Phosphorus-doped Fe7S8@C nanowires for efficient electrochemical hydrogen and oxygen evolutions: Controlled synthesis and electronic modulation on active sites

doi:10.1016/j.jmst.2020.08.060

Abstract

Abstract:

Developing low-cost, efficient, and stable non-precious-metal electrocatalysts with controlled crystal structure, morphology and compositions are highly desirable for hydrogen and oxygen evolution reactions. Herein, a series of phosphorus-doped Fe₇S₈ nanowires integrated within carbon (P-Fe₇S₈@C) are rationally synthesized via a one-step phosphorization of one-dimensional (1D) Fe-based organic-inorganic nanowires. The as-obtained P-Fe₇S₈@C catalysts with modified electronic configurations present typical porous structure, providing plentiful active sites for rapid reaction kinetics. Density functional calculations demonstrate that the doping Fe₇S₈ with P can effectively enhance the electron density of Fe₇S₈ around the Fermi level and weaken the Fe-H bonding, leading to the decrease of adsorption free energy barrier on active sites. As a result, the optimal catalyst of P-Fe₇S₈-600@C exhibits a relatively low overpotential of 136 mV for hydrogen evolution reaction (HER) to reach the current density of 10 mA/cm², and a significantly low overpotential of 210 mV for oxygen evolution reaction (OER) at 20 mA/cm² in alkaline media. The work presented here may pave the way to design and synthesis of other prominent Fe-based catalysts for water splitting via electronic regulation.

Key words: Ron sulfide, P-doping, Hydrogen and oxygen evolution reaction, Electrocatalysis

Thanh-Tung Le, Xiao Liu, Peijun Xin, Qing Wang, Chunyan Gao, Ye Wu, Yong Jiang, Zhangjun Hu, Shoushuang Huang, Zhiwen Chen. Phosphorus-doped Fe₇S₈@C nanowires for efficient electrochemical hydrogen and oxygen evolutions: Controlled synthesis and electronic modulation on active sites[J]. J. Mater. Sci. Technol., 2021, 74: 168-175.

Figures/Tables 7

Fig. 1. (a) Schematic illustration for the preparation of P-Fe7S8@C NWs. (b, d, f) SEM images and (c, e, g) TEM images of (b, c) Fe7S8@C, (d, e) P-Fe7S8-300@C, (f, g) P-Fe7S8-600@C, and (h, i) P-Fe7S8-900@C samples. (j, k) Magnified TEM, (l, m) HRTEM images, and (n) SAED pattern of the P600-Fe7S8@C catalyst.

Fig. 2. (a) XRD pattern of the as-synthesized Fe7S8@C, P-Fe7S8-300@C, P-Fe7S8-600@C and P-Fe7S8-900@C. The XPS (b) survey spectrum and corresponding (c) Fe 2p, (d) S 2p, (e) C 1s, and (f) P 2p spectra of P-Fe7S8-600@C.

Fig. 3. Evaluation of HER performance: (a) The LSV profiles, (b) the Tafel plots, and (c) summary of the overpotentials and the corresponding Tafel plots at 10 mA/cm2. (d) The Cdl of different catalysts. (e) The TOF values of different catalysts at the overpotential of 200 mV. (f) LSV curves of P-Fe7S8-600@C before and after 1000 cycles at 100 mA/cm2. The insert showed the long-term HER stability test of the P-Fe7S8-600@C at a current density of 10 mA/cm2.

Table 1 Summarization of HER performance of the as-synthesized catalysts.

Catalysts	η₁₀ (mV)	Tafel plot (mV/dec)	C_dl (mF/cm²)
Fe₇S₈@C	212	140.2	2.10
P-Fe₇S₈-300@C	183	128.5	8.42
P-Fe₇S₈-600@C	136	113.9	17.78
P-Fe₇S₈-900@C	156	125.3	16.61

Fig. 4. The optimized crystal structure of (a) Fe7S8 and (b) P-Fe7S8. (c) Schematic illustration of water activation, H* intermediate formation and hydrogen generation processes on P-doped Fe7S8 catalyst in 1.0 M KOH. (d) The calculated reaction energy diagram at different stages of H2O dissociation toward H2 generation in basic solution. (e) Total DOS of Fe7S8 and P-Fe7S8. The Fermi level is set at 0 eV. Fe atoms: dark green; S atoms: yellow; P atoms: blue; O atoms: red; H atoms: lilac.

Fig. 5. Evaluation of OER performance: (a) The LSV profiles, (b) the Tafel plots, and (c) summary of the overpotentials and the corresponding Tafel plots at 20 and 50 mA cm-2. (d) The Cdl of different catalysts. (e) The TOF values of different catalysts at the overpotential of 200 mV. (f) LSV curves of P-Fe7S8-600@C before and after 1000 cycles at 100 mA/cm2. The insert showed the long-term OER stability test of the P-Fe7S8-600@C at a current density of 10 mA/cm2.

Table 2 Summarization of OER performance of the as-synthesized catalysts.

Catalysts	η₂₀ (mV)	η₅₀ (mV)	Tafel plot (mV/dec)	C_dl (mF/cm²)
Fe₇S₈@C	289	307	47.6	3.19
P-Fe₇S₈-300@C	233	253	47.1	6.21
P-Fe₇S₈-600@C	210	243	42.5	11.01
P-Fe₇S₈-900@C	221	249	43.5	7.50

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Phosphorus-doped Fe₇S₈@C nanowires for efficient electrochemical hydrogen and oxygen evolutions: Controlled synthesis and electronic modulation on active sites

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