 

  27. 27.

    Heine, C., Lechner, B. A. J., Bluhm, H. & Salmeron, M. Recycling of CO2: probing the chemical state of the Ni(111) surface during the methanation reaction with ambient-pressure X-ray photoelectron spectroscopy. J. Am. Chem. Soc. 138, 13246–13252 (2016).

    CAS  Article  Google Scholar 

  28. 28.

    Czekaj, I., Loviat, F., Raimondi, F., Biollaz, S. & Wokaun, A. Characterization of surface processes at the Ni-based catalyst during the methanation of biomass-derived synthesis gas: X-ray photoelectron spectroscopy (XPS). Appl. Catal. A 329, 68–78 (2007).

    CAS  Article  Google Scholar 

  29. 29.

    Marwood, M., Doepper, R. & Renken, A. In-situ surface and gas phase analysis for kinetic studies under transient conditions. The catalytic hydrogenation of CO2. Appl. Catal. A 151, 223–246 (1997).

    CAS  Article  Google Scholar 

  30. 30.

    Tao, F. et al. Reaction-driven restructuring of Rh-Pd and Pt-Pd core-shell nanoparticles. Science 322, 932–934 (2008).

  31. 31.

    Tao, F. et al. Break-up of stepped platinum catalyst surfaces by high CO coverage. Science 327, 850–853 (2010).

    CAS  Article  Google Scholar 

  32. 32.

    Miao, D. et al. Water-gas shift reaction over platinum/strontium apatite catalysts. Appl. Catal. B 202, 587–596 (2017).

    CAS  Article  Google Scholar 

  33. 33.

    Lamberti, C., Zecchina, A., Groppo, E. & Bordiga, S. Probing the surfaces of heterogeneous catalysts by in situ IR spectroscopy. Chem. Soc. Rev. 12, 4951–5001 (2010).

    Article  Google Scholar 

  34. 34.

    Yardimci, D., Serna, P. & Gates, B. C. Surface-mediated synthesis of dimeric rhodium catalysts on MgO: Tracking changes in the nuclearity and ligand environment of the catalytically active sites by X-ray absorption and infrared spectroscopies. Chem. Eur. J. 19, 1235–1245 (2013).

    CAS  Article  Google Scholar 

  35. 35.

    Kalz, K. F. et al. Future challenges in heterogeneous catalysis: understanding catalysts under dynamic reaction conditions. ChemCatChem 9, 17–29 (2017).

  36. 36.

    Camputano, J. C. & Greenler, R. G. The adsorption sites of CO on Ni(111) as determined by infrared reflection-absorption spectroscopy. Surf. Sci. 83, 301–312 (1979).

    Article  Google Scholar 

  37. 37.

    Trenary, M., Uram, K. J. & Yates, J. T. An infrared reflection-absorption study of CO chemisorbed on clean and sulfided Ni(111)—evidence for local surface interactions. Surf. Sci. 157, 512–538 (1985).

    CAS  Article  Google Scholar 

  38. 38.

    Layman, K. A. & Bussell, M. E. Infrared spectroscopic investigation of CO adsorption on silica-supported nickel phosphide catalysts. J. Phys. Chem. B 108, 10930–10941 (2004).

    CAS  Article  Google Scholar 

  39. 39.

    Courtois, M. & Teichner, S. J. Infrared studies of CO, O2 and CO2 gases and their interaction products, chemically adsorbed on nickel oxide. J. Catal. 135, 121–135 (1962).

    Article  Google Scholar 

  40. 40.

    Vesselli, E., Schweicher, J., Bundhoo, A., Frennet, A. & Kruse, N. Catalytic CO2 hydrogenation on nickel: novel insight by chemical transient kinetics. J. Phys. Chem. C. 115, 1255–1260 (2011).

    CAS  Article  Google Scholar 

  41. 41.

    van Bokhoven, J. A. & Lamberti, C. X-Ray Absorption and X-Ray Emission Spectroscopy: Theory and Applications (John Wiley & Sons: New York, NY, 2016).

    Google Scholar 

  42. 42.

    Bordiga, S., Groppo, E., Agostini, G., Van Bokhoven, J. A. & Lamberti, C. Reactivity of surface species in heterogeneous catalysts probed by in situ X-ray absorption techniques. Chem. Rev. 113, 1736–1850 (2013).

    CAS  Article  Google Scholar 

  43. 43.

    Van Helden, P., Ciobica, I. M. & Coetzer, R. L. J. The size-dependent site composition of FCC cobalt nanocrystals. Catal. Today 261, 48–59 (2016).

    Article  Google Scholar 

  44. 44.

    Enger, B. C. & Holmen, A. Nickel and Fischer-Tropsch synthesis. Catal. Rev. Sci. Eng. 54, 437–488 (2012).

  45. 45.

    Munnik, P., Velthoen, M. E. Z., de Jongh, P. E., De Jong, K. P. & Gommes, C. J. Nanoparticle growth in supported nickel catalysts during methanation reaction-larger is better. Angew. Chem. Int. Ed. 53, 9493–9497 (2014).

    CAS  Article  Google Scholar 

  46. 46.

    Ermakova, M. A. & Ermakov, D. Y. High-loaded nickel-silica catalysts for hydrogenation, prepared by sol-gel route: structure and catalytic behavior. Appl. Catal. A 245, 277–288 (2003).

    CAS  Article  Google Scholar 

  47. 47.

    De Jong, K. P. in Synthesis of Solid Catalysts (ed. De Jong, K. P.) 111–134 (Wiley-VCH Verlag, Weinheim, 2009).

  48. 48.

    Lok, M. in Synthesis of Solid Catalysts (ed. De Jong, K. P.) 135–151 (Wiley-VCH Verlag, Weinheim, 2009)..

  49. 49.

    Liu, Y. et al. TXM-Wizard: A program for advanced data collection and evaluation in full-field transmission X-ray microscopy. J. Synchrotron. Radiat. 19, 281–287 (2012).

    CAS  Article  Google Scholar 

  50. 50.

    Ravel, B. & Newville, M. ATHENA, ARTEMIS, HEPHAESTUS: data analysis for X-ray absorption spectroscopy using IFEFFIT. J. Synchrotron. Radiat. 12, 537–541 (2005).

    CAS  Article  Google Scholar 

  51. 51.

    Frenkel, A. I., Hills, C. W. & Nuzzo, R. G. A view from the inside: complexity in the atomic scale ordering of supported metal nanoparticles. J. Phys. Chem. B 105, 12689–12703 (2001).

    CAS  Article  Google Scholar 

  52. 52.

    Chukin, G. D. & Malevich, V. I. Infrared spectra of silica. Zhurnal Prikl. Spektrosk. 26, 223–229 (1977).

    Google Scholar 

  53. 53.

    Socrates, G. Infrared and Raman Characteristic Group Frequencies (Wiley, Chichester, 2001).

  54. 54.

    Erley, W., Wagner, H. & Ibach, H. Adsorption sites and long range order —vibrational spectra for CO on Ni(111). Surf. Sci. 80, 612–619 (1979).

    CAS  Article  Google Scholar 

  55. 55.

    Erley, W. & Wagner, H. Thermal decomposition of CO on a stepped Ni surface. Surf. Sci. 74, 333–341 (1978).

    CAS  Article  Google Scholar 

  56. 56.

    Chumakova, A. V. et al. Periodic order and defects in Ni-based inverse opal-like crystals on the mesoscopic and atomic scale. Phys. Rev. B 90, 1–9 (2014).

    Article  Google Scholar 

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The authors thank NWO and BASF for a TA-CHIPP grant. B.M.W. also thanks NWO for a Gravitation programme (Netherlands Center for Multiscale Catalytic Energy Conversion (MCEC)). Furthermore, S. Parker and J. Palle (Utrecht University, UU) are acknowledged for their contributions in measuring FT-IR spectra and activity data. F. Soulimani (UU) and P. de Peinder (UU) are acknowledged for discussions regarding FT-IR data. J. Geus (UU) is also acknowledged for fruitful discussions. A. van der Eerden, M. Filez and H. Schaink, all from UU, are acknowledged for (technical) support in measuring XAS. O. Sofanova (PSI) is thanked for reading the manuscript carefully prior to submission.

Author information




E.G. made the set of catalyst samples. C.V., F.M. and B.M.W. conceived and designed the operando experiments. C.V. performed the operando spectroscopic experiments. FT-IR data analysis was performed by C.V. with input from B.M.W., while quick XAS data analysis was performed by F.M. and C.V. L.L. and C.J.K performed and interpreted HAADF–STEM measurements; G.K., E.G. and P.H.B. performed and interpreted H2 chemisorption measurements and prepared reference XAS samples. M.N. aided in the set-up, and provided support with the operando quick XAS measurements. C.V., F.M. and B.M.W. wrote the paper. All authors discussed the results and commented on the manuscript.

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Correspondence to Bert M. Weckhuysen.

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A correction to this article is available online at https://doi.org/10.1038/s41929-018-0036-2.

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Vogt, C., Groeneveld, E., Kamsma, G. et al. Unravelling structure sensitivity in CO2 hydrogenation over nickel. Nat Catal 1, 127–134 (2018). https://doi.org/10.1038/s41929-017-0016-y

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