Multi-shell Hollow FeP Microspheres as Efficient Electrocatalyst for Hydrogen Evolution at All pH Values †

doi:10.7503/cjcu20190308

Abstract

Abstract:

Multi-shell hollow microspheres of iron phosphide(FeP) were synthesized by directly phosphorization of iron oxide microspheres. The prepared microstructures were characterized by SEM, TEM, XRD and XPS. Then their performance for hydrogen evolution reaction(HER) of FeP was investigated in a standard three-electrode system. The results show that the FeP/CNT composite doped with carbon nanotube(CNT) exhibit good catalytic behavior towards HER not only at extreme pH values(0 and 14), but also in neutral medium(pH=7), the Tafel slope are 55, 64.9, 163.2 mV/dec in 0.5 mol/L H₂SO₄, 1.0 mol/L KOH and 1.0 mol/L Na₂SO₄, respectively. When the current density reaches 10 mA/cm ², the overpotentials are 97, 169, 495 mV(vs. RHE), respectively.

Key words: FeP, Multi-shell hollow microsphere, Electrocatalyst, Hydrogen evolution reaction

CLC Number:

O646.51

TrendMD:

TANG Jiayi,YAO Junjie,ZHANG Xiaojun,MA Liang,ZHANG Tingmei,NIU Zheng,CHEN Xiangzhen,ZHAO Liang,JIANG Lin,SUN Yinghui. Multi-shell Hollow FeP Microspheres as Efficient Electrocatalyst for Hydrogen Evolution at All pH Values ^†[J]. Chem. J. Chinese Universities, 2019, 40(11): 2340.

Figures/Tables 10

Fig.1 SEM(A), TEM(B) and HRTEM(C) images of multi-shell hollow porous FeP microspheres

Fig.2 STEM image(A) and the corresponding EDX elemental mapping images of Fe-K(B), Fe-L(C) and P-K(D) in a single FeP microsphere

Fig.3 XRD pattern(A) and XPS spectra(B, C) of FeP microspheres (B) Fe2p; (C) P2p.

Fig.4 SEM image of FeP/CNT microspheres

Fig.5 HER performances in 0.5 mol/L H2SO4 solution (A) Polarization curves(scan rate: 10 mV/s); (B) Tafel plots; (C) polarization stability plot of FeP/CNT(scan rate 500 mV/s); (D) impedance plots. a. Pt/C; b. FeP/CNT; c. FeP; d. CNT. Inset is current density curves for 10 h under constant overpotential of 97 mV.

Electrolyte	a/mV	b /(mV·dec^-1)	$j 0$ /(mA·cm^-2)
0.5 mol/L H₂SO₄	220	55.0	0.266
1.0 mol/L KOH	320	64.9	0.021
1.0 mol/L Na₂SO₄	920	163.2	0.012

Electrolyte	a/mV	b /(mV·dec^-1)	$j 0$ /(mA·cm^-2)
0.5 mol/L H₂SO₄	220	55.0	0.266
1.0 mol/L KOH	320	64.9	0.021
1.0 mol/L Na₂SO₄	920	163.2	0.012

Catalyst	Electrolyte	η₁₀/mA	Tafel slope/(mV·dec^-1)	Ref.
FeP/CNT	0.5 mol/L H₂SO₄	97	55	This work
	1.0 mol/L KOH	169	64.9	This work
	1.0 mol/L Na₂SO₄	495	163.2	This work
FeP powder/carbon	0.5 mol/L H₂SO₄	110	57	[20]
	1.0 mol/L KOH	185	93	[20]
FeP bond carbon nanowires networks	0.5 mol/L H₂SO₄	256	75.8	[30]
Nanoporous FeP nanosheets	0.5 mol/L H₂SO₄	230	67	[31]
FeP nanowires	0.5 mol/L H₂SO₄	96	37	[32]
	1.0 mol/L KOH	194	67	[32]
FeP NPs@NPC	0.5 mol/L H₂SO₄	130	67	[33]
	1.0 mol/L KOH	214	82	[33]
	1.0 mol/L PBS	386	136	[33]
FeP NPs @hollow carbon nanobox	0.5 mol/L H₂SO₄	88	49	[34]
	1.0 mol/L KOH	180	71	[34]
Ni-doped FeP/C hollow nanorods	0.5 mol/L H₂SO₄	72	54	[21]
	1.0 mol/L KOH	95	72	[21]
	1.0 mol/L PBS	117	70	[21]
FeP NCs@NCNs	0.5 mol/L H₂SO₄	114	84	[35]
	1.0 mol/L KOH	205	70	[35]
	1.0 mol/L PBS	409	92	[35]
CoP/Co₂P NPs@NC	0.5 mol/L H₂SO₄	126	79	[36]
	1.0 mol/L KOH	198	82	[36]
	1.0 mol/L PBS	459	——	[36]
NiP NPs	0.5 mol/L H₂SO₄	115	46	[37]

Fig.6 HER performances in 1.0 mol/L KOH solution (A) Polarization curves(scan rate: 10 mV/s); (B) Tafel plot; (C) polarization stability plot of FeP(scan rate 500 mV/s); (D) impedance plots. a. Pt/C; b. FeP/CNT; c. FeP; d. CNT. The inset is current density curves for 10 h under constant overpotential of 169 mV.

Fig.7 HER performances in 1.0 mol/L Na2SO4 solution (A) Polarization curves(scan rate: 10 mV/s); (B) Tafel plot. a. Pt/C; b. FeP/CNT; c. FeP; d. CNT.

Fig.8 Exchange current densities of FeP/CNT electrocatalyst in different electrolytes calculated by the extrapolation of Tafel curves Electrolyte: (A) 0.5 mol/L H2SO4; (B) 1.0 mol/L KOH; (C) 1.0 mol/L Na2SO4 solution.

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