Developing a stable and high-performance W-CoMnP electrocatalyst by mitigating the Jahn-Teller effect through W doping strategy

doi:10.1016/S1872-2067(25)64669-9

Abstract

Abstract:

Manganese-based materials are influenced by the Jahn-Teller effect, causing the spontaneous dismutation of Mn³⁺ (2Mn³⁺ → Mn²⁺ + Mn⁴⁺) and the dissolution of Mn²⁺, which often results in diminished activity. This study uniquely employs a W doping strategy to suppress this effect. Externally, a simple template-free method was initially used to prepare cobalt- and manganese-based precursors, followed by a W doping process during the synthesis of transition bimetallic phosphides. Ultimately, W-doped bimetallic phosphides (W-CoMnP) were obtained. The W-CoMnP material demonstrates excellent HER and OER performance with low overpotentials of 95 mV (η₁₀ HER) and 225 mV (η₅₀ OER), and can achieve overall water splitting at a voltage of 1.52 V while maintaining stable cycling for 24 h. To enable commercial application, W-CoMnP was incorporated into an anion exchange membrane (AEM) electrolysis water device, demonstrating continuous and stable hydrogen production under ambient temperature conditions. This study offers a promising strategy for the future development of catalysts for AEM electrolysis water devices.

Key words: Bimetallic phosphide, Density functional theory calculation, Jiang-Taylor effect, W doping, Anion exchange membrane water electrolysis device

Bohan An, Xin Li, Weilong Liu, Jipeng Dong, Ruichao Bian, Luyao Zhang, Ning Li, Yangqin Gao, Lei Ge. Developing a stable and high-performance W-CoMnP electrocatalyst by mitigating the Jahn-Teller effect through W doping strategy[J]. Chinese Journal of Catalysis, 2025, 74: 264-278.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64669-9

https://www.cjcatal.com/EN/Y2025/V74/I7/264

Figures/Tables 10

Fig. 1. (a) Process flowchart for preparing W-CoMnP. (b) SEM image of W-CoMnP. (c) TEM images of W-CoMnP; (d-f) high resolution HRTEM images of W-CoMnP. (g) SAED image of W-CoMnP. (h-o) EDS elemental mapping images for C, N, O, Co, Mn, P and W separately.

Fig. 2. XRD patterns of W-CoMnP (a), MnP and CoP3 (b), W-MnP and W-CoP3 (c). (d) Raman spectra of W-CoMnP and CoMnP. (e) Infrared spectra of W-CoMnP and CoMnP. (f) SBET image of W-CoMnP and CoMnP. (g) Comparison graph of Co XPS peaks. (h) Comparison graph of Mn XPS peaks. (i) Comparison graph of P XPS peaks.

Fig. 3. (a) The LSV curves of W-CoMnP, CoMnP, W-CoP3, W-MnP, CoP3, MnP and CG. (b) Tafel slops of W-CoMnP, W-CoMnP, W-CoP3, W-MnP, CoP3, MnP and CG. (c) Relevant overpotentials at η10, η50 and η100 of the samples. (d) EIS Impedance of the prepared catalyst. (e) Double layer capacitance Cdl curves. (f) HER stability test of W-CoMnP. (g) Comparison of HER performance with other catalysts. (h) Comparison of HER LSV before and after stability testing.

Fig. 4. (a) LSV curves of W-CoMnP, CoMnP, W-CoP3, W-MnP, CoP3, MnP and CG. (b) Tafel slops of W-CoMnP, W-CoMnP, W-CoP3, W-MnP, CoP3, MnP and CG. (c) Relevant overpotentials at η50, η100 and η150 of the samples. (d) EIS Impedance of the prepared catalyst. (e) Double layer capacitance Cdl curves. (f) OER stability test of W-CoMnP. (g) Comparison of OER performance with other catalysts. (h) Comparison of OER LSV before and after stability testing.

Fig. 5. (a) Overall water splitting LSV curves of as-prepared catalysts at 1 mol/L KOH. (b) Activity comparison with other electrocatalysts. (c) XRD pattern of W-CoMnP recovered for OER reaction.

Fig. 6. (a) Structural diagram of AEM equipment. (b) Conductivity of W-CoMnP. (c) Internal diagram of AEM equipment electrolysis water operation. (d) LSV curves of catalysts at 1 mol/L KOH in AEM equipment.

Fig. 7. (a) In situ Raman spectra of W-CoMnP in 1 mol/L NaOH. (b) In situ Raman spectroscopy, peak information of W-CoMnP. (c) Explanation of the formation of CoOOH. (d) Schematic representation of the electronic coupling between Co and Mn in W-CoMnP.

Fig. 8. (a) Free energy diagram of HER intermediates at different U values. (b) The reaction pathway of the HER process (U = 0); image is most likely OER mechanism. Gibbs free energy profiles along the reaction pathway of CoMnP (c) and W-CoMnP (d). The differential charge density diagram of W-CoMnP catalyzer (yellow: loss electrons, blue: obtain electrons) of top (e) and slide (f). (g) Schematic diagram of OER process.

Fig. 9. Density of states projected on the d-states of Co in W-CoMnP (a), Mn in W-CoMnP (b), Co in CoMnP (c), and Mn in CoMnP (d). Dashed-dotted lines and the numbers show the position of d-band center. Eg density of states projected on the d-states of Co in W-CoMnP(e), Mn in W-CoMnP (f), Co in CoMnP (g), and Mn in CoMnP (h). (i) The atomic structure of Mn and its typical valence states in cathode materials. (j) Schematic diagrams of Mn 3d orbitals with high-/low-spin Mn3+ ions. (k) Schematic diagram of octahedral Mn based material before and after J-T distortion. (l) The molecular orbital energy diagram of the octahedral Mn based material and the electronic orbitals of Mn2+/Mn3+/Mn4+ ions.

Fig. 10. The trade-off between CoNi based catalysts and Mn based catalysts.

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