包覆氮化铁的Fe, N掺杂碳纳米纤维的制备及对氧还原反应的催化性能

doi:10.7503/cjcu20180459

高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (11): 2492.doi: 10.7503/cjcu20180459

包覆氮化铁的Fe, N掺杂碳纳米纤维的制备及对氧还原反应的催化性能

刘培^1,^2,³, 程庆庆^1,³, 陈驰¹, 邹亮亮¹, 邹志青¹, 杨辉^1,²()

1. 中国科学院上海高等研究院, 上海 201210
2. 上海科技大学物质科学与技术学院, 上海 201210
3. 中国科学院大学, 北京 100039

收稿日期:2018-06-26 出版日期:2018-11-10 发布日期:2018-08-31
作者简介:联系人简介: 杨辉, 男, 博士, 研究员, 主要从事燃料电池和液流电池等研究. E-mail: yangh@sari.ac.cn
基金资助:
国家重点研究发展计划项目(批准号: 2017YFA0206500)和国家自然科学基金(批准号: 21673275, 21533005)资助.

Preparation and Oxygen Reduction Reaction Catalytic Performance of Fe, N Co-doped Carbon Nanofibers with Encapsulated Iron Nitride^†

LIU Pei^1,^2,³, CHENG Qingqing^1,³, CHEN Chi¹, ZOU Liangliang¹, ZOU Zhiqing¹, YANG Hui^1,^2,^*()

1. Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201210, China
2. School of Physical Science and Technology, ShanghaiTech University, Shanghai 201210, China
3. University of Chinese Academy of Sciences, Beijing 100039, China

Received:2018-06-26 Online:2018-11-10 Published:2018-08-31
Contact: YANG Hui E-mail:yangh@sari.ac.cn
Supported by:
† Supported by the National Key Research and Development Program of China(No. 2017YFA0206500) and the National Natural Science Foundation of China(Nos.21673275, 21533005).

摘要/Abstract

摘要：

通过静电纺丝、碳化和氨气刻蚀制备了具有核-壳结构的包覆氮化铁(Fe_xN)纳米颗粒的Fe, N共掺杂多孔碳纳米纤维(Fe_xN@Fe-N-C), 并研究了其在酸性和碱性介质中对氧还原反应(ORR)的电催化性能. 结果表明, 该催化剂具有优异的氧还原催化活性, 在酸性介质中的半波电位(E_1/2)可达0.81 V(vs. RHE), 在碱性条件下的E_1/2高达0.897 V, 高于商业Pt/C催化剂. 在酸性介质中经过10000周加速衰减测试后, Fe_xN@Fe-N-C的E_1/2仅衰减了26 mV, 展示出极佳的耐久性. 离子探针和浓酸刻蚀实验结果表明, Fe-N_x以及Fe_xN纳米颗粒均对ORR有重要催化作用.

关键词: Fe-N-C, 氮化铁, 氧还原反应, 碳纳米纤维, 氨气刻蚀

Abstract:

Fe, N co-doped porous carbon nanofibers with iron nitride(Fe_xN) nanoparticles encapsulated in Fe, N co-doped carbon shell(Fe_xN@Fe-N-C) were preparated through electrospinning, carbonization and NH₃-etching. The Fe_xN@Fe-N-C catalyst exhibits excellent catalytic activity for oxygen reduction reaction(ORR) in both acid and alkaline media. The half-wave potential(E_1/2) in acidic medium can reach to 0.81 V(vs. RHE), while the E_1/2 in alkaline medium is 0.897 V(vs. RHE), which is even higher than that of commercial Pt/C catalyst. After 10000 cycles of accelerated durability test in acid media, the E_1/2 only decreases by 26 mV, demonstrating the excellent durability of Fe_xN@Fe-N-C. Ion probing and acid-etching experiments indicate that both Fe-N_x sites and Fe_xN nanoparticles contribute to the ORR activity.

Key words: Fe-N-C, Iron nitride, Oxygen reduction reaction(ORR), Carbon nanofibers, NH₃-etching

中图分类号:

O646

TrendMD:

刘培, 程庆庆, 陈驰, 邹亮亮, 邹志青, 杨辉. 包覆氮化铁的Fe, N掺杂碳纳米纤维的制备及对氧还原反应的催化性能. 高等学校化学学报, 2018, 39(11): 2492.

