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Abstract

Electrochemical CO₂ reduction (CO₂RR) is a rising technology, aiming to reduce the energy sector dependence on fossil fuels and to produce carbon-neutral raw materials. Metal-nitrogen-doped carbons (M-N-C) are emerging, cost-effective catalysts for this reaction; however, their long-term stability is a major issue. To overcome this, understanding their structural evolution is crucial, requiring systematic in-depth operando studies. Here a series of M-N-C catalysts (M = Fe, Sn, Cu, Co, Ni, Zn) was investigated using operando X-ray absorption spectroscopy. We found that the Fe-N-C and Sn-N-C are prone to the oxide clusters formation even before CO2RR. In contrast, the respective metal cations were singly dispersed in the as-prepared Cu-N-C, Co-N-C, Ni-N-C and (Zn)-N-C. During CO₂RR, metallic clusters/nanoparticles reversibly formed in all catalysts, except for the Ni-N-C. This phenomenon, previously observed only in Cu-N-C, thus is ubiquitous in M-N-C catalysts. The competition between M-O and M-N interactions is an important factor determining the mobility of metal species in M-N-C. Specifically, the strong interaction between the Ni centers and the N-functional groups of the carbon support results in higher stability of the Ni single-sites, leading to the excellent performance of Ni-N-C in the CO₂ to CO conversion, in comparison to other transition metals.