Synergistic phosphorized NiFeCo and MXene interaction inspired the formation of high-valence metal sites for efficient oxygen evolution

doi:10.1016/j.jmst.2021.08.007

Abstract

Abstract:

Exploring low-cost, high-performance, and stable electrocatalysts toward the oxygen evolution reaction (OER) is highly desired but remains challenging. Transition metal hydroxide has been wildly utilized as a promising candidate, but practical implementation is impeded by insufficient catalytic activity, easy agglomeration, and poor conductivity. Here, we report that both phosphorization and combination with MXnene can improve the catalysts’ intrinsic activity and conductivity. Besides, MXene also prevents the agglomeration of the nanoparticles, resulting in the enhanced exposure of active sites. Experimental characterizing and density functional theory simulations revealed that P species can attract electrons to promote the formation of high-valence states of adjacent metal atoms, and coupling MXene support can effectively modulate the electronic structure and optimize the d-band center, which boosts the OER performance. Consequently, the optimized NiFeCoP/Mxene catalyst exhibits a low overpotential of 240 mV at a current density of 10 mA cm^-2, a small Tafel slope of 55 mV dec^-1, and superior long-term stability of 40 h in 1 M KOH electrolyte, which is superior to other counterparts.

Key words: Transition metal phosphide, Ti₃C₂T_x Mxene, Electrocatalyst, Oxygen evolution

Ning Li, Jingrui Han, Kaili Yao, Mei Han, Zumin Wang, Yongchang Liu, Lihua Liu, Hongyan Liang. Synergistic phosphorized NiFeCo and MXene interaction inspired the formation of high-valence metal sites for efficient oxygen evolution[J]. J. Mater. Sci. Technol., 2022, 106: 90-97.

Figures/Tables 5

Fig. 1. (a) Schematic illustration for the preparation of NiFeCoP/MXene, (b) XRD patterns, (c) SEM image, (d) HRTEM image and (e) EDS elemental mapping images of the NiFeCoP/MXene.

Fig. 2. OER performance measurement in 1 M KOH. (a) LSV polarization curves, (b) overpotential at the current density of 10 mA cm-2 and (c) Tafel plots of NiFeCoP/Mxene, NiFeCo-OH/MXene, NiFeCoP and NiFeCo-OH, (d) Nyquist plots of the as-prepared samples, (e) LSV polarization curves of NiFeCoP/MXene before and after 5000 CV cycles, (f) chronoamperomery curve at an overpotential of 300 mV.

Fig. 3. (a) Ni 2p, (b) Fe 2p and (c) Co 2p XPS spectra of NiFeCo-OH, NiFeCo-OH/MXene and NiFeCoP/MXene, (d) P 2p XPS spectrum of NiFeCoP/MXene.

Fig. 4. In situ Raman spectra of (a) NiFeCo-OH, (b) NiFeCo-OH/MXene, (c) NiFeCoP and (d) NiFeCoP/MXene.

Fig. 5. Optimized structure for (a) NiFeCo-OH, (b) NiFeCo-OH/MXene, and (c) NiFeCoP/MXene theoretical model (red: O, white: H, green: Ni, blue: Co, orange: Fe, dark gray: C, light gray: Ti), (d) density of states for NiFeCoP/MXene, NiFeCo-OH/MXene and NiFeCo-OH (the energy is referred to the Fermi level), (e) projected density on to 3d orbitals Ni of NiFeCo-OH and NiFeCoP/MXene (the dashed lines indicate the d-band center for each system). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

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