Phosphorus vacancy-engineered Ru,Pv-CoP as a hydrogen spillover catalyst for enhanced industrial alkaline water electrolysis

doi:10.1016/S1872-2067(26)65195-9

Abstract

Abstract:

Developing industrial-grade electrocatalysts based on the hydrogen spillover (HSo) mechanism is a key approach for translating lab-scale performance into industrial applications. Herein, a novel HSo catalyst (Ru,P_v-CoP/CF) was constructed by introducing phosphorus vacancies (P_v) into a CoP support decorated with Ru nanocrystals (Ru NCs) and Ru single atoms (Ru SAs) via defect-engineering strategy. The creation of P_v modulates the interfacial properties between Ru species and CoP, enabling electronic coupling between Ru and Co through phosphorus bridging and forming a “Ru-Co” donor-acceptor electron pair. Multidimensional in-situ electrochemical measurements reveal that P_v accelerates the polarization/dissociation of water molecules and the capture/migration of adsorbed hydrogen (H*). Further density functional theory calculations underscore that P_v narrows the work function difference between Ru NC and Ru_SA-CoP, which enhances the electron supply from Ru NC to Co, thereby triggering an efficient H* cross-phase transmission. Specifically, Ru NCs primarily facilitate H₂O dissociation, and the generated H* subsequently spillover to adjacent Co sites for H₂ desorption. Benefiting from the P_v-mediated relay catalysis, the Ru,P_v-CoP/CF catalyst exhibits top-level HER properties in 1.0 mol L^-1 KOH, requiring only 86 mV at an industrial current density of 1.0 A cm^-2 with exceptional durability over 1200 h. This work advances the fundamental understanding of vacancy-guided HSo mechanism, providing unique insights for designing transition metal phosphides-based electrocatalysts for industrial alkaline water electrolysis.

Key words: Hydrogen spillover, Phosphorus vacancies, Ru nanocrystals, Transition metal phosphides, Industrial alkaline water electrolysis

Juan Xiao, Tingting Huang, Xia Liu, Yuying Feng, Guancheng Xu, Li Zhang. Phosphorus vacancy-engineered Ru,P_v-CoP as a hydrogen spillover catalyst for enhanced industrial alkaline water electrolysis[J]. Chinese Journal of Catalysis, 2026, 91: 192-209.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65195-9

https://www.cjcatal.com/EN/Y2026/V91/I12/192

Figures/Tables 8

Scheme 1. Schematic illustration of the synthesis of Ru,Pv-CoP/CF.

Fig. 1. XRD (a), SEM (b,c), TEM (d), AC-STEM (e-h), EELS (i), and TEM-elemental mapping (l-p) images of Ru,Pv-CoP/CF.

Fig. 2. High-resolution XPS spectra of Co 2p (a), P 2p (b) for Ru,Pv-CoP/CF and CoP/CF. (c) Ru 3p for Ru,Pv-CoP/CF and Ru-CoP/CF. EPR spectra (d), the normalized Co K-edge XANES spectra (e) and FT-EXAFS spectra (f) of Ru,Pv-CoP/CF, Ru-CoP/CF, CoP/CF, Co foil and Co2O3. WT-EXAFS spectra for Co K-edge (g), the normalized Ru K-edge (h) XANES spectra, the FT-EXAFS spectra (i-j) of Ru,Pv-CoP/CF, Ru-CoP/CF, Ru foil, RuCl3 and RuO2. WT-EXAFS spectra for Ru K-edge (k) and the R space comparison chart (l) for Ru,Pv-CoP/CF and Ru-CoP/CF. (m) Schematics of the electronic coupling in the Ru-Pv··-Co bridge.

Fig. 3. (a) iR-corrected LSV curves of HER. (b) Overpotentials at current density of 50, 100, 500 and 1000 mA cm-2. (c) Comparison of overpotentials (at 1 A cm-2) and Tafel slopes of various reported self-supported TMP-based HER catalysts. Tafel slope plots (d), double-layer capacitances (e), Nyquist plots (f), and TOF curves (g) of Ru,Pv-CoP/CF, Ru-CoP/CF, Pv-CoP/CF and CoP/CF. (h) TOF values comparison at an overpotential of 100 mV. (i) Mass activity of Ru,Pv-CoP/CF and Ru-CoP/CF. (j) Mass activity comparison at an overpotential of 100 mV. (k) Chronopotentiometric E-t test of Ru,Pv-CoP/CF.

Fig. 4. (a) HER LSV curves of Ru,Pv-CoP/CF in 1.0 mol L-1 KOH electrolyte with various pH. (b) The linear plots of log|j@-50 mV vs. RHE| versus pH for Ru,Pv-CoP/CF, Ru-CoP/CF, Pv-CoP/CF and CoP/CF. (c) CV curves of Ru,Pv-CoP/CF. (d) Plots of hydrogen desorption peak position versus scan rates of the Ru,Pv-CoP/CF and Ru-CoP/CF. (e) EIS-derived Tafel plots. (f) Plots of Cϕ versus η. (g,h) In-situ Raman of Ru,Pv-CoP/CF and Ru-CoP/CF catalysts in 1.0 mol L-1 KOH under various potentials (V vs. RHE). (i-k) Evolution of interfacial water configurations at the interface of Ru,Pv-CoP/CF and Ru-CoP/CF with applied potentials. (l) In-situ ATR-FTIR spectra of Ru,Pv-CoP/CF in 0.1 mol L-1 KOH solution.

Fig. 5. Calculated DOS plots of CoP (a), Ru,Pv-CoP (b). (c) PDOS of Co 3d orbitals of CoP and Ru,Pv-CoP. (d) The work function between the Ru NC, RuSA-CoP and RuSA,Pv-CoP. (e) Planar average potential along the Z-direction. (f) The charge-density difference at the interface. H2O adsorption energy (ΔEH2O*) (g), H2O dissociation (h) and H-adsorption (i) of each system. (j) Hydrogen adsorption transfer pathway diagram. (k) Schematic diagram of the enhanced HER mechanism for Ru,Pv-CoP.

Fig. 6. (a) iR-corrected LSV curves of OER. (b) Overpotentials at current density of 50, 100, 500 and 1000 mA cm-2. (c) Comparison of overpotentials (at 1 A cm-2) and Tafel slopes of various reported self-supported TMP-based OER catalysts. Tafel slope plots (d), double-layer capacitances (e), Nyquist plots (f), operando-EIS tests (g-l) of Ru,Pv-CoP/CF, Ru-CoP/CF, Pv-CoP/CF and CoP/CF. (m) Potential dependence of the phase angle. (n) Chronopotentiometric E-t test of Ru,Pv-CoP/CF.

Fig. 7. AEMWE device performance. (a) Schematic of the AEMWE device. (b) Polarization curves of Ru,Pv-CoP/CF‖Ru,Pv-CoP/CF paired electrodes for AEMWE under 25 °C and 60 °C. (c) The voltage comparison at different current densities. (d,e) Long-term stability of the AEMWE system at 1 A cm-2 under 25 and 60 °C. (f) The comparison of the AEMWE performance of this work with other electrocatalysts reported to date.

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