Coordination-tailored d-Orbital Occupancy: A Catalytic Descriptor for Single-atom Electrocatalysts in Oxygen Reduction Reaction

doi:10.1007/s40242-026-5259-1

Abstract

Abstract: Carbon-supported transition metal single-atom catalysts (TM-SACs) demonstrate exceptional promise for the electrochemical oxygen reduction reaction (ORR). Here, we carry out density functional theory (DFT) calculations and reveal a linear correlation between the adsorption free energy of the key intermediate OH (ΔG_OH) and the TM-OH bond strength. The TM-OH bond strength is governed by the symmetry-dependent contributions of different d orbitals to the bonding and antibonding interactions at the active site. The local in-plane coordination environment modulates the energy levels of the d_xy and \begin{document}$ d_{x^2-y^2} $\end{document} orbitals, resulting in the occupancy variation of the out-of-plane d orbitals (d_xz, d_yz, and \begin{document}$ d_{z^2} $\end{document}). Therefore, we introduce a descriptor (\begin{document}$ \theta_{\rm{OH}}=\theta_{d_{xz}}+\theta_{d_{yz}}+|1-\theta_{d_{z^2}}| $\end{document}, \begin{document}$ \theta_{\rm{d_{xz}}} $\end{document}, \begin{document}$ \theta_{\rm{d_{yz}}} $\end{document} and \begin{document}$ \theta_{d_{z^2}} $\end{document} indicating the occupancy of d_xz, d_yz, and \begin{document}$ d_{z^2} $\end{document} orbitals in the coordinated TM) to predict the catalytic performance of TM-Z_x SACs (TM=3d transition metals, Z=N, C, O, x=3, 4, 5) towards ORR. Furthermore, we develop a generalized descriptor φ, which only depends on the geometric and elemental characteristics of the TM, coordinating atoms (Z) and adsorbates. The descriptor can capture both the electronic properties and catalytic activity of TM-Z_x-C SACs without the need for additional calculations. Our findings provide an efficient and convenient strategy for optimizing catalytic performance through tailored geometric and electronic configurations.

Key words: Single atom catalyst, Oxygen reduction reaction, Rational catalyst design, Electrochemical reaction, Density functional theory

YANG Hui, TAO Lei, DU Shixuan. Coordination-tailored d-Orbital Occupancy: A Catalytic Descriptor for Single-atom Electrocatalysts in Oxygen Reduction Reaction[J]. Chemical Research in Chinese Universities, 2026, 42(3): 881-890.

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