棒状多孔NiCo2O4粉末的可控制备及其电催化性能研究

doi:10.15541/jim20160140

摘要/Abstract

摘要：

以NiCl₂·6H₂O, CoCl₂·6H₂O和草酸为原料, 利用氨水为配位剂和溶液pH调节剂, 通过配位共沉淀-热分解法制备了棒状多孔NiCo₂O₄粉末, 采用X射线衍射、扫描电镜、透射电镜以及比表面积仪对前驱体和NiCo₂O₄粉末的形貌和结构进行了表征, 考察了溶液pH对前驱体粉末形貌和分散性的影响; 采用循环伏安法和计时电流法研究了乙醇在棒状多孔NiCo₂O₄粉末修饰的玻碳电极上的电催化性能。结果表明: 前驱体的形貌与溶液的pH有关, 热分解得到的NiCo₂O₄粉末继承了前驱体形貌, 呈多孔棒状, 比表面积为89 m²/g, 平均孔径为12.56 nm。该粉末对乙醇具有良好的电催化活性, 氧化峰电流与乙醇浓度、扫速的平方根均呈直线关系, 表明棒状多孔NiCo₂O₄粉末对乙醇的催化反应机理为扩散控制。

关键词: 直接乙醇燃料电池, 电催化, 乙醇氧化, NiCo2O4, 配位共沉淀

Abstract:

Porous rod-like NiCo₂O₄ powders were synthesized by coordination precipitation-thermal decomposition using NiCl₂·6H₂O, CoCl₂·6H₂O and oxalate as starting materials, and ammonia as coordination agent and pH adjustor. Morphology and structure of the precursor and as-prepared porous NiCo₂O₄ rods were characterized by X-ray diffraction, scanning electron microscope, transmission electron microscope, and N₂ adsorption/desorption analysis. Influence of solution pH on the morphology of the precurosr was investigated. Cyclic voltammetry and chronoamperometry were applied to investigate the electrochemical oxidation of ethanol on porous NiCo₂O₄ rods modified glassy carbon electrode in alkaline medium. The results show that morphology of the precursor depends on pH of the solution. The as-prepared NiCo₂O₄ rod inherits the morphology of the precursor and shows porous structures consisting of mesopores with a significantly high specific surface area of 89 m²/g and average pore diameter of 12.56 nm. Porous rod-like NiCo₂O₄ powders exhibit high electrocatalytic activity in cyclic voltammetry measurement. The linear relationships between oxidation peak current and ethanol concentration, and square root of scan rate indicate that ethanol diffusion is a rate-determining step in its oxidation on as-prepared porous NiCo₂O₄ rods.

Key words: direct ethanol fuel cell, electrocatalysis, ethanol oxidation, NiCo2O4 rod, coordination co-precipitation

中图分类号:

O614

湛菁, 陆二聚, 蔡梦, 马雅琳, 张传福. 棒状多孔NiCo₂O₄粉末的可控制备及其电催化性能研究[J]. 无机材料学报, 2017, 32(1): 11-17.

ZHAN Jing, LU Er-Ju, CAI Meng, MA Ya-Lin, ZHANG Chuan-Fu. Controlled Synthesis and Electrocatalytic Performance of Porous Nickel Cobaltite Rods[J]. Journal of Inorganic Materials, 2017, 32(1): 11-17.

图/表 10

图1 不同pH反应溶液合成的NiCo2O4前驱体SEM照片

Fig. 1 SEM images of NiCo2O4 precursors prepared in solution with different Ph(a) 3.0; (b) 5.0; (c) 7.0; (d) 8.0

图2 不同pH反应溶液合成的NiCo2O4前驱体粉末的XRD图谱

Fig. 2 XRD patterns of NiCo2O4 precursor prepared in solution with different pH

图3 棒状NiCo2O4粉末的XRD图谱

Fig. 3 XRD pattern of NiCo2O4 rods powders

图4 多孔棒状钴酸镍的(a)SEM、(b)TEM、(c)HRTEM照片和(d)SAED图案

Fig. 4 (a) SEM, (b) TEM, (c) HRTEM images and (d) SAED pattern of NiCo2O4 rods powders

图5 钴酸镍粉末N2吸脱附等温曲线(a)和孔径分布图(b)

Fig. 5 N2 adsorption/desorption isotherms and pore size distribution of NiCo2O4 rods

图6 1 mol/L NaOH中扫描速度为10 mV/s时, 0和0.1 mol/L乙醇在NiCo2O4/GCE电极的CV曲线图

Fig. 6 CVs of NiCo2O4/GCE in 0 and 0.1 mol/L ethanol in 1 mol/L NaOH solution at scan rate of 10 mV/sInset is the zoomed main panel of line b

图7 在不同乙醇浓度的1 mol/L NaOH中NiCo2O4/GCE电极的CV曲线图(扫描速度为10 mV/s)

Fig. 7 CV curves of NiCo2O4/GCE in 1 mol/L NaOH solution in the presence of ethanol with various concentrations at scan rate of 10 mV/sInset is peak current versus the ethanol concentration

图8 在含0.1 mol/L乙醇的1 mol/L NaOH中, 在不同扫描速度下NiCo2O4/GCE电极的CV曲线图

Fig. 8 CV curves of NiCo2O4/GCE in 1 mol/L NaOH solution contained 0.1 mol/L ethanol at different scan rates (10 mV/s to 50 mV/s)Inset is proportionality of anodic peak currents to the square root of the scan rates

图9 在不同乙醇浓度1 mol/L NaOH中NiCo2O4/GCE电极的极化曲线图

Fig. 9 Polarization curves of NiCo2O4/GCE in 1 mol/L NaOH solution in the presence of ethanol with various concentrationsInset is anodic current versus the ethanol concentration at t = 15 s

图10 在含有0.1 mol/L乙醇的NaOH溶液中NiCo2O4/GCE电极在不同扫描周期的CV曲线图

Fig. 10 CV curves of NiCo2O4/GCE in the presence of 0.1 mol/L ethanol in 1 mol/L NaOH solution at different scans the 1st (line a), 500th (line b) scan from continuous cycling and the 501st scan (line c) using a new electrolyte at the scan rate of 10 mV/s

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棒状多孔NiCo₂O₄粉末的可控制备及其电催化性能研究

Controlled Synthesis and Electrocatalytic Performance of Porous Nickel Cobaltite Rods

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