KOH碱化处理对Fe3N纳米颗粒电催化制氢性能影响

doi:10.15541/jim20170350

摘要/Abstract

摘要：

采用KOH溶液在通电条件下对Fe₃N纳米颗粒表面改性的方法, 探究了碱化处理对Fe₃N纳米颗粒电催化性能的影响。采用XRD、TEM、EDX、XPS、拉曼光谱和傅立叶变换红外光谱对碱化前后的Fe₃N样品进行形貌和成分的表征, 采用时间电流曲线、LSV曲线、Tafel斜率、交流阻抗法和CV曲线对碱化前后的Fe₃N样品进行电催化制氢(HER)性能的分析。结果表明, 用KOH处理的Fe₃N样品, 平均晶粒尺寸由(80±10) nm缩小为(70±10) nm, 形状由破碎的链状结构变为椭圆形结构, 物相由ε-Fe₃N相部分转变为α-Fe₂O₃相; 尺寸、形貌和成分的改变, 使得碱化后的样品有更多的电催化活性位点暴露。由电流密度为10 mA/cm²的过电位0.429 V降为0.204 V, Tafel斜率由103 mV/dec降为95 mV/dec。过电势降低, 交流阻抗变小, 电化学活性面积增大, 表明KOH碱化处理后的样品电催化制氢的能力得到大大提高。

关键词: Fe₃N纳米颗粒, KOH碱化处理, 电催化, 析氢反应

Abstract:

Surface modification of Fe₃N nanoparticles by KOH solution under electrification conditions was carried out, and effect of alkalization on the catalytic performance of Fe₃N nanoparticles was investigated. Morphology and composition of Fe₃N nanoparticles and alkalized Fe₃N nanoparticles were characterized by XRD, TEM, EDX, XPS, Raman spectra, and Fourier Transform Infrared spectroscopy. Electrocatalytic hydrogen evolution reaction (HER) performance of Fe₃N nanoparticles and alkalized Fe₃N nanoparticles was analyzed by time-current curve, linear sweep voltammetry, Tafel slope, AC impedance method, and CV curve. It was found that, for alkalized Fe₃N nanoparticles, their average grain sizes decreased from (80±10) nm to (70±10) nm. Their morphology changed from broken chain structure to elliptical structure, while their the phase changed partly from ε-Fe₃N to α-Fe₂O₃, which brought about more exposed electrocatalytic activity sites when compared with the Fe₃N before alkalization. Overpotential at 10 mA/cm² the alkalized Fe₃N nanoparticles was reduced from 0.429 V to 0.204 V and Tafel slope was reduced from 103 mV/dec to 95 mV/dec. Low opening voltage, small Tafel slope, low over-potential, small AC impedance and larg chemically active surface area were achieved by the alkalized Fe₃N nanoparticles, demonstrating that alkalized Fe₃N is a promising excellent electrocatalyst for water splitting.

Key words: Fe₃N nanoparticles, KOH alkalization treatment, electrocatalysis, hydrogen evolution reaction

中图分类号:

O646

王辉, 俞有幸. KOH碱化处理对Fe₃N纳米颗粒电催化制氢性能影响[J]. 无机材料学报, 2018, 33(6): 653-658.

WANG Hui, YU You-Xing. KOH Alkalized Fe₃N Nanoparticles on Electrocatalytic Hydrogen Evolution Reaction[J]. Journal of Inorganic Materials, 2018, 33(6): 653-658.

图/表 11

图1 Fe3N纳米颗粒碱化前后的XRD图谱

Fig. 1 XRD patterns of Fe3N nanoparticles and alkalized Fe3N nanoparticles

图2 Fe3N纳米颗粒碱化前(a)、(b)和后(c)、(d)的TEM照片

Fig. 2 TEM images of Fe3N nanoparticles(a), (b) and alkalized Fe3N nanoparticles(c), (d)

表1 Fe3N纳米颗粒碱化前后不同元素相对含量对比

Tabel 1 Different elements relative content of Fe3N nanoparticles and alkalized Fe3N nanoparticles

Element	N K/at%	O K/at%	Fe K/at%
Fe₃N	22.80	4.83	72.37
Alkalized Fe₃N	13.50	12.30	74.20

图3 Fe3N纳米颗粒碱化前后的拉曼光谱图

Fig. 3 Raman spectra of Fe3N nanoparticles and alkalized Fe3N nanoparticles

图4 Fe3N纳米颗粒碱化前后FT-IR谱图

Fig. 4 FT-IR spectra of Fe3N and alkalized Fe3N nanoparticles

图5 Fe3N纳米颗粒碱化前后XPS图谱

Fig. 5 XPS spectra for Fe3N and alkalized Fe3N nanoparticles

图6 Fe3N纳米颗粒在1.0 mol/L KOH溶液中-0.3 V的电压条件下的时间电流曲线

Fig. 6 Current-time (I-t) curve obtained for HER with Fe3N nanoparticles at overpotential of -0.3 V (vs. RHE) in 1.0 mol/L KOH

图7 Fe3N纳米颗粒碱化前后的线性扫描伏安法曲线, 扫描速度为5 mV/s

Fig. 7 Linear sweep voltammetry (LSV) curves for HER of Fe3N and alkalized Fe3N nanoparticles measured at 5 mV/s scan rate

图8 Fe3N纳米颗粒碱化前后的Tafel斜率图

Fig. 8 Corresponding Tafel plots of Fe3N and alkalized Fe3N nanoparticles

图9 Fe3N纳米颗粒碱化前后的交流阻抗图

Fig. 9 EIS Nyquist plots at -0.3 V (vs. RHE) of Fe3N and alkalized Fe3N nanoparticles

图10 Fe3N纳米颗粒碱化前后测试电容图

Fig. 10 Measured capacitive currents plotted as a function of scan rate indicated alongside the curve

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KOH碱化处理对Fe₃N纳米颗粒电催化制氢性能影响

KOH Alkalized Fe₃N Nanoparticles on Electrocatalytic Hydrogen Evolution Reaction

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