Preparation of Nanoporous Ni and NiO and Their Electrocatalytic Activities for Oxygen Evolution Reaction †

doi:10.7503/cjcu20190340

Abstract

Abstract:

Nanoporous Ni was prepared by a combined method of rapid quenching and dealloying, and then the prepared samples were heat-treated to synthesize the nanoporous NiO. The phase, morphology, microstructure and pore-size distribution of nanoporous Ni and NiO were analyzed by X-ray diffraction(XRD), scanning electron microscopy(SEM), transmission electron microscopy(TEM) and N₂ adsorption-desorption analysis, respectively. Their electrochemical performance was investigated by cyclic voltammetry, electrochemical stea-dy-state polarization and electrochemical impendence spectroscopy(EIS). The results show that the nanoporous Ni obtained from Ni₃₀Al₇₀ has multi-stage nanoporous structure, when the current density is 10 mA/cm ², the oxygen evolution overpotential is only 224 mV, the exchange current density is 0.63297 mA/cm ², and the apparent activation free energy is 40.297 kJ/mol; after 1000 cycles of voltammetry, the overpotential decreases by 5 mV(j=10 mA/cm ²), showing fine catalysis stability and durability.

Key words: Rapid quenching, Dealloying, Nanoporous Ni, Electrocatalytic activity, Oxygen evolution reaction

CLC Number:

O646.5

TrendMD:

REN Xiangrong,ZHOU Qi. Preparation of Nanoporous Ni and NiO and Their Electrocatalytic Activities for Oxygen Evolution Reaction ^†[J]. Chem. J. Chinese Universities, 2020, 41(1): 162.

Figures/Tables 22

Fig.1 XRD patterns of Ni25Al75(a) and Ni30Al70(b) alloys

Fig.2 XRD patterns of dealloyed Ni25Al75(a) and Ni30Al70(b)

Alloy	w(%)
Alloy	O	Ni	Al
Ni₂₅Al₇₅	7.35	88.55	4.10
Ni₃₀Al₇₀	5.27	91.54	3.18

Fig.3 SEM images of dealloyed Ni25Al75(A) and Ni30Al70(B)

Fig.4 TEM(A, C) and HRTEM(B, D) images of dealloyed Ni25Al75(A, B) and Ni30Al70(C, D) The insets in upper left corner and the lower right corner of (B) and (D) show a local enlarged image and a selected area electron diffraction pattern of the corresponding samples, respectively.

Fig.5 XRD patterns of NiO formed from Ni25Al75(a) and Ni30Al70(b)

Fig.6 XPS spectra of Ni2p(A) and O1s(B) of NiO

Fig.7 SEM images of NiO formed from Ni25Al75(A) and Ni30Al70(B)

Fig.8 TEM(A, C) and HRTEM(B, D) images of NiO formed from Ni25Al75(A, B) and Ni30Al70(C, D) The insets in the upper left corner and the lower right corner of (B) and (D) show a local enlarged image and a selected area electron diffraction of the corresponding samples, respectively.

Fig.9 N2 adsorption-desorption isotherms(A1—C1) and the pore size distributions(A2—C2) of Ni and NiO (A) Nanoporous Ni formed from Ni25Al75; (B, C) nanoporous Ni and NiO formed from Ni30Al70, respectively.

Fig.10 Anodic polarization plots of the Ni, NiO electrode(A) and overpotential histogram of the Ni, NiO electrodes obtained from graph(A) at 10 mA/cm2(B) a. Ni from Ni25Al75; b. Ni from Ni30A70; c. NiO from Ni25Al75; d. NiO from Ni30Al70; e. foam Ni.

Electrode	b/(mV·dec^-1)	a/mV	j⁰/(mA·cm^-2)
Ni from Ni₂₅Al₇₅	261.09	1106.49	0.05781
Ni from Ni₃₀Al₇₀	194.06	620.72	0.63297
NiO from Ni₂₅Al₇₅	201.90	846.87	0.06390
NiO from Ni₃₀Al₇₀	232.23	769.06	0.48794

Fig.11 Tafel curves of nanoporous Ni(A) and NiO(B) obtained from Ni30Al70 at different temperatures in 1 mol/L NaOH solution and OER Arrhenius plots on the Ni, NiO electrode formed from Ni30Al70 alloy(C)

Fig.12 Nyquist plots for the Ni(A), NiO(B) electrodes at equilibrium potential Insets of (A) are equivalent circuit models of nanoporous Ni formed from Ni25Al75(up) and Ni30Al70(down) alloys, respectively; Insets of (B) are equivalent circuit models of nanoporous NiO formed from Ni25Al75(up) and Ni30Al70(down) alloys, respectively.

Electrode	R_s/(Ω·cm^-2)	CPE/F	R_ct/(Ω·cm^-2)	C/F	Warburg Y₀/ (Ω^-1·cm^-2· $S 0.5$ )
Ni from Ni₂₅Al₇₅	1.724	0.005269	456.6
Ni from Ni₃₀Al₇₀	1.587	0.004831	4.125	0.521	0.1069
NiO from Ni₂₅Al₇₅	1.773	0.01208	173.1
NiO from Ni₃₀Al₇₀	1.864	0.00539	6.754	0.371	0.01938

Electrode	R_s/(Ω·cm^-2)	CPE/F	R_ct/(Ω·cm^-2)	C/F	Warburg Y₀/ (Ω^-1·cm^-2· $S 0.5$ )
Ni from Ni₂₅Al₇₅	1.724	0.005269	456.6
Ni from Ni₃₀Al₇₀	1.587	0.004831	4.125	0.521	0.1069
NiO from Ni₂₅Al₇₅	1.773	0.01208	173.1
NiO from Ni₃₀Al₇₀	1.864	0.00539	6.754	0.371	0.01938

Fig.13 Nyquist plots for the Ni electrode formed from Ni30Al70 alloy at different overpotential(A) and the overpotential vs. lgRtotal-1 plot(B) The inset is equivalent circuit model of nanoporous Ni formed from Ni30Al70 alloy at different overpotential.

η/V	R_s/(Ω·cm^-2)	CPE/F	R_ct/(Ω·cm^-2)	R_p/(Ω·cm^-2)	Warburg Y₀/ (Ω^-1·cm^-2·S^0.5)
0.29	1.551	0.01469	3.021	30.36	0.2573
0.31	1.6	0.0027	1.95	8.745	0.1455
0.33	1.344	0.003215	1.639	7.347	0.1733

E/V(vs. SCE)	10¹⁵/(cm²·s^-1)
E/V(vs. SCE)	Ni	NiO
0.16	3.653	0.3442
0.21	4.628	0.2108
0.26	6.507	0.2685
0.31	15.520	0.3689
0.36	69.970	0.6541

Fig.14 I-t response curve of nanoporous Ni and NiO formed from Ni30Al70 alloy

Electrode	C_dl/μF	S/cm²	r	(j⁰/r)/(mA·cm^-2)
Ni	642333	32117	32117	1.9708×10^-5
NiO	562440	28122	28122	1.7351×10^-5

Fig.15 Electrochemical properties and kinetics of nanoporous Ni formed from Ni30Al70 alloy (A) CV curves at 1—5 mV/s; (B) relationship between lgip and lgv; (C) area contribution of capacitance curve at 5 mV/s; (D) contribution diagram of capacitance at different scanning rates.

Fig.16 Anodic polarization of the Ni and NiO electrode before and after 1000 CV cycles

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