The limited electronic-level understanding of the active center and reaction pathway hinders the further development of high-efficient catalysts for electrochemical CO2 reduction reaction (CO2RR) towards practical application. In this work, we provide a thorough study of the underlying CO2RR mechanism over a model single-Fe-atom catalyst comprised of phthalocyanine (Pc) coordinated high-spin (HS) Fe(III). Operando Mossbauer and X-ray absorption spectroscopy (XAS) results evidenced the regular variation of the electronic and coordination structure of single-Fe-atom center during CO2RR. Combining with in-situ Raman spectroscopy, the transfer of first electron to the Pc-ligand with the generation of Fe(II)Pc- species were captured. Furthermore, the density functional calculations reveal that the reduction of Pc ring modifies the d-band center of the HS Fe(II) site, resulting the strongest binding strength of CO2 with HS Fe(II)Pc- species and boosting the catalytic performance.

Operando observing the electron transfer in electrochemical CO2 reduction over a model single-Fe-atom catalyst

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Operando</i> observing the electron transfer in electrochemical CO<sub>2</sub> reduction over a model single-Fe-atom catalyst