Sacrificial conversion of metal sulfide precursors into active oxyhydroxide catalysts for enhanced oxygen evolution reaction

doi:10.1016/S1872-2067(25)64876-5

Abstract

Abstract:

Transition metal sulfides (TMSs) are promising electrocatalysts for the oxygen evolution reaction (OER) due to their tunable spin states, diverse metal-sulfur coordination environments, and controllable electronic structures. However, their structural instability under anodic conditions remains a critical challenge. In particular, the mechanisms governing active-phase formation and the identification of true catalytically active sites during surface reconstruction require further investigation. Herein, we report a cubic, self-assembled FeCoS₂/FeS₂ heterostructure catalysts. Through sulfur doping and electrochemical activation-induced surface reconstruction, the catalyst achieves 10 mA cm⁻² current density at an overpotential of only 287 mV in 1.0 mol L⁻¹ KOH after 1000 cycles. Experimental and in-situ spectroscopy analyses reveal that the heterogeneous interface enhances electron transfer, while dynamic reconstruction generates a highly active metal (oxy)hydroxide phase as the primary catalytically active species. This work provides mechanistic insights into the surface reconstruction of TMSs, and offers a viable strategy for designing efficient and durable non-noble metal electrocatalysts.

Key words: Surface reconstruction, Transition metal sulfides, Oxygen evolution reaction, Heterostructure, Electrochemical activation

Xinran Sun, Mengtian Huo, Jianhang Sun, Yu Liang, Kaichi Qin, Haoyang Zhang, Zihao Xing, Jinfa Chang. Sacrificial conversion of metal sulfide precursors into active oxyhydroxide catalysts for enhanced oxygen evolution reaction[J]. Chinese Journal of Catalysis, 2026, 82: 84-91.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64876-5

https://www.cjcatal.com/EN/Y2026/V82/I3/84

Figures/Tables 4

Fig. 1. Synthesis and structural profiling of the FeCoS2/FeS2 catalyst. (a) Schematic illustration of the synthetic procedure for FeCoS2/FeS2. SEM (b) and TEM (c) micrographs of FeCo PBA. SEM (d) and TEM (e) micrographs of FeCoS2/FeS2. (f) HR-TEM image of FeCoS2/FeS2 with clearly resolved lattice fringes corresponding to the (131) plane of FeS2 and (101) plane of FeCoS2. (d) EDS elemental mapping images of the FeCoS2/FeS2.

Fig. 2. (a) The XRD pattern of FeCoS2/FeS2. (b) The XPS spectra of Fe 2p for FeCoS2/FeS2 and FeCo. (c) The XPS spectra of Co 2p for FeCoS2/FeS2 and FeCo. (d) The XPS spectra of S 2p for FeCoS2/FeS2 and FeCo. (e) EXAFS of Fe K-edge for the FeCoS2/FeS2, Fe2O3 and Fe foil. (f) EXAFS of Co K-edge for the FeCoS2/FeS2, CoO and Co foil.

Fig. 3. OER performance for FeCoS2/FeS2, FeCo and Commercial RuO2. (a) LSV curves. (b) Tafel plots. (c) Histograms of overpotential and Tafel slopes for FeCoS2/FeS2, FeCo and Commercial RuO2. EIS (d) and Cdl (e) of FeCoS2/FeS2, FeCo and Commercial RuO2. (f) Long-term stability tests for FeCoS2/FeS2 and Commercial RuO2 at 100 mA cm?2.

Fig. 4. LSV curves of (a) precatalyst (FeCoS2/FeS2) after CV activation in 1 mol L?1 KOH. 1000 CVs cycles were done in a 1.0?1.7 V range at 100 mV s?1. (b) EXAFS of Fe K-edge for the precatalyst (FeCoS2/FeS2) and reconstructed catalyst. (c) EXAFS of Co K-edge for the precatalyst (FeCoS2/FeS2) and reconstructed catalyst. (d) In-situ Raman spectra of pre-FeCoS2/FeS2 at 150?1000 cm?1 under OER conditions. Bode diagrams of precatalyst (FeCoS2/FeS2) (e) and precatalyst (FeCo) (f) at 1.455?1.600 V for in-situ EIS.

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