Fe2P nanoparticles embedded on Ni2P nanosheets as highly efficient and stable bifunctional electrocatalysts for water splitting

doi:10.1016/j.jmst.2021.06.080

Abstract

Abstract:

It is urgent to develop highly efficient, stable and low-cost bifunctional electrocatalysts for overall water splitting. Herein, an iron-nickel phosphide (Fe₂P/Ni₂P) heterostructure, constructed by Fe₂P nanoparticles embedded on Ni₂P nanosheets, is strategically fabricated on nickel foam via a facile process. As a bifunctional electrocatalyst, the Fe₂P/Ni₂P heterostructure delivers a very low overpotential of 64 mV (or 185 mV) to reach current density of 10 mA cm^-2 for hydrogen (or oxygen) evolution reaction. When simultaneously employed as both the anode and cathode electrodes, it demonstrates an ultralow cell voltage of 1.49 V@10 mA cm^-2 for full water splitting with nearly 100% Faradaic efficiency, and superior long-term stability even over 100 h. Density functional theory calculations manifest that a strong heterointerface interaction could cause electron redistribution near the Fe₂P/Ni₂P heterointerface and optimize the ΔG_H* of P sites, thus enhancing catalytic activity. Additionally, the 3D porous heterostructure is benefit to expose rich active sites and facilitate ion diffusion and gas bubble release, thus promoting the catalytic performance. This work opens up a new strategical approach for rational design of metal phosphide-based heterostructures as highly efficient and stable bifunctional electrocatalysts for water splitting.

Key words: Heterostructure, Nanosheets, Electrocatalyst, Overall water splitting

Xinqiang Wang, Bin Wang, Yuanfu Chen, Mengya Wang, Qi Wu, Katam Srinivas, Bo Yu, Xiaojuan Zhang, Fei Ma, Wanli Zhang. Fe₂P nanoparticles embedded on Ni₂P nanosheets as highly efficient and stable bifunctional electrocatalysts for water splitting[J]. J. Mater. Sci. Technol., 2022, 105: 266-273.

Figures/Tables 6

Fig. 1. (a) Schematic representation of Fe2P/Ni2P HS/NF fabrication strategy. (b) SEM image of Ni(OH)2 NS/NF. (c, d) SEM images of Fe2P/Ni2P HS/NF. (e) TEM image of Fe2P/Ni2P HS. (f) HRTEM image of Fe2P/Ni2P HS. (g) The selected area electron diffraction of Fe2P/Ni2P HS. (h-k) STEM and corresponding EDS elemental mapping images of Fe2P/Ni2P HS.

Fig. 2. (a) Powder X-ray diffraction patterns of bare NF, Ni2P NS/NF, and Fe2P/Ni2P HS/NF. (b) The zoom-in XRD patterns of Ni2P NS/NF and Fe2P/Ni2P HS/NF. The XPS core level spectra of Ni2P NS/NF and Fe2P/Ni2P HS/NF: (c) Ni 2p, (d) Fe 2p, and (e) P 2p. (f) Valence-band XPS spectra of Ni2P NS/NF and Fe2P/Ni2P HS/NF.

Fig. 3. (a) Polarization curves of NF, Ni2P NS/NF, Fe2P NP/NF, Fe2P/Ni2P HS/NF, and RuO2/NF electrodes. (b) The OER activity comparisons at overpotentials of 10 and 50 mA cm-2 for NF, Ni2P NS/NF, Fe2P NP/NF, Fe2P/Ni2P HS/NF, and RuO2/NF. (c) Tafel slopes of NF, Ni2P NS/NF, Fe2P NP/NF, Fe2P/Ni2P HS/NF, and RuO2/NF. (d) Nyquist plots of Ni2P NS/NF, Fe2P NP/NF, and Fe2P/Ni2P HS/NF. (e) Estimated Cdl and corresponding ECSA of Ni2P NS/NF, Fe2P NP/NF, and Fe2P/Ni2P HS/NF. (f) Chronoamperometric current density curve (i-t) of Fe2P/Ni2P HS/NF (inset: corresponding CV cycling stability curves).

Fig. 4. (a) LSV polarization curves of NF, Ni2P NS/NF, Fe2P NP/NF, Fe2P/Ni2P HS/NF, and Pt/C/NF electrodes. (b) The HER activity comparisons at overpotentials of 10 and 50 mA cm-2 for NF, Ni2P NS/NF, Fe2P NP/NF, Fe2P/Ni2P HS/NF, and Pt/C/NF electrodes. (c) Tafel slopes of NF, Ni2P NS/NF, Fe2P NP/NF, Fe2P/Ni2P HS/NF, and Pt/C/NF. (d) Nyquist plots of Ni2P NS/NF, Fe2P NP/NF, and Fe2P/Ni2P HS/NF. (e) Estimated Cdl and corresponding ECSA of Ni2P NS/NF, Fe2P NP/NF, and Fe2P/Ni2P HS/NF. (f) Chronoamperometric current density curve (i-t) of Fe2P/Ni2P HS/NF (inset: corresponding CV cycling stability curves).

Fig. 5. (a) Optimized schematic models for Fe2P, Ni2P, and Fe2P/Ni2P HS with H adsorbed on adsorption sites. (b) Corresponding Gibbs free-energy diagrams of Fe2P(001), Ni2P(001), and Fe2P/Ni2P HS. (c) Charge density difference plot at the Fe2P/Ni2P interface. (Yellow stands for electron accumulation and cyan indicates the electron depletion) (d) The density of states (DOS) plots of the optimized Fe2P, Ni2P and Fe2P/Ni2P HS.

Fig. 6. (a) LSV polarization curves of NF||NF, RuO2/NF||Pt/C/NF, and Fe2P/Ni2P HS/NF||Fe2P/Ni2P HS/NF couples in 1.0 M KOH. (b) The water splitting performance comparison (ƞ10) between Fe2P/Ni2P HS/NF and recently reported catalysts. (c) The digital photograph of water electrolysis for Fe2P/Ni2P HS/NF||Fe2P/Ni2P HS/NF couple in a two-electrode device. (d) Theoretically calculated quantities of O2 and H2 versus its actual production of Fe2P/Ni2P HS/NF||Fe2P/Ni2P HS/NF couple under a constant current density of 10 mA cm-2 in 1.0 M KOH. (e) Chronoamperometric current density curve (i-t) of Fe2P/Ni2P HS/NF||Fe2P/Ni2P HS/NF couple in 1.0 M KOH.

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Fe₂P nanoparticles embedded on Ni₂P nanosheets as highly efficient and stable bifunctional electrocatalysts for water splitting

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