蜂窝状碳负载铁基单原子催化剂的制备及ORR催化性能研究

doi:10.15541/jim20200624

无机材料学报 ›› 2021, Vol. 36 ›› Issue (9): 943-949.DOI: 10.15541/jim20200624

所属专题：【虚拟专辑】燃料电池(2020~2021)

蜂窝状碳负载铁基单原子催化剂的制备及ORR催化性能研究

刘自若(), 刘炜, 郝策, 胡金文, 史彦涛()

大连理工大学化工学院, 化学系, 大连 116024

收稿日期:2020-11-04 修回日期:2020-12-07 出版日期:2021-09-20 网络出版日期:2020-12-30
通讯作者: 史彦涛, 教授. E-mail: shiyantao@dlut.edu.cn
作者简介:刘自若(1996-), 女, 硕士研究生. E-mail: lzr@mail.dlut.edu.cn
基金资助:
国家自然科学基金(51773025)

Honeycomb-like Carbon-supported Fe Single Atom Catalyst: Preparation and Electrocatalytic Performance in Oxygen Reduction Reaction

LIU Ziruo(), LIU Wei, HAO Ce, HU Jinwen, SHI Yantao()

Department of Chemistry, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, China

Received:2020-11-04 Revised:2020-12-07 Published:2021-09-20 Online:2020-12-30
Contact: SHI Yantao, professor. E-mail: shiyantao@dlut.edu.cn
About author:LIU Ziruo(1996-), female, Master candidate. E-mail: lzr@mail.dlut.edu.cn
Supported by:
National Natural Science Foundation of China(51773025)

摘要/Abstract

摘要：

单原子催化剂(SACs)以近100%的原子利用率以及优秀的催化活性等, 在促进多相催化方面受到了广泛关注。然而, 由于金属原子在高温下易烧结, SACs的合成仍然具有挑战性。本研究利用熔融盐(MS)提供的强极性环境, 制备了以氮掺杂碳为载体的铁基单原子催化剂(Fe SA-NC)。结果表明, Fe SA-NC显示出蜂窝状的多孔形貌, 比表面积高达2072 m²·g^-1, 其中Fe元素的重量百分比含量为0.57%。通过球差电镜直接观察到了孤立存在的Fe单原子, 并通过X射线吸收精细结构(XAFS)分析确定Fe单原子以Fe-N₄配位体形式分散在碳基材料上。Fe SA-NC催化剂在0.1 mol/L KOH 溶液中半波电位为0.85 V, 极限电流密度为5.79 mA·cm^-2, 优于商业Pt/C催化剂。Fe SA-NC催化剂不仅对ORR四电子途径显示出高选择性(H₂O₂产率<2%, 转移电子数为3.9), 同时表现出优秀的抗甲醇性能。

关键词: 单原子催化剂, 多孔, 氮掺杂碳, 氧还原反应

Abstract:

Single atom catalysts (SACs) have emerged as an attractive concept for promoting heterogeneous reactions due to the unique properties, such as high activity and nearly 100% atom utilization. However, the synthesis of SACs remains a challenge due to the sintering of metal atoms at high temperature. In this study, Fe single atom on N doped porous carbon (Fe SA-NC) catalyst was obtained by ultrastrong polarity of molten salt (MS). Fe SA-NC shows honeycomb-like porous morphology and possesses a high specific surface area of 2072 m²·g^-1. The content of Fe element in Fe SA-NC is 0.57wt%. The isolated Fe atoms are observed by AC HAADF-STEM, and the X-ray absorption fine structure (XAFS) analysis confirms that Fe atoms disperse in the form of Fe-N₄ on the carbon substrate. Fe SA-NC shows 0.85 V half-wave potential and 5.79 mA·cm^-2maximum current density for ORR in 0.1 mol/L KOH solution. Fe SA-NC displays high selectivity for ORR four electron pathway (H₂O₂ yield<2%, electron transfer number is 3.9), outstanding stability, and good methanol tolerance.

Key words: single atom catalyst, porous, nitrogen-doped carbons, oxygen reduction reaction

中图分类号:

O646

刘自若, 刘炜, 郝策, 胡金文, 史彦涛. 蜂窝状碳负载铁基单原子催化剂的制备及ORR催化性能研究[J]. 无机材料学报, 2021, 36(9): 943-949.

LIU Ziruo, LIU Wei, HAO Ce, HU Jinwen, SHI Yantao. Honeycomb-like Carbon-supported Fe Single Atom Catalyst: Preparation and Electrocatalytic Performance in Oxygen Reduction Reaction[J]. Journal of Inorganic Materials, 2021, 36(9): 943-949.

图/表 8

图1 (a)Fe-NC和(b)Fe SA-NC的扫描电镜照片; (c)Fe SA-NC在77 K下的N2吸脱附曲线; (d) Fe SA-NC的孔径分布图

Fig. 1 SEM images of (a) Fe-NC and (b)Fe SA-NC, (c)nitrogen adsorption/desorption plots of Fe SA-NC at 77 K, and (d) pore size distribution of Fe SA-NC

图2 (a)次黄嘌呤以及次黄嘌呤和熔融盐共存时的TGA曲线; Fe SA-NC和Fe-NC的催化剂的(b)拉曼光谱以及(c)XRD图谱

Fig. 2 (a) TGA curves of hypoxanthine and hypoxanthine with molten salt; (b) Raman spectra and (c) XRD patterns of Fe SA-NC and Fe-NC

图3 Fe SA-NC的(a, b)球差矫正高角环形暗场扫描透射电镜照片, (c)N1s和(d)Fe2p的高分辨XPS图谱

Fig. 3 (a, b) AC HAADF-STEM images, high-resolution X-ray photoelectron spectra (XPS) of (c) N1s and (c) Fe2p of the Fe SA-NC catalyst

表1 Fe SA-NC催化剂中各元素含量的XPS测试结果

Table 1 XPS results of element composition in Fe SA-NC catalyst

Element	C	N	O	Fe
Atomatic percent/%	74.54	14.18	10.15	0.60

图4 Fe SA-NC、FePc、FeO和Fe2O3的Fe K边(a)X射线吸收近边结构(XANES)光谱和(b)径向结构函数; (c)Fe SA-NC的R空间EXAFS拟合曲线

Fig. 4 Fe K-edge (a) XANES spectra (b) k2-weighted FT spectra for the Fe SA-NC, FePc, FeO and Fe2O3 and (c) EXAFS fitting curves in R space for Fe SA-NC Insets in (c): EXAFS fitting curves in k space (up) and schematic models of Fe SA-NC (down); C (gray), N (blue), Fe (orange), O (red)

表2 Fe SA-NC样品的EXAFS拟合参数

Table 2 EXAFS fitting parameters of Fe SA-NC sample

Sample	Path	N	R/nm	σ²/(×10^-5, nm²)	ΔE₀/eV	R factor
Fe SA-NC	Fe-N	3.9	0.209	5.7	4.7	0.093
Fe SA-NC	Fe-O	1.0	0.190	5.7	4.7	0.093

图5 (a)Fe SA-NC在氮气和氧气饱和的0.1 mol/L KOH电解质溶液中的 CV 曲线; (b)氧饱和的0.1 mol/L KOH电解质溶液(1600 r/min, 10 mV s-1)中不同催化剂的LSV曲线; (c)Fe SA-NC在氧气饱和0.1 mol/L KOH 溶液条件中, 不同转速条件的LSV曲线; (d)图(c)对应的K-L方程图; (e)Fe SA-NC的ORR转移电子数和H2O2产率; (f)氧气饱和溶液中不同催化剂材料的塔菲尔斜率

Fig. 5 (a) CV curves of the Fe SA-NC in a N2-saturated and O2-saturated 0.1 mol/L KOH solution, respectively; (b) LSV curves of Fe SA-NC, NC and Pt/C in O2-saturated 0.1 mol/L KOH solution (1600 r/min, 10 mV·s-1); (c) ORR polarization curves of Fe SA-NC recorded at different rotating speeds; (d) K-L plots derived from Fig. (c); (e) ORR electron transfer number and H2O2 yield of Fe SA-NC; (f) Tafel slopes of Fe SA-NC, NC and Pt/C in O2-saturated 0.1 mol/L KOH solution

图6 Fe SA-NC在1600 r/min转速下氧气饱和0.1 mol/L KOH溶液中的(a)耐久性试验和(b)抗甲醇能力测试

Fig. 6 (a) Durability test and (b) methanol resistance test for Fe SA-NC in O2-saturated 0.1 mol/L KOH solution (1600 r/min)

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蜂窝状碳负载铁基单原子催化剂的制备及ORR催化性能研究

Honeycomb-like Carbon-supported Fe Single Atom Catalyst: Preparation and Electrocatalytic Performance in Oxygen Reduction Reaction

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