Probing the Synergistic Effects of Mg²⁺ on CO₂ Reduction Reaction on CoPc by In Situ Electrochemical Scanning...

We report herein the in situ electrochemical scanning tunneling microscopy (ECSTM) study on the synergistic effect of Mg²⁺ in CO₂ reduction reaction (CO₂RR) catalyzed by cobalt phthalocyanine (CoPc). ECSTM measurement molecularly resolves the self-assembled CoPc monolayer on the Au(111) substrate. In the CO₂ environment, high-contrast species are observed in the adlayer and assigned to the CO₂ adsorption on CoPc. Furthermore, the contrast of the CO₂-bound complex is higher in Mg²⁺-containing electrolytes than in Mg²⁺-free electrolytes, indicating the formation of the CoPc-CO₂-Mg²⁺ complex. The surface coverage of adsorbed CO₂ is positively correlated with the Mg²⁺ concentration as the additive in electrolytes up to a plateau of 30.8 ± 2.7% when c(Mg²⁺) > 30 mM. The potential step experiment indicates the higher CO₂ adsorption dynamics in Mg²⁺-containing electrolytes than without Mg²⁺. The rate constants of CO₂ adsorption and dissociation in different electrolytes are extracted from the data fitting of statistical results from in situ ECSTM experiments.