Construction of Ni2P/CoP interface for highly efficient electrolysis of urea-assisted hydrogen production at industrial current densities

doi:10.1016/S1872-2067(24)60198-1

Abstract

Abstract:

Interface chemical modulation strategies are considered as promising method to prepare electrocatalysts for the urea oxidation reaction (UOR). However, conventional interface catalysts are generally limited by the inherent activity and incompatibility of the individual components themselves, and the irregular charge distribution and slow charge transfer ability between interfaces severely limit the activity of UOR. Therefore, we optimized and designed a Ni₂P/CoP interface with modulated surface charge distribution and directed charge transfer to promote UOR activity. Density functional theorycalculations first predict a regular charge transfer from CoP to Ni₂P, which creates a built-in electric field between Ni₂P and CoP interface. Optimization of the adsorption/desorption process of UOR/HER reaction intermediates leads to the improvement of catalytic activity. Electrochemical impedance spectroscopy and ex situ X-ray photoelectron spectroscopy characterization confirm the unique mechanism of facilitated reaction at the Ni₂P/CoP interface. Electrochemical tests further validated the prediction with excellent UOR/HER activities of 1.28 V and 19.7 mV vs. RHE, at 10 mA cm^-2, respectively. Furthermore, Ni₂P/CoP achieves industrial-grade current densities (500 mA cm^-2) at 1.75 V and 1.87 V in the overall urea electrolyzer (UOR||HER) and overall human urine electrolyzer (HUOR||HER), respectively, and demonstrates considerable durability.

Key words: Interface chemical strategy, Theoretical predictions, Advanced interface construction, Directed charge transfer, Urea oxidation reaction

Borong Lu, Chunmei Lv, Ying Xie, Kai Zhu, Ke Ye, Xiaojin Li. Construction of Ni₂P/CoP interface for highly efficient electrolysis of urea-assisted hydrogen production at industrial current densities[J]. Chinese Journal of Catalysis, 2025, 69: 163-175.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60198-1

https://www.cjcatal.com/EN/Y2025/V69/I2/163

Figures/Tables 6

Fig. 1. (a) Schematic representation of directional charge transfer at the Ni2P/CoP interface. (b) TDOS of CoP, Ni2P, and Ni2P/CoP. (c) The work function of CoP, Ni2P, and Ni2P/CoP. (d) Schematic diagram of Ф for CoP and Ni2P. (e) Schematic of electron transfer from CoP to Ni2P. (f) Gibbes free energy diagrams of various catalysts for the adsorption of H*. (g) Gibbes free energy diagrams of various catalysts during UOR processes.

Fig. 2. (a) Schematic diagram of preparation process of Ni2P/CoP. The SEM images of Ni2P (b,c) and Ni2P/CoP (d,e). TEM (f,g) and the HRTEM (h) images of Ni2P/CoP. HAADF (i) and the EDS mapping (j-l) images of Ni2P/CoP (Ni, Co, P elements).

Fig. 3. Characterization of the electronic structure of Ni2P/CoP. XPS spectra: Co 2p (a), Ni 2p (b), and Co 2p (c) of CoP and Ni2P/CoP. XAFS characterizations: (d) normalized XANES spectra of Co K-edge. (e) FT-EXAFS spectra at the Co K-edge. (f) WT plots for the k3-weighted EXAFS signals of Co K-edge for Ni2P/CoP. (g) Normalized XANES spectra of Ni K-edge. (h) Corresponding FT-EXAFS spectra. (i) WT plots for the k3-weighted EXAFS signals of Co K-edge for CoP.

Fig. 4. (a) The LSV plots (with iR compensation) for the OER and UOR of Ni2P/CoP with a scan rate of 5 mV s-1. (b) UOR LSV plots of related catalysts in 1 mol L?1 KOH with 0.5 mol L?1 urea. (c) Tafel slopes. (d) The measurements of Cdl. (e) Corresponding ECSA. (f) The LSV plots for HER of Ni2P/CoP and other electrocatalysts with a scan rate of 5 mV s-1 in 1 mol L?1 KOH. (g) Corresponding Tafel Slope. (h) Exchange current density (j0) of electrocatalysts. (i) The measurements of Cdl.

Fig. 5. (a) LSV plots of Ni2P/CoP in HER||UOR and HER||OER. (b) LSV plots of Ni2P/CoP and catalysts in HER||UOR. (c) Comparison of HER||UOR performance with previously reported catalysts. (d) LSV plots in HER||HUOR. (e) UV spectrum of Ni2P/CoP. (f) Corresponding urea degradation rate. (g) Faradaic efficiency in systems HER||UOR and HER||HUOR. (h) Chronopotentiometry tests of Ni2P/CoP in HER||UOR and HER||HUOR under 500 mA c?2.

Fig. 6. (a,b) Dynamic evaluation of the UOR reaction mechanism of catalysts: advanced UOR reaction mechanism diagram for Ni2P/CoP interface. Bode plots of Ni2P (c), CoP (d), and Ni2P/CoP (e). Ex situ XPS analysis for Ni 2p of Ni2P/CoP (f) and (g). (h?j) In situ optical microscopy of Ni2P/CoP during the dynamics of the HER reaction.

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Construction of Ni₂P/CoP interface for highly efficient electrolysis of urea-assisted hydrogen production at industrial current densities

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