Enhanced oxygen evolution and reduction by phosphorus-doped Co9S8 derived from MOFs: Toward high-performance zinc-air batteries

doi:10.1016/S1872-2067(26)65028-0

Abstract

Abstract:

Developing high-performance electrocatalysts for the oxygen evolution (OER) and reduction reactions (ORR) is key to further developing rechargeable zinc-air batteries (ZABs). In this work, we demonstrate phosphorus-doped hollow cobalt pentlandite (P-Co₉S₈) nanocubes, derived from ZIF-67, which combine MOF-inherited porosity with phosphorus-induced electronic modulation, as a bifunctional oxygen electrocatalyst. As a cathode catalyst, P-Co₉S₈ achieves a high power density of 177 mW cm^-1, a specific capacity of 775 mAh g_Zn^-1, and remarkable cycling stability over 900 h. Comprehensive experiments and density functional theory show that P doping tunes the local coordination environment, optimizes the d-band center, and lowers reaction energy barriers, enabling fast, durable, and selective oxygen electrocatalysis. This study establishes a generalizable strategy for designing advanced chalcogenide-based electrocatalysts for next-generation energy storage devices.

Key words: Metal-organic framework, Phosphorus doping, Cobalt sulfide, Bifunctional electrocatalyst, Oxygen evolution reaction, Oxygen reduction reaction, Zinc-air battery

Xiang Wang, Min Zhou, Xiaobin Liao, Xu Han, Congcong Xing, René Bes, Simo Huotari, Jordi Arbiol, Andreu Cabot. Enhanced oxygen evolution and reduction by phosphorus-doped Co₉S₈ derived from MOFs: Toward high-performance zinc-air batteries[J]. Chinese Journal of Catalysis, 2026, 85: 204-215.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65028-0

https://www.cjcatal.com/EN/Y2026/V85/I6/204

Figures/Tables 6

Fig. 1. (a) Schematic illustration of the synthesis process for P-Co9S8. SEM images of ZIF-67 (b), Co9S8 (c), and P-Co9S8 (d). (e,f) TEM images of P-Co9S8. (g) HRTEM image and corresponding FFT spectrum (insert). The P-Co9S8 lattice fringe distances were measured to be 0.235, 0.288, and 0.296 nm, at 52.92° and 130.11°, which could be interpreted as the cubic Co9S8 phase, visualized along its [011] zone axis. (h,i) HAADF-STEM images and EELS chemical composition maps obtained from the red squared area of the STEM micrograph. Individual Co L2,3-edges at 779 eV (red), P L2,3-edges at 132 eV (green), S L2,3-edges at 165 eV (blue), and composites of Co-P, Co-S, Co-P-S.

Fig. 2. XRD patterns (a) and P 2p (b), S 2p (c), and Co 2p (d) high-resolution XPS spectra of Co9S8 and P-Co9S8. (e) Normalized XANES at the Co K-edge. (f) Calculated Co valence state from the XANES. Corresponding FT-EXAFS spectra (h) and Wavelet transform for the k2-weighted EXAFS signals (i) of Co for Co9S8 and P-Co9S8.

Fig. 3. (a) LSV polarization curves. (b) Corresponding Tafel plots. (c) Overpotential at 10 mA cm-2 and extracted Tafel slopes for the as-prepared catalysts. (d) Capacitive current density. (e) EIS Nyquist responses. (f) LSV curves of P-Co9S8 recorded before and after 5000 cycles. (g) Chronoamperometric stability of P-Co9S8 compared with IrO2. (h) Benchmarking of overpotential at 10 mA cm-2 and Tafel slopes against reported sulfide-based OER catalysts (Table S2).

Fig. 4. LSV polarization curves (a), Tafel plots (b), and Ehalf together with jk (0.85 V vs. RHE) (c) for Co9S8, P-Co9S8, P-Co3S4, and Pt/C measured in O2-saturated 0.1 mol L-1 KOH at 1600 rpm. RDE polarization curves of P-Co9S8 acquired at different rotation rates (d), with the corresponding K-L plots (e). (f) Electron-transfer number and H2O2 yield of P-Co9S8 (inset: RRDE LSV curves at 1600 rpm). (g) Chronoamperometric stability tests. (h) LSV curves of P-Co9S8 before and after 2000 CV cycles. (i) Methanol crossover tolerance at 0.7 V for P-Co9S8 and commercial Pt/C.

Fig. 5. (a) Atomic structure models of P-Co9S8 (b,c) PDOS and d band center of Co9S8 and P-Co9S8. Gibbs free energy evolution for OER of the different P-Co9S8 models at 1.23 V (d), and of Co9S8 and P-Co9S8 at different potentials (e).

Fig. 6. (a) Schematic diagram of an aqueous ZAB. Open circuit potentials (b), discharge polarization curves and corresponding peak powder density (c), specific capacities (d), and long-term charge-discharge cycling stabilities (e) of Pt/C +RuO2, Co9S8 and P-Co9S8 cells.

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Enhanced oxygen evolution and reduction by phosphorus-doped Co₉S₈ derived from MOFs: Toward high-performance zinc-air batteries

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