Ni Single Atom Catalysts for CO₂ Activation

Abstract

We report on the activation of CO 2 on Ni single-atom catalysts. These catalysts were synthesized using a solid solution approach by controlled substitution of 1–10 atom % of Mg 2+ by Ni 2+ inside the MgO structure. The Ni atoms are preferentially located on the surface of the MgO and, as predicted by hybrid-functional calculations, favor low-coordinated sites. The isolated Ni atoms are active for CO 2 conversion through the reverse water–gas shift (rWGS) but are unable to conduct its further hydrogenation to CH 4 (or MeOH), for which Ni clusters are needed. The CO formation rates correlate linearly with the concentration of Ni on the surface evidenced by XPS and microcalorimetry. The calculations show that the substitution of Mg atoms by Ni atoms on the surface of the oxide structure reduces the strength of the CO 2 binding at low-coordinated sites and also promotes H 2 dissociation. Astonishingly, the single-atom catalysts stayed stable over 100 h on stream, after which no clusters or particle formation could be detected. Upon catalysis, a surface carbonate adsorbate-layer was formed, of which the decompositions appear to be directly linked to the aggregation of Ni. This study on atomically dispersed Ni species brings new fundamental understanding of Ni active sites for reactions involving CO 2 and clearly evidence the limits of single-atom catalysis for complex reactions.

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Highly dispersed nickel catalysts via a facile pyrolysis generated protective carbon layer

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