LIU Pei, CHENG Qingqing, CHEN Chi, ZOU Liangliang, ZOU Zhiqing, YANG Hui. Preparation and Oxygen Reduction Reaction Catalytic Performance of Fe, N Co-doped Carbon Nanofibers with Encapsulated Iron Nitride^†. Chem. J. Chinese Universities, 2018, 39(11): 2492.

图/表 12

Scheme 1 Schematic illustration of the synthesis of FexN@Fe-N-C catalysts

Fig.1 TEM images of the Fe-N-CNF after carbonization and acid-leaching(A) and FexN@Fe-N-C-20 after NH3-treatment for 20 min(B) and high-resolution TEM image of FexN nanoparticle(C)

Fig.2 TEM images(A, A') and the elemental EDS-mapping analysis(B—D, B'—D') of C, N and Fe in the regions of FexN nanoparticle(A—D) and carbon nanofiber(A'—D') in FexN@Fe-N-C-20

Fig.3 XRD patterns of Fe-N-CNF(a) and FexN@Fe-N-C-20(b)

Fig.4 N2 adsorption/desorption isotherms(A) and pore size distributions(B) of Fe-N-CNF(a) and FexN@Fe-N-C-20(b)

Fig.5 XPS survey spectrum of FexN@Fe-N-C-20(A) and Raman spectra of Fe-N-CNF(a) and FexN@Fe-N-C-20(b)(B)Inset shows the deconvoluted high-resolution N1s XPS spectrum.

Table 1 Atomic fractions(%) of Fe-N-CNF and FexN@Fe-N-C-t(t=10, 20, 40) measured by XPS

Sample	C	N	O	Fe
Fe-N-CNF	85.63	3.38	10.40	0.59
Fe_xN@Fe-N-C-10	92.61	3.30	4.28	0.36
Fe_xN@Fe-N-C-20	93.09	3.25	3.32	0.34
Fe_xN@Fe-N-C-40	95.30	2.01	2.36	0.32

Fig.6 ORR polarization curves of Fe-N-CNF, FexN@Fe-N-C-t(t=10, 20, 40) and Pt/C in O2-saturated 0.1 mol/L HClO4(A), ORR polarization curves of FexN@Fe-N-C-20 at various rotation rates in 0.1 mol/L HClO4(B) and the corresponding K-L plots at various potentials(C)

Fig.7 ORR polarization curves of FexN@Fe-N-C-20 and Pt/C in O2-saturated 0.1 mol/L KOH(A), ORR polarization curves of FexN@Fe-N-C-20 at various rotation rates in 0.1 mol/L KOH(B) and the corresponding K-L plots at various potentials(C)

Fig.8 ORR polarization curves of FexN@Fe-N-C-20(A) and Pt/C(B) before and after 10000 cycles of accelerated durability test in O2-saturated 0.1 mol/L HClO4Potential range: 0.6—1.0 V; scan rate: 50 mV/s.

Fig.9 ORR polarization curves of N/CNF and FexN@Fe-N-C-20 with various amount of SCN- in 0.1 mol/L HClO4(A) and the comparison of the corresponding half-wave potentials(B)a. Initial; b. 5 mL SCN-; c. 25 mL SCN-; d. 40 mL SCN-; e. N/CNF.

Fig.10 ORR polarization curves of FexN@Fe-N-C-20 before and after second acid-leaching in 0.1 mol/L HClO4(A) and ORR polarization curves of Fe-N/CNF-H2, Fe-N/CNF-N2 and FexN@Fe-N-C-20(B)

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包覆氮化铁的Fe, N掺杂碳纳米纤维的制备及对氧还原反应的催化性能

Preparation and Oxygen Reduction Reaction Catalytic Performance of Fe, N Co-doped Carbon Nanofibers with Encapsulated Iron Nitride^†

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包覆氮化铁的Fe, N掺杂碳纳米纤维的制备及对氧还原反应的催化性能

Preparation and Oxygen Reduction Reaction Catalytic Performance of Fe, N Co-doped Carbon Nanofibers with Encapsulated Iron Nitride†

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Preparation and Oxygen Reduction Reaction Catalytic Performance of Fe, N Co-doped Carbon Nanofibers with Encapsulated Iron Nitride^†