Heteroatom doping and surface engineering co-modulated electronic structure of prussian blue analogs for efficient overall water splitting

doi:10.1016/S1872-2067(26)65222-9

Abstract

Abstract:

Overall water splitting based on Prussian blue analogues (PBAs) electrocatalysts has attracted increasing attention due to its tunable structures, facile synthesis, reducing costs and promoting green energy applications. However, it is usually hindered by structural instability and limited active sites of electrocatalysts. Herein, we have constructed vanadium-doped and surface-phosphated NiFeP PBAs/Ni foam (V-NiFeP PBAs/NF) nanocubes (NCs) with excellent stability and catalytic performance by heteroatom doping and surface engineering strategy. Benefiting from optimized electronic structures and reconstructed active oxyhydroxides, the V-NiFeP PBAs/NF NCs as pre-catalysts exhibited exceptional oxygen evolution reaction (OER) activity in alkaline media (~257 mV at 100 mA·cm^-2), which was ~42% lower than commercial RuO₂ (~443 mV) and excellent stability (500 h at 50 mA·cm^-2). Experimental and theoretical results indicated that the V-doping of the V-NiFeP PBAs/NF NCs could effectively modulate its electronic configuration by upward-shifting d-band center of Ni and Fe, thereby increasing its conductivity and active sites. The V-NiFeP PBAs/NF NCs had lower reaction energy barrier for lattice oxygen mechanism pathway than that for adsorption evolution mechanism pathway. The V-NiFeP PBAs/NF NCs had excellent hydrogen evolution (~170 mV at 20 mA·cm^-2) and overall water splitting performance (~1.59 V at 10 mA·cm^-2). This work provides a synthetic paradigm for in-situ growth of surface-engineered PBAs on conductive substrates and offers fundamental insights for designing high-performance OER catalysts.

Key words: Transition metal phosphide, V-doping, Surface reconstruction, Oxygen evolution reaction, Overall water splitting, Lattice oxygen mechanism

Yuchan Liu, Wenjing Gao, Qintong Huang, Xiaoxiong Liu, Huihuan Ouyang, Rongkai Ye, Minsi Li, Jianqiang Hu. Heteroatom doping and surface engineering co-modulated electronic structure of prussian blue analogs for efficient overall water splitting[J]. Chinese Journal of Catalysis, 2027, 92: 170-181.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65222-9

https://www.cjcatal.com/EN/Y2027/V92/I1/170

Figures/Tables 6

Fig. 1. Schematic illustration of the V-NiFeP PBAs/NF nanocubes fabricated by the present study.

Fig. 2. SEM images of NiV LDHs (a), V-NiFe PBAs/NF (b), NiFe PBAs/NF (c) and V-NiFeP PBAs/NF NCs (d). (e,f) HRTEM images of the V-NiFeP PBAs/NF NCs. (g-l) STEM and EDS elemental mappings of the V-NiFeP PBAs/NF NCs.

Fig. 3. High-resolution XPS spectra of Ni 2p (a), Fe 2p (b) and V 2p (c) of NiFe PBAs/NF, V-NiFe PBAs/NF and V-NiFeP PBAs/NF NCs. XANES spectra at Ni K-edge (d) and Fe K-edge (e) of NiFe PBAs/NF, V-NiFe PBAs/NF and V-NiFeP PBAs/NF NCs, in which the inset plots are enlarged plots of selected area. (f,g) Fourier-transformed EXAFS spectra of NiFe PBAs/NF, V-NiFe PBAs/NF, V-NiFeP PBAs/NF NCs and references (Ni and Fe foils). (h,i) Wavelet transforms of k3-weighted Ni K-edge and Fe K-edge EXAFS signals of V-NiFeP PBAs/NF NCs.

Fig. 4. OER performance of the NiFe PBAs/NF, V-NiFe PBAs/NF, V-NiFeP PBAs/NF, RuO2/NF and blank NF. LSV curves (a), overpotential at the current density of 50 and 100 mA·cm-2 (b), Tafel plots (c), EIS plots (d), and Cdl versus scan rates (e). (f) Chronopotentiometry curve of the V-NiFeP PBAs/NF NCs at 50 mA·cm-2 for 500 h (inset: LSV of V-NiFeP PBAs/NF NCs before and after OER stability test).

Fig. 5. HER performance of NiFe PBAs/NF, V-NiFe PBAs/NF, V-NiFeP PBAs/NF NCs, Pt/NF and blank NF. LSV curves (a), overpotential at the current density of 20 mA·cm-2 (b), Tafel plots (c), and EIS plots (d) of water-splitting performance of the electrolyzer assembled with V-NiFeP PBAs/NF ||V-NiFeP PBAs/NF. LSV curves (e) and stability test (f) at the current density of 50 mA·cm-2 of the V-NiFeP PBAs/NF ||V-NiFeP PBAs/NF electrolyzer in 1 M KOH, inset shows the photograph of the assembled electrolyzer.

Fig. 6. (a) LSV curves of V-NiFeP PBAs/NF NCs in KOH electrolyte with different pH values. (b) LSV curves of V-NiFeP PBAs NCs in different electrolytes. Gibbs free energy diagrams of NiFeOOH/NF and V-NiFeOOH/NF at U = 1.23 V for LOM (c) and AEM (d) pathways. (e) PDOS of NiFeOOH/NF and V-NiFeOOH/NF. (f) Charge density difference of the V-NiFeOOH/NF, in which the yellow and blue regions represent electron accumulation and depletion, respectively. Schematic plot of OER pathway for LOM (g) and AEM (h) based on Fe sites in the optimized model of the V-NiFeOOH/NF with different reaction intermediates.

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