The electrochemical promotion of catalytic activity by non-noble transition metals is rarely reported in the literature. Here, Co nanoparticles were utilized for the electrochemical activation of CO2 hydrogenation under atmospheric pressure conditions. A range of transient kinetic experiments in conjunction with X-ray photoelectron spectroscopy and imaging techniques were employed to correlate the observed catalytic activity with the electronic and morphological characteristics of the cobalt catalyst surface. Our results show that migrating ions from the solid electrolyte to the catalyst surface has a dual effect, which has an impact on the observed catalytic behavior. First, they lead to an electrochemically formed double layer on the catalyst surface, which effectively modifies the catalyst work function and consequently alters the observed catalytic rate. Second, they have a profound effect on the oxidation state of cobalt and therefore on the structure of the cobalt oxide particles formed. The presence of Co oxide phases upon anodic polarization shows up to a 5-fold increase in the catalytic rate of the reverse water gas shift (RWGS) reaction. The enhancement of the catalytic activity observed in this work, with a relatively inexpensive cobalt oxide film, is comparable to that obtained with noble metal catalysts in classical EPOC studies. The present study also demonstrates that the formation of different oxide phases can be controlled accurately by electrochemical means and used to tune the catalytic activity and selectivity of cobalt. The reported results could guide the design and operation of more selective and active catalytic processes for the RWGS reaction.

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