Unravelling ligand topology effect on the binding of oxygen reduction reaction intermediates on Fe-Nx-C single-atom catalysts

doi:10.1016/S1872-2067(23)64621-2

Abstract

Abstract:

The rational design of Fe-N-C single-atom catalysts (SAC) requires a priori estimation of its activity with descriptors that require no additional calculations. In this study, we conducted a thorough investigation into the effect of the amount and the location of N and the position of edge atoms on intermediate adsorption energies, and then unveiled the critical topological factors. Our density functional theory calculations, energy decomposition analysis and bonding analysis on OH adsorption on finite graphitic Fe-N_x-C (x = 0-4) models discover that nitrogen not only concentrates electrons on the ligand onto donor atoms but also induces a more ionic nature in the Fe-ligand (Fe-L) bonds and partially disrupts the aromaticity of the ligand. The latter effect strongly correlates to the location of N. These effects influence the electrostatic, Pauli repulsive and orbital interactions that are involved in the Fe-O bond formation. Furthermore, our investigation also reveals that the size of SAC plays a role in binding only when the edge atom is situated in the ring containing donor atoms. Our work for the first time provides a comprehensive mechanism of OH adsorption on SAC and the influence of N and the size. It emphasizes the necessity of considering the quantity and the location of nitrogen, as well as the atoms surrounding the donor atoms when developing descriptors.

Key words: Single-atom catalysts, Oxygen reduction reaction, Ligand topology effect, Energy decomposition analysis, Density functional theory

De-Gui Wu, Xiao-Gen Xiong, Zhong-Dong Zhao, Shu-Qin Song, Zhao-Bin Ding. Unravelling ligand topology effect on the binding of oxygen reduction reaction intermediates on Fe-N_x-C single-atom catalysts[J]. Chinese Journal of Catalysis, 2024, 59: 214-224.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64621-2

https://www.cjcatal.com/EN/Y2024/V59/I4/214

Figures/Tables 10

Fig. 1. Schemes of Fe-Nx-C SAC. Each model is denoted as CXX-CxNy, where XX represents the number of atoms apart from the donor atoms and Fe, x and y represent the number of C and N as donor atoms, respectively. The a-d present models for C10-C4N0, C10-C3N1, C10-C1N3 and C10-C0N4, respectively. The e-g shows models for C10-p-C2N2, C10-o-5m-C2N2 and C10-o-6m-C2N2, respectively. The h-i are the models of C22-C4N0 and C54-C0N4. The orange, blue, grey, and white colours represent Fe, N, C and H atoms, respectively.

Fig. 2. Adsorption energies of OH for all SAC models investigated in this work.

Fig. 3. EDA results for different Fe-Nx-C SAC. (a-d) are Eestat, Exrep, Eorb, and Eprep respectively. All terms are defined in Eq. (2).

Fig. 4. Bader charge on pristine (a) C10 (b) C22 and (c) C54 Fe-Nx-C surfaces. Charges on H at the edge are excluded. (d) The relationship between summed Bader charge on Fe and donor atoms and Eestat in 21 SAC models.

Fig. 5. Pauli repulsion density of electrons of (a) C22-C4N0 and (b) C22-C0N4. (c) Charge density difference diagram of C22-p-N2. The orange, blue, grey, and white colours represent Fe, N, C and H atoms, respectively. The light blue region indicates charge depletion and the yellow region indicates charge cumulation. Isosurface is set to be 0.002 a.u.

Fig. 6. Correlation between repulsive interaction, Exrep, and electrostatic interaction energy, Eestat.

Fig. 7. The three orbital pairs that contribute the most to Eorb on (a) C22-C4N0, (b) C22-p-C2N2, (c) C22-o-6m-C2N2 and (d) C22-C0N4. The percentage of the contribution to Eorb is shown below each orbital pair. Isosurfaces are set to be 0.002 a.u.

Fig. 8. Effect of N doping on the conjugated π-bonds on ligands represented by LOL-π plots for (a) C22-C4N0, (b) C22-C3N1, (c) C22-p-C2N2, (d) C22-o-5m-C2N2, (e) C22-o-6m-C2N2.

Fig. 9. Impacts of N doping on orbital interactions on different sizes of SAC represented by: ETS-NOCV results for the most contributed orbital pairs on (a) C10-C4N0 (b) C10-C0N4 (c) C54-C4N0 (showing two orbital pairs) and (d) C54-C0N4, and LOL-π results for (e) C10-p-C2N2 and (f) C10-o-5m-C2N2 (g) C10-o-6m-C2N2 (h) C54-p-C2N2. Isosurfaces are set to be 0.005 a.u.

Fig. 10. (a) Correlation between Fe-L bond energy and Eprep (b) Correlation between the quantity of N and the Fe-L bond energy.

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