碱性溶液中不同微观结构的Fe-N/C催化剂氧还原性能的稳定性对比研究

doi:10.15541/jim20190547

无机材料学报 ›› 2020, Vol. 35 ›› Issue (8): 953-958.DOI: 10.15541/jim20190547

所属专题：能源材料论文精选(四)：光催化与电催化(2020)；【虚拟专辑】燃料电池(2020~2021)

• 研究快报 • 上一篇

碱性溶液中不同微观结构的Fe-N/C催化剂氧还原性能的稳定性对比研究

丁昇¹(),宁锴¹,袁斌霞¹,潘卫国^1,²,尹诗斌³,刘建峰^1,^2,³()

1.上海电力大学能源与机械工程学院, 上海 200090
2.机械工业清洁发电环保技术重点实验室, 上海 200090
3.有色金属及材料加工新技术教育部重点实验室, 广西有色金属及特色材料加工重点实验室, 南宁 530004

收稿日期:2019-10-28 修回日期:2020-02-28 出版日期:2020-08-20 网络出版日期:2020-03-06
作者简介:丁昇(1994-), 男, 硕士研究生. E-mail: <email>dingsheng1994@foxmail.com</email><br/>DING Sheng (1994-), male, Master candidate. E-mail: <email>dingsheng1994@foxmail.com</email>

Durability of Fe-N/C Catalysts with Different Nanostructures for Electrochemical Oxygen Reduction in Alkaline Solution

DING Sheng¹(),NING Kai¹,YUAN Binxia¹,PAN Weiguo^1,²,YIN Shibin³,LIU Jianfeng^1,^2,³()

1. College of Energy and Mechanical Engineering, Shanghai University of Electric Power, Shanghai 200090, China
2. Key Laboratory of Environmental Protection Technology for Clean Power Generation in Machinery Industry, Shanghai 200090, China
3. Key Laboratory of New Processing Technology for Non-ferrous Metals and Materials (Ministry of Education), Guangxi Key Laboratory of Processing for Non-ferrous Metals and Featured Materials, Nanning 530004, China

Received:2019-10-28 Revised:2020-02-28 Published:2020-08-20 Online:2020-03-06
Supported by:
Young Eastern Scholar(QD 2016052);Open Foundation of Guangxi Key Laboratory of Processing for Non-ferrous Metal and Featured Materials(2020GXYSOF17)

摘要/Abstract

摘要：

Fe-N/C催化剂在氧还原反应中的作用机理对于开发高效、可持续使用的非贵金属催化剂在聚合物电解质膜燃料电池中的应用至关重要, 但目前仍存在很多的难以攻克的问题。为了揭示纳米结构与电化学活性的关系, 本研究开发了一种具有高电化学活性的Fe-N/C氧还原催化剂, 该催化剂含有Fe-N_x位点和被氮掺杂的碳纳米管包裹的Fe/Fe₃C纳米晶体两种具有氧还原反应电化学活性的纳米结构。尽管不含贵金属铂, 本研究合成的Fe-N/C催化剂在碱性条件下仍显示出较高的ORR活性, 半波电势为0.86 V(vs RHE), 质量活性为18.84 A/g(0.77 V(vs RHE), 极限电流密度为-4.3 mA·cm ^-2。同时, 电子转移数为3.7(0.2 V(vs RHE), 说明Fe-N/C催化剂中4电子ORR反应的比例较高。石墨烯包覆的金属Fe/Fe₃C纳米晶生长N-CNTs后, 材料的导电性有所提高, 并且Fe-N_x活性位点在Fe/Fe₃C纳米颗粒表面分布均匀, 改善了材料的电化学活性。本研究为非贵金属氧还原电催化剂的继续深入研究以及广泛应用于商业化生产提供了一定的借鉴和依据。

关键词: 电化学, 催化剂, 纳米材料, 氧还原反应

Abstract:

The mechanism of Fe-N/C catalysts in oxygen reduction reactions is critical to the development of efficient, sustainable non-noble metal catalysts in polymer electrolyte membrane fuel cells, but it is still in controversy. In order to understand the relationship between composition and the nanostructure of material and the electrochemical activity, this study developed a type of Fe-N/C catalyst with high electrochemical activity, which contained Fe-N_x active sites and Fe/Fe₃C nanocrystals encapsulated with nitrogen-doped carbon nanotubes. Despite being free of precious metals, the as-prepared catalyst displays high oxygen reduction reactions (ORR) activity in alkaline medium with the half-wave potential of 0.86 V(vs RHE), the mass activity of 18.84 A/g at 0.77 V(vs RHE), and the maximum current density of -4.3 mA·cm ^-2. Meanwhile, the electron transfer number is 3.7 at 0.2 V(vs RHE), revealing that the 4-electron ORR reaction exists in the catalyst. The excellent electrochemical activity is attributed to the graphene-encapsulated metallic Fe/Fe₃C nanocrystals which improves the conductivity after the growth of N-doped carbon nanotubes, and the relatively high proportion of Fe-N_x active sites distributed on the surface of Fe/Fe₃C nanoparticles. This study provides a certain reference and basis for the further study of non-noble metal catalyst and their wide application in commercial production.

Key words: electrochemistry, catalyst, nanomaterial, oxygen reduction reaction

中图分类号:

O643

丁昇, 宁锴, 袁斌霞, 潘卫国, 尹诗斌, 刘建峰. 碱性溶液中不同微观结构的Fe-N/C催化剂氧还原性能的稳定性对比研究[J]. 无机材料学报, 2020, 35(8): 953-958.

DING Sheng, NING Kai, YUAN Binxia, PAN Weiguo, YIN Shibin, LIU Jianfeng. Durability of Fe-N/C Catalysts with Different Nanostructures for Electrochemical Oxygen Reduction in Alkaline Solution[J]. Journal of Inorganic Materials, 2020, 35(8): 953-958.

图/表 9

Fig. 1 SEM images of (a) FeNC-DCDA and (b) FeNC-MM; HRTEM images of (c) FeNC-DCDA and (d) FeNC-MM with insets showing corresponding FFT patterns; TEM images of (e) FeNC-DCDA and (f) FeNC-MM with insets showing corresponding SAED images

Fig. 2 XRD patterns (a), XPS wide scan (b), XPS C1s spectra (c), XPS N1s spectra (d) for FeNC-DCDA and FeNC-MM

Fig. 3 LSV curves (a), CV curves (b), H2O2 yield (c) and electron transfer number (d) for Pt/C, FeNC-DCDA, FeNC-MM and KB in O2-saturated 0.1 mol·L-1 KOH at 1600 r·min-1

Fig. 4 CV curves in N2-saturated 0.1 mol·L-1 KOH and LSV curves in O2-saturated 0.1 mol·L-1 KOH of the catalysts for 30000 load potential cycles (a-b) Pt/C; (c-d) FeNC-MM; (e-f) FeNC-DCDA

Fig. S1 HRTEM images of FeNC-DCDA

Fig. S2 LSV curves of as-prepared and acid-leached FeNC-DCDA measured in O2-saturated 0.1 mol·L-1 KOH (a) and LSV curves of SCN- poisoned FeNC-DCDA measured in O2-saturated 0.1 mol·L-1 KOH (1600 r·min-1, 10 mV s-1) (b)

Fig. S3 Comparison of maximum current densities of catalysts before and after the durability tests

Table S1 Elemental compositions of Fe-N/C catalysts synthesized with different nitrogen sources obtained from XPS analysis

Compositon	FeNC-DCDA/at%	FeNC-MM/at%
Carbon	97.05	96.14
Nitrogen	0.25	1.85
Oxygen	2.21	1.54
Iron	0.49	0.48

Table S2 Nitrogen contents and deconvoluted N 1s peak positions in Fe-N/C catalysts from XPS data

Catalyst	N-C		Fe-N_x		Graphitic nitrogen		Oxygenated nitrogen
Catalyst	Position/eV	Fraction/%	Position/eV	Fraction/%	Position/eV	Fraction/%	Position/eV	Fraction/%
FeNC-DCDA	398.71	35.66	399.82	10.02	401.38	24.79	403.51	29.52
FeNC-MM	398.68	34.54	400.07	8.4	401.26	13.2	404.2	43.86

参考文献 14

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碱性溶液中不同微观结构的Fe-N/C催化剂氧还原性能的稳定性对比研究

Durability of Fe-N/C Catalysts with Different Nanostructures for Electrochemical Oxygen Reduction in Alkaline Solution

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