聚合酞菁铁/多壁碳纳米管复合材料的制备及氧还原催化性能

doi:10.7503/cjcu20150121

摘要/Abstract

摘要：

采用高效、便捷的微波合成法制备了4种不同结构的聚合酞菁铁/多壁碳纳米管(Poly-FePc/MWCNTs)复合材料并进行了表征. 结果表明, 聚合酞菁铁均匀地包裹在多壁碳纳米管上. 利用线性扫描电位法(LSV)和电化学阻抗法(EIS)对材料的氧还原催化活性进行了研究, 发现FePPc/MWCNTs复合材料具有最好的氧还原催化活性. 采用X射线光电子能谱(XPS)和X射线吸收精细结构光谱(XAFS)研究了Poly-FePc/MWCNTs复合材料中酞菁铁结构变化与氧还原催化性能的相关性. 结果表明, FePPc/MWCNTs复合材料中Fe-N₄接近平面结构, 聚合酞菁铁能够更好地与MWCNTs产生协同作用, 从而加速氧还原过程中电子的转移, 提高氧还原活性.

关键词: X射线吸收精细结构光谱, 微波合成, 聚合酞菁铁, 多壁碳纳米管, 氧还原

Abstract:

Four iron-phthalocyanine polymers/multi-walled carbon nanotubