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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A correction to this article is available online at https://doi.org/10.1038/s41929-018-0036-2.
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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.
Supplementary Information, Supplementary Figures 1–29, Supplementary Tables 1–4, Supplementary References
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