Unexpected effect of second-shell defect in iron-nitrogen-carbon catalyst for electrochemical CO2 reduction reaction: A DFT study

doi:10.1016/S1872-2067(24)60131-2

Abstract

Abstract:

Metal-nitrogen-carbon catalysts (M-N-C) with single-atom active site are highly efficient catalysts for electrochemical CO₂ reduction reactions (CO₂RR). Abundant M-N-C catalysts have been developed, and the coordinated adjacent nitrogen atoms as first-shell environment have been the focus of research of activity-tuning. However, the effect of second-shell carbon environment around the metal-nitrogen moiety is still unclear. Moreover, it is confusing for the discrepancy between the experimental onset potential of around -0.2 V (vs. reversible hydrogen electrode, RHE, unless otherwise noted) and theoretical predictions of -0.5 V or higher by the widely-used computational hydrogen electrode (CHE) model. Herein, using the explicit solvent model and constant potential method (CPM), the electrochemical interface on Fe-N-C is simulated for CO₂RR. It reveals that the *COOH formation is facilitated in water solvent environment, while the CO₂ adsorption is potential-dependent. The predicted onset potential of around -0.2 V on Fe-N-C is consistent with experimental results. The sp² non-hexatomic defects introduced into second-shell carbon environment are significantly influential for the CO₂RR. The double five-seven ring (5577) defect is the most active, compared to that with triple five-seven ring (55577) or five-eight ring (58) defects. The highly flexible structure and altered density of states of Fe site induced by 5775 defects are key to CO₂adsorption. This study provides new insights into the role of second-shell carbon environment for effective CO₂RR, and underlines the importance of CPM and solvent environment in accurate simulation for electrochemical interface.

Key words: Iron-nitrogen-carbon catalysts, Electrochemical CO₂ reduction reaction, Defect engineering, Constant potential method, Density functional theory calculations

Mengna Wang, Qi Wang, Tianfu Liu, Guoxiong Wang. Unexpected effect of second-shell defect in iron-nitrogen-carbon catalyst for electrochemical CO₂ reduction reaction: A DFT study[J]. Chinese Journal of Catalysis, 2024, 66: 247-256.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60131-2

https://www.cjcatal.com/EN/Y2024/V66/I11/247

Figures/Tables 6

Fig. 1. (a) The configurations of pristine, 5577, 55577, and 58 Fe-N-C catalysts. (b) The formation energy and the Fe binding energy of catalysts. Color code: grey for carbon, blue for nitrogen, orange for iron.

Fig. 2. (a) The illustration of weak adsorption of CO2 on Fe-N-C and the *COOH formation as the potential-determining step (PDS). (b) The CO2 adsorption energy and *COOH formation free energy. (c) The atomic configurations of CO2 adsorption and *COOH formation on Fe-N-C catalysts. Color code: grey for carbon, blue for nitrogen, white for hydrogen, red for oxygen, orange for iron.

Fig. 3. (a-d) The energy profile of the *COOH formation on Fe-N-C. The initial state (IS), transition state (TS), final state (FS) are shown in the inset figures. Noted that for pristine, 5577, and 58 catalysts, one of the intermediate images was used as TS, and the FS is the one with the highest energy. Color code: grey for carbon, blue for nitrogen, white for hydrogen, red for oxygen, orange for iron.

Fig. 4. (a) The energy change between the final states and initial states on pristine, 5577, 58 or transition state and initial state on 55577 dependent on applied potentials, (b) illustration of *COOH formation in aqueous solution facilitated by hydrogen-bond network and applied potential. Color code: dark grey for carbon, blue for nitrogen, light grey for hydrogen, red for oxygen, orange for iron.

Fig. 5. (a) The configurations CO2 adsorption on Fe-N-C at the applied potential of 0 V. (b) The CO2 adsorption free energy of energy profile with applied potential. The line serves as a visual guide, with markers representing the actual data points. Color code: grey for carbon, blue for nitrogen, white for hydrogen, red for oxygen, orange for iron.

Fig. 6. (a) The CO2 adsorption configurations using CHE model and CPM at potential of 0 V. The distance between C in CO2 and Fe site and the angle of O-C-O are shown. Color code: grey for carbon, blue for nitrogen, white for hydrogen, red for oxygen, orange for iron. (b) The partial density of states (PDOS) on the d-orbital of Fe site on pristine, 5577, 55577, and 58 Fe-N-C.

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Unexpected effect of second-shell defect in iron-nitrogen-carbon catalyst for electrochemical CO₂ reduction reaction: A DFT study

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