Group IIIA metals-induced p-d orbital hybridization enhances the oxygen reduction performance of Pd based metallene in zinc-air batteries

doi:10.1016/S1872-2067(26)64964-9

Abstract

Abstract:

ABSTRACT：p-d orbital hybridization offers a powerful strategy to optimize oxygen adsorption energies and accelerate the oxygen reduction reaction (ORR) in zinc-air batteries (ZABs). Here, we introduce Group IIIA elements (Al, Ga, In) into PdPtMo metallenes to systematically tune p-d orbital interactions. Among them, Ga exhibits the smallest atomic radius mismatch and optimal orbital energy alignment, and the enhanced p-d orbital hybridization in PdPtMoGa metallenes promotes electron transfer. The PdPtMoGa metallene/C catalyst achieves an exceptionally high mass activity of 6.07 A mg^-1_Pt at 0.9 V vs. RHE and a half-wave potential of 0.94 V, surpassing commercial Pt/C. Density functional theory calculations, X-ray absorption spectroscopy, in-situ Fourier-transform infrared spectroscopy, and other characterizations reveal that the strong p-d orbital hybridization induced by Ga coordination with Pd in PdPtMoGa metallenes lowers the d-band center and weakens the adsorption of oxygen intermediates. Remarkably, the catalyst retains stability over 30,000 cycles. When deployed in ZABs, PdPtMoGa metallene/C achieves a peak power density of 207.2 mW cm^-2 and stable operation exceeding 180 h. Overall, this study presents a rational design strategy for high-activity and durable Pd-based electrocatalysts and elucidates the specific roles of Group IIIA elements in modulating p-d orbital hybridization.

Key words: p-d orbital hybridization, Group IIIA elements, Pd-based metallenes, Electronic structure, Oxygen reduction reaction, Zinc-air batteries

Wenning Liu, Li An, Jinming Wang, Ruyue Li, Jie Mu, Yongde Long, Dan Qu, Yichang Liu, Yuxiang Hu, Xiayan Wang, Ning Jiang, Zaicheng Sun. Group IIIA metals-induced p-d orbital hybridization enhances the oxygen reduction performance of Pd based metallene in zinc-air batteries[J]. Chinese Journal of Catalysis, 2026, 84: 144-158.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)64964-9

https://www.cjcatal.com/EN/Y2026/V84/I5/144

Figures/Tables 7

Scheme 1. Schematic diagram of orbital hybridization.

Fig. 1. Atomic radii (a), electronegativities (b) and negative orbital energies (c) of neutral atoms for Pd, Pt, Mo, Al, Ga, and In, along with the corresponding calculated differences. (d) PDOS of the PdPtMoX (X = Al, Ga, In) models (inset shows a partial enlargement for clarifying p-d orbital hybridization). Calculated free energy diagrams for the ORR at Pt (111) (e), PdPtMoAl (111) (f), PdPtMoGa (111) (g) and the PdPtMoIn (111) (h) surfaces. (i) The free energy diagrams at U = 0 V.

Fig. 2. (a) XRD patterns of PdPtMo, PdPtMoAl, PdPtMoGa, PdPtMoIn metallenes/C. (b-d) Low-resolution TEM images of PdPtMoX (X = Al, Ga, In) metallene. (e,f) AC-HAADF-STEM image of different regions of the PdPtMoGa metallene. (g) STEM-EDS elemental mapping images of PdPtMoGa metallene. (h) AFM image of PdPtMoGa metallene.

Fig. 3. (a) High resolution XPS spectra of Pd 3d for Pd/C and PdPtMoX (X = Al, Ga, In) metallens/C. (b) High resolution XPS spectra of Pt 4f for Pt/C and PdPtMoX (X = Al, Ga, In) metallenes/C. (c) Comparison of the binding energies of Pd0, Pt0, and Mo0 in PdPtMoX (X = Al, Ga, In) electrocatalysts, respectively. (d) XPS valence band spectra of Pd/C, PdPtMoAl metallene/C, PdPtMoGa metallene/C, and PdPtMoIn metallene/C. Normalized XANES spectra at the Pd K-dege (e) and Pt L3-edge (f). The FT-EXAFS spectra at the Pd K-edge (g) and Pt L3-edge (h). (i) Wavelet transforms of the k3-weighted EXAFS signals for Pt and Pd in PdPtMoGa, Pd foil, and Pt foil.

Fig. 4. (a) ORR polarization curves of Pt/C, PdPtMo metallene/C, PdPtMoAl metallene/C, PdPtMoGa metallene/C, PdPtMoIn metallene/C in O2-saturated 0.1 mol L?1 KOH at 10 mV s-1 under 1600 rpm. (b) The mass activity at 0.9 V vs. RHE of PdPtMoAl metallene/C, PdPtMoGa metallene/C, PdPtMoIn metallene/C. (c) TOF of commercial Pt/C and PdPtMoX metallene/C calculated from ORR dynamic current. (d) LSV curves of PdPtMoGa metallene/C at various rotating speed rates. (e) RRDE curves of PdPtMoGa metallene/C at 1600 rpm, showing H2O2 yield and electron transfer number. (f) Mass activities of PdPtMoGa metallene/C and Pt/C at 0.8, 0.85 and 0.9 V vs. RHE. (g-i) Three-dimensional in-situ ATR-FTIR on PdPtMoX (X = Al, Ga, In) metallene/C in O2-saturated 0.1 mol L?1 KOH.

Fig. 5. ORR polarization curves of Pt/C (a) and PdPtMoGa metallene/C (b) after 30000 cycles in the voltage range of 0.6-1.0 V vs. RHE. The chronoamperometry measurements of (c) PdPtMoGa metallene/C and Pt/C. High-resolution XPS spectra of Pd 3d (d), Pt 4f (e), Ga 3d (f), and Mo 3d (g) in PdPtMoGa metallene/C before and after 12 h chronoamperometric testing in 0.1 mol L?1 KOH.

Fig. 6. (a) Schematic diagram of the working principle of a Zn-air battery. (b) Open-circuit voltage plots of the Zn-air battery assembled with the Pt/C+RuO2, PdPtMoAl metallene/C, PdPtMoGa metallene/C and PdPtMoIn metallene/C air electrodes. (c) Galvanodynamic discharge/charge polarization curves. (d) Discharge polarization curves and the corresponding power density plots. (e) Specific capacity of zinc-air batteries at a constant current density of 5 mA cm-2. (f) Voltage retention throughout the current densities range of 5-100 mA cm-2. (g) Galvanostatic discharge/charge cycling curves at a constant current density of 5 mA cm-2 of Pt/C+RuO2 and PdPtMoGa metallene/C.

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