多壳层中空FeP微球的制备及全pH范围的电催化产氢性能

doi:10.7503/cjcu20190308

高等学校化学学报 ›› 2019, Vol. 40 ›› Issue (11): 2340.doi: 10.7503/cjcu20190308

多壳层中空FeP微球的制备及全pH范围的电催化产氢性能

唐佳易¹,姚俊杰¹,张晓君²,马梁²,张婷妹³,牛峥¹,陈祥祯¹,赵亮¹,江林³,孙迎辉^1,^*()

^1. 苏州大学能源学院, 能源与材料创新研究院, 苏州 215006
^2. 东北电力大学化学工程学院, 吉林 132012
^3. 苏州大学功能纳米与软物质研究院, 苏州 215123

收稿日期:2019-05-28 出版日期:2019-11-10 发布日期:2019-08-20
通讯作者: 孙迎辉 E-mail:yinghuisun@suda.edu.cn
基金资助:
国家重点研发计划项目(2016YFE0129800);国家重点研发计划项目(2018YFE0200702);国家自然科学基金(21822202);江苏省碳基功能材料与器件高技术研究重点实验室开放课题资助(KJS1807)

Multi-shell Hollow FeP Microspheres as Efficient Electrocatalyst for Hydrogen Evolution at All pH Values ^†

TANG Jiayi¹,YAO Junjie¹,ZHANG Xiaojun²,MA Liang²,ZHANG Tingmei³,NIU Zheng¹,CHEN Xiangzhen¹,ZHAO Liang¹,JIANG Lin³,SUN Yinghui^1,^*()

^1. College of Energy & Soochow Institute for Energy and Materials Innovations, Soochow University, Suzhou 215006, China
^2. College of Chemical Engineering, Northeast Electric Power University, Jilin 132012, China
^3. Institute of Functional Nano & Soft Materials Laboratory(FUNSOM), Soochow University, Suzhou 215123, China

Received:2019-05-28 Online:2019-11-10 Published:2019-08-20
Contact: SUN Yinghui E-mail:yinghuisun@suda.edu.cn
Supported by:
? Supported by the National Key Research and Development Program of China(2016YFE0129800);? Supported by the National Key Research and Development Program of China(2018YFE0200702);The National Natural Science Foundation of China(21822202);The Open Project of Jiangsu Key Laboratory for Carbon-Based Functional Materials & Devices, China(KJS1807)

摘要/Abstract

摘要：

设计合成了一种多壳层中空多孔结构的磷化铁(FeP)微球, 通过扫描电子显微镜(SEM)、透射电子显微镜(TEM)、 X射线衍射(XRD)和X射线光电子能谱(XPS)对微球的表面形貌和物相组成等进行表征, 并通过电化学工作站测试了材料的析氢性能. 结果表明, FeP微球和掺杂导电剂碳纳米管(CNT)后的FeP/CNT复合电催化剂在宽pH范围的电解液中均展现出了优异的电催化活性, 在酸性、碱性和中性条件下析氢反应过程中的塔菲尔斜率分别为55.0, 64.9, 163.2 mV/dec, 当电流密度达到10 mA/cm ²时, 过电势仅分别为97, 169, 495 mV(vs. RHE), 且表现出了超长的循环稳定性.

关键词: 磷化铁, 多壳层中空微球, 电催化剂, 析氢反应

Abstract:

Multi-shell hollow microspheres of iron phosphide(FeP) were synthesized by directly phosphorization of iron oxide microspheres. The prepared microstructures were characterized by SEM, TEM, XRD and XPS. Then their performance for hydrogen evolution reaction(HER) of FeP was investigated in a standard three-electrode system. The results show that the FeP/CNT composite doped with carbon nanotube(CNT) exhibit good catalytic behavior towards HER not only at extreme pH values(0 and 14), but also in neutral medium(pH=7), the Tafel slope are 55, 64.9, 163.2 mV/dec in 0.5 mol/L H₂SO₄, 1.0 mol/L KOH and 1.0 mol/L Na₂SO₄, respectively. When the current density reaches 10 mA/cm ², the overpotentials are 97, 169, 495 mV(vs. RHE), respectively.

Key words: FeP, Multi-shell hollow microsphere, Electrocatalyst, Hydrogen evolution reaction

中图分类号:

O646.51

TrendMD:

唐佳易,姚俊杰,张晓君,马梁,张婷妹,牛峥,陈祥祯,赵亮,江林,孙迎辉. 多壳层中空FeP微球的制备及全pH范围的电催化产氢性能. 高等学校化学学报, 2019, 40(11): 2340.

TANG Jiayi,YAO Junjie,ZHANG Xiaojun,MA Liang,ZHANG Tingmei,NIU Zheng,CHEN Xiangzhen,ZHAO Liang,JIANG Lin,SUN Yinghui. Multi-shell Hollow FeP Microspheres as Efficient Electrocatalyst for Hydrogen Evolution at All pH Values ^†. Chem. J. Chinese Universities, 2019, 40(11): 2340.

图/表 10

Fig.1 SEM(A), TEM(B) and HRTEM(C) images of multi-shell hollow porous FeP microspheres

Fig.2 STEM image(A) and the corresponding EDX elemental mapping images of Fe-K(B), Fe-L(C) and P-K(D) in a single FeP microsphere

Fig.3 XRD pattern(A) and XPS spectra(B, C) of FeP microspheres (B) Fe2p; (C) P2p.

Fig.4 SEM image of FeP/CNT microspheres

Fig.5 HER performances in 0.5 mol/L H2SO4 solution (A) Polarization curves(scan rate: 10 mV/s); (B) Tafel plots; (C) polarization stability plot of FeP/CNT(scan rate 500 mV/s); (D) impedance plots. a. Pt/C; b. FeP/CNT; c. FeP; d. CNT. Inset is current density curves for 10 h under constant overpotential of 97 mV.

Table 1 Tafel kinetic parameters for the HER on FeP/CNT/GC electrode in different electrolytes

Electrolyte	a/mV	b /(mV·dec^-1)	$j 0$ /(mA·cm^-2)
0.5 mol/L H₂SO₄	220	55.0	0.266
1.0 mol/L KOH	320	64.9	0.021
1.0 mol/L Na₂SO₄	920	163.2	0.012

Table 1 Tafel kinetic parameters for the HER on FeP/CNT/GC electrode in different electrolytes

Electrolyte	a/mV	b /(mV·dec^-1)	$j 0$ /(mA·cm^-2)
0.5 mol/L H₂SO₄	220	55.0	0.266
1.0 mol/L KOH	320	64.9	0.021
1.0 mol/L Na₂SO₄	920	163.2	0.012

Table 2 Comparison of the electrocatalytic activities of FeP/CNT with representative HER electrocatalysts in electrolytes

Catalyst	Electrolyte	η₁₀/mA	Tafel slope/(mV·dec^-1)	Ref.
FeP/CNT	0.5 mol/L H₂SO₄	97	55	This work
	1.0 mol/L KOH	169	64.9	This work
	1.0 mol/L Na₂SO₄	495	163.2	This work
FeP powder/carbon	0.5 mol/L H₂SO₄	110	57	[20]
	1.0 mol/L KOH	185	93	[20]
FeP bond carbon nanowires networks	0.5 mol/L H₂SO₄	256	75.8	[30]
Nanoporous FeP nanosheets	0.5 mol/L H₂SO₄	230	67	[31]
FeP nanowires	0.5 mol/L H₂SO₄	96	37	[32]
	1.0 mol/L KOH	194	67	[32]
FeP NPs@NPC	0.5 mol/L H₂SO₄	130	67	[33]
	1.0 mol/L KOH	214	82	[33]
	1.0 mol/L PBS	386	136	[33]
FeP NPs @hollow carbon nanobox	0.5 mol/L H₂SO₄	88	49	[34]
	1.0 mol/L KOH	180	71	[34]
Ni-doped FeP/C hollow nanorods	0.5 mol/L H₂SO₄	72	54	[21]
	1.0 mol/L KOH	95	72	[21]
	1.0 mol/L PBS	117	70	[21]
FeP NCs@NCNs	0.5 mol/L H₂SO₄	114	84	[35]
	1.0 mol/L KOH	205	70	[35]
	1.0 mol/L PBS	409	92	[35]
CoP/Co₂P NPs@NC	0.5 mol/L H₂SO₄	126	79	[36]
	1.0 mol/L KOH	198	82	[36]
	1.0 mol/L PBS	459	——	[36]
NiP NPs	0.5 mol/L H₂SO₄	115	46	[37]

Fig.6 HER performances in 1.0 mol/L KOH solution (A) Polarization curves(scan rate: 10 mV/s); (B) Tafel plot; (C) polarization stability plot of FeP(scan rate 500 mV/s); (D) impedance plots. a. Pt/C; b. FeP/CNT; c. FeP; d. CNT. The inset is current density curves for 10 h under constant overpotential of 169 mV.

Fig.7 HER performances in 1.0 mol/L Na2SO4 solution (A) Polarization curves(scan rate: 10 mV/s); (B) Tafel plot. a. Pt/C; b. FeP/CNT; c. FeP; d. CNT.

Fig.8 Exchange current densities of FeP/CNT electrocatalyst in different electrolytes calculated by the extrapolation of Tafel curves Electrolyte: (A) 0.5 mol/L H2SO4; (B) 1.0 mol/L KOH; (C) 1.0 mol/L Na2SO4 solution.

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多壳层中空FeP微球的制备及全pH范围的电催化产氢性能

Multi-shell Hollow FeP Microspheres as Efficient Electrocatalyst for Hydrogen Evolution at All pH Values ^†

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多壳层中空FeP微球的制备及全pH范围的电催化产氢性能

Multi-shell Hollow FeP Microspheres as Efficient Electrocatalyst for Hydrogen Evolution at All pH Values †

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Multi-shell Hollow FeP Microspheres as Efficient Electrocatalyst for Hydrogen Evolution at All pH Values ^†