碳纳米纤维负载铁钴镍硼化物可控制备及其电催化析氢性能研究

梁珂明; 姜彬; 黄焱; 鲁萌萌; 王秋静

碳纳米纤维负载铁钴镍硼化物可控制备及其电催化析氢性能研究

西北大学城市与环境学院陕西省地表系统与环境承载力重点实验室, 陕西西安 710127

基金项目:

国家自然科学基金 21902127

详细信息

中图分类号: O646
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- 被引次数: 0
出版历程
- 收稿日期: 2020-07-29
- 修回日期: 2020-09-07
- 网络出版日期: 2021-01-23
- 刊出日期: 2020-10-10

Controllable synthesis of carbon nanofibers with plated FeCoNiB as high performance composite catalysts for electrocatalytic hydrogen evolution

Shaanxi Provincial Key Laboratory of Earth Surface System and Environmental Carrying Capacity, College of Urban and Environmental Science, Northwest University, Xi'an 710127, China

Funds:

The National Natural Science Foundation of China 21902127

More Information

Corresponding author: JIANG Bin, E-mail:jb1987@nwu.edu.cn

摘要

摘要: 通过乙醇催化燃烧法制备了碳纳米纤维（CNFs），采用化学沉积法在CNFs载体上负载铁钴镍硼化物（FeCoNiB），并以多种测试手段对其表征，研究了化学沉积工艺条件对FeCoNiB粒径、分散、成分及结构的影响，建立了碳纳米纤维负载的铁钴镍硼化物（FeCoNiB/CNFs）可控制备方法。采用电化学测试手段研究了FeCoNiB/CNFs在碱性环境下的氢气析出反应（HER）催化性能。结果表明，在100 mA/cm²的电流密度下，FeCoNiB/CNFs的过电位仅为366 mV，塔菲尔斜率低至41 mV/dec；在持续10 h的稳定性测试中电位衰减幅度很小，基本保持不变。这说明FeCoNiB/CNFs制备成本低，但其高稳定性可媲美贵金属的高催化活性HER催化剂；该研究可为非贵金属HER催化剂的研制及低成本电解水制氢技术的规模化应用提供参考。
- 非贵金属 /
- 氢气析出反应 /
- 铁钴镍硼化物 /
- 碳纳米纤维 /
- 化学沉积法
Abstract: Carbon nanofibers (CNFs) were synthesized by ethanol catalytic combustion method and FeCoNiB was loaded on the CNFs by electroless plating (chemical deposition) method. The effect of electroless plating condition on the particle size, dispersion, composition and structure of FeCoNiB was then investigated, to establish the process for the controllable synthesis of carbon nanofibers with plated FeCoNiB (FeCoNiB/CNFs). In addition, the electrocatalytic performance of FeCoNiB/CNFs was evaluated for the hydrogen evolution reaction (HER) in alkaline environment. The results illustrate that the FeCoNiB/CNFs shows a low overpotential of 366 mV at 100 mA/cm² and a quite low Tafel slope value of 41 mV/dec, as well as a stable potential without attenuation during the stability test for 10 h, displaying a stable and high catalytic performance that is comparable to that of noble metal catalysts. This study is probably helpful for the development of efficient non-noble metal catalyst for HER as well as the application of large-scale electrolytic water hydrogen production in industry.
- non-precious metals /
- hydrogen evolution reaction /
- FeCoNiB /
- carbon nanofibers /
- electroless plating

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图 1 不同主盐浓度条件下((a)-(c))和不同反应时间下((d)-(f))合成FeCoNiB/CNFs的SEM照片

Figure 1 SEM images of FeCoNiB/CNFs synthesized with different main salt concentrations ((a)-(c)) and different reaction times ((d)-(f))

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图 2 CNFs ((a), (b))和FeCoNiB/CNFs ((c), (d))不同放大倍数的SEM照片; FeCoNiB/CNFs的EDS能谱分析图(e)和元素映射图((f)-(k))

Figure 2 SEM images of CNFs ((a) and (b)) and FeCoNiB/CNFs ((c) and (d)) with different magnifications EDS image (e) and elemental maps ((f)-(k)) of FeCoNiB/CNFs

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图 3 FeCoNiB/CNFs的TEM照片((a), (b))、HRTEM照片(c)以及XRD谱图(d)

Figure 3 TEM image ((a) and (b)), HRTEM image (c) and XRD pattern (d) of FeCoNiB/CNFs

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图 4 FeCoNiB/CNFs的XPS能谱图(a), FeCoNiB/CNFs中B 1s、O 1s、Fe 2p、Co 2p、Ni 2p的高分辨XPS能谱图((b)-(f))

Figure 4 Overscan XPS spectrum (a) as well as the B 1s (b), O 1s (c), Fe 2p (d), Co 2p (e) and Ni 2p (f) XPS spectra of FeCoNiB/CNFs

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图 5 CNFs、FeB/CNFs、CoB/CNFs、NiB/CNFs、FeCoB/CNFs、FeNiB/CNFs、CoNiB/CNFs、FeCoNiB/CNFs和Pt/C/CNFs在1.0 mol/L KOH溶液中测得的C_dl图

Figure 5 Electrochemical double-layer capacitance of CNFs, FeB/CNFs, CoB/CNFs, NiB/CNFs, FeCoB/CNFs, FeNiB/CNFs, CoNiB/CNFs, FeCoNiB/CNFs and Pt/C/CNFs in 1.0 mol/L KOH solution

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图 6 CNFs、FeB/CNFs、CoB/CNFs、NiB/CNFs、FeCoB/CNFs、FeNiB/CNFs、CoNiB/CNFs、FeCoNiB/CNFs和Pt/C/CNFs在1.0 mol/L KOH溶液中的LSV曲线(a)以及塔菲尔斜率图(b)

Figure 6 Linear sweep voltammetry (LSV) curves (a) and Tafel plots (b) of CNFs, FeB/CNFs, CoB/CNFs, NiB/CNFs, FeCoB/CNFs, FeNiB/CNFs, CoNiB/CNFs, FeCoNiB/CNFs and Pt/C/CNFs in 1.0 mol/L KOH solution

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图 7 CNFs、FeB/CNFs、CoB/CNFs、NiB/CNFs、FeCoB/CNFs、FeNiB/CNFs、CoNiB/CNFs和FeCoNiB/CNFs在1.0 mol/L KOH中的电化学阻抗谱图

Figure 7 Nyquist plots of electrochemical impedance spectra (EIS) of CNFs, FeB/CNFs, CoB/CNFs, NiB/CNFs, FeCoB/CNFs, FeNiB/CNFs, CoNiB/CNFs and FeCoNiB/CNFs in 1.0 mol/L KOH

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图 8 用计时电位法测试FeCoNiB/CNFs在1.0 mol/L KOH中的稳定性; 插图为三电极体系下电解水产氢的照片

Figure 8 Catalytic stability of FeCoNiB/CNFs, as investigated by chronopotentiometry (CP) in 1.0 mol/L KOH solutions (insert: photo of electrolytic water splitting with a three-electrode system)

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表 1 主要化学试剂基本信息

Table 1 Basic information of main chemical reagents

Reagent	Chemical formula	Purity	Manufacturer
Copper sheet	Cu	AR	Sinopharm Group Chemical Reagent Co., Ltd
Alumina polishing powder	Al₂O₃	85%	Sinopharm Group Chemical Reagent Co., Ltd
Potassium hydroxide	KOH	AR	Tianjin Shengao Chemical Reagent Co., Ltd
Anhydrous ethanol	C₂H₅OH	AR	Guangdong Guanghua Technology Co., Ltd
Isopropanol	(CH₃) ₂CHOH	AR	Guangdong Guanghua Technology Co., Ltd
Ferric chloride hexahydrate	FeCl₃·6H₂O	AR	Shanghai Aladdin Biochemical Technology Co., Ltd
Nickel sulfate hexahydrate	NiSO₄·6H₂O	AR	Shanghai Aladdin Biochemical Technology Co., Ltd
Cobalt sulfate heptahydrate	CoSO₄·7H₂O	AR	Shanghai Aladdin Biochemical Technology Co., Ltd
Ferrous sulfate heptahydrate	FeSO₄·7H₂O	AR	Shanghai Macklin Biochemical Technology Electric Co., Ltd
Sodium citrate	Na₃C₆H₅O₇	98%	Shanghai Aladdin Biochemical Technology Co., Ltd
Dimethylaminomethylborane	C₂H₁₀BN	10%	Shanghai Aladdin Biochemical Technology Co., Ltd
Perfluorinated resin solution	nafion	5%	Shanghai Macklin Biochemical Technology Electric Co., Ltd
Platinum carbon catalyst	Pt/ C	20%	Shanghai Macklin Biochemical Technology Electric Co., Ltd

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表 2 本研究与各种已开发的非贵金属析氢电催化剂在碱性条件下的催化性能

Table 2 Comparison in the catalytic performance for HER between the FeCoNiB/CNFs catalyst of this study and various non-precious metal electrocatalysts reported in literature under alkaline conditions

Electrocatalyst	Electrolyte	Overpotential / mV	Tafel / (mV·dec^-1)	Reference
FeCoNiB/CNFs	1. 0 mol/ L KOH	η₁₀₀=366	41	this study
NiCoFeB	1. 0 mol/ L KOH	η₁₀=345	98	[33]
Co₂B-500	1. 0 mol/ L KOH	η₁₀≈780	177	[45]
Co-B/ CC	1. 0 mol/ L KOH	η₁₀₀≈370	-	[15]
Ni NP	1. 0 mol/ L KOH	η₁₀₀≈480	167	[46]
Ni/ Fe NP	1. 0 mol/ L KOH	η₁₀₀≈510	212	[46]
Fe NP	1. 0 mol/ L KOH	η₁₀₀≈730	186	[46]
η₁₀ = overpotential for HER to achieve-10 mA/cm²; η₁₀₀ = overpotential for HER to achieve-100 mA/cm²; CC: carbon cloth; NP: nanoparticles

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