Suppressing catalyst reconstruction in neutral electrolyte: stabilizing Co-O-Mo point-to-point connection of cobalt molybdate by tungsten doping for oxygen evolution reaction

doi:10.1016/S1872-2067(25)64748-6

Abstract

Abstract:

Neutral oxygen evolution reaction (OER) is a crucial half-reaction for electrocatalytic chemical production under mild condition, but with limited development due to low activity and poor stability. Herein, a tungsten-doped cobalt molybdate (WDCMO) catalyst was synthesized for efficient and durable OER under neutral electrolyte. It is demonstrated that catalyst reconstruction is suppressed by W doping, which stabilizes the Co-O-Mo point-to-point connection in CoMoO₄ architecture and stimulates to a lower valence state of active sites over the surface phase. Thereby, the surface structure maintains to avoid compound dissolution caused by over-oxidation during OER. Meanwhile, the WDCMO catalyst promotes charge transfer and optimizes *OH intermediate adsorption, which improves reaction kinetics and intrinsic activity. Consequently, the WDCMO electrode exhibits an overpotential of 302 mV at 10 mA cm^-2 in neutral electrolyte with an improvement of 182 mV compared with CoMoO₄ electrode. Furthermore, W doping significantly improves the electrode stability from 50 h to more than 320 h, with a suppressive potential attenuation from 2.82 to 0.29 mV h^-1. This work will shed new light on designing rational electrocatalysts for neutral OER.

Key words: Neutral oxygen evolution reaction, Suppressive catalyst reconstruction, Cobalt molybdate, Tungsten doping, Stability

Zhouzhou Wang, Qiancheng Zhou, Li Luo, Yaran Shi, Haoran Li, Chunchun Wang, Kesheng Lin, Chengsi Wang, Libing Zhu, Linyun Han, Zhuo Xing, Ying Yu. Suppressing catalyst reconstruction in neutral electrolyte: stabilizing Co-O-Mo point-to-point connection of cobalt molybdate by tungsten doping for oxygen evolution reaction[J]. Chinese Journal of Catalysis, 2025, 76: 146-158.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64748-6

https://www.cjcatal.com/EN/Y2025/V76/I9/146

Figures/Tables 7

Fig. 1. Material preparation and morphology characterization. (a) Schematics of the material preparation. SEM image (b), HRTEM image (inset: SAED pattern) (c), the enlarged images of the blue dotted circle (d) and red dotted box (e) in Fig. 1(c). (f) Dark field TEM image and corresponding EDS elemental mapping of WDCMO, respectively.

Fig. 2. Chemical structure characterization. XRD patterns (a) and the enlarged region of the dotted box (b) in Fig. 2(a) for WDCMO and CMO catalysts. Raman spectra (c) and the enlarged region of the dotted box (d) in Fig. 2(c) for WDCMO and CMO catalysts. High resolution of Co 2p (e), Mo 3d (f), and W 4f (g) XPS spectra for WDCMO and CMO catalysts over the bulk and surface phase. Co K-edge XANES spectra (h), FT k3-weighted EXAFS signals (i), and WT-EXAFS (j) for Co foil, WDCMO, and CMO.

Fig. 3. Neutral OER performance in 1 mol L−1 PBS. Polarization curves at a scan rate of 5 mV s−1 (a), overpotentials at 10 and 100 mA cm−2 (b), Tafel plots (c), polarization curves normalized by ECSA (d), and Nyquist plots (e) for various electrodes. (f) Chronopotentiometry curves of WDCMO and CMO at a current density of 10 mA cm−2.

Fig. 4. Stability analysis. High resolution of outer Co 2p (a), inner Co 2p (b), outer W 4f (c), and inner W 4f XPS (d) spectra for WDCMO before and after OER over the bulk and surface phase. (e) XRD pattern of WDCMO-OER and CMO-OER electrodes. (f) Content of Mo for WDCMO and CMO before and after OER determined by ICP-OES. Raman spectrum of CMO-KOH (g) and WDCMO-KOH (h) electrode immersed in 1 mol L−1 KOH for different time. (i) XES of Co Kβ for WDCMO and CMO electrodes, as well as CMO-KOH and WDCMO-KOH electrode immersed in 1 mol L−1 KOH for 300 minutes.

Fig. 5. Kinetic analysis. Operando Bode phase plots of WDCMO (a) and CMO (b). The peak of phase angles varies with the potentials at low (c) and high (d) frequency region for WDCMO and CMO. (e) In-situ Raman spectrum of WDCMO electrode.

Fig. 6. Mechanism analysis. (a) Formation energy of the models for W replacing Co sites and Mo sites. (b) Bader charge analysis of outer W1 site and surrounding Co sites for WDCMO. (c) Electron localization function diagram for outer W1 site of WDCMO compare with the initial Mo site of CMO. (d) PDOS plots of Mo d, Co d, and O p states in WDCMO and CMO. (e) CO stripping curves of WDCMO and CMO. (f) Energy profiles for OER path over WDCMO and CMO. (g) Schematics of stability improvement by W doping.

Fig. 7. Neutral overall water splitting in 1 mol L−1 PBS. Polarization curves of HER (a), overpotentials at −10 mA cm−2 and current density at −0.2 V (vs. RHE) (b), Tafel plots (c), and polarization curves (d) of water electrolysis of as-prepared WDCMP and CMP electrodes. (e) Chronopotentiometry curves of WDCMO||WDCMP and CMO||CMP at a current density of 10 mA cm−2.

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