纳米多孔Ni和NiO的制备及电催化析氧性能

doi:10.7503/cjcu20190340

摘要/Abstract

摘要：

采用快速凝固与脱合金相结合的方法制备了纳米多孔Ni, 经热处理氧化获得纳米多孔NiO, 利用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)和氮气吸附-脱附仪(BET)对纳米多孔Ni和NiO的物相、形貌结构和孔径分布进行了表征, 并通过循环伏安、稳态极化和电化学阻抗分析研究了电极的电催化析氧性能. 结果表明, 由Ni₃₀Al₇₀所得纳米多孔Ni具有多层次纳米多孔结构, 在10 mA/cm ²电流密度下析氧过电位仅为224 mV, 交换电流密度为0.63297 mA/cm ², 表观活化自由能为40.297 kJ/mol, 经1000次循环后, 过电位降低了5 mV(j=10 mA/cm ²), 表现出良好的催化稳定性和耐久性; 热处理氧化降低了NiO的比表面积与电化学活性面积, 平衡电位下扩散传质速率明显减小, 析氧活性较Ni电极有所下降.

关键词: 快速凝固, 脱合金化, 纳米多孔镍, 电催化活性, 析氧反应

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

中图分类号:

O646.5

TrendMD:

任向荣,周琦. 纳米多孔Ni和NiO的制备及电催化析氧性能. 高等学校化学学报, 2020, 41(1): 162.

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

图/表 22

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

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

Table 1 Composition of dealloyed Ni25Al75 and Ni30Al70

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.

Table 2 Kinetic parameters for oxygen evolution reaction on different electrodes*

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.

Table 3 Fitted parameters of the electrode equivalent circuit on porous Ni, NiO electrodes at equilibrium potential*

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

Table 3 Fitted parameters of the electrode equivalent circuit on porous Ni, NiO electrodes at equilibrium potential*

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.

Table 4 Fitted parameters of the electrode equivalent circuit on porous Ni electrode formed from Ni30Al70 alloy at different overpotentials

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

Table 5 Diffusion coefficient values of Ni and NiO electrodes formed from Ni30Al70 alloy at different potentials

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

Table 6 Surface parameters of Ni and NiO electrode 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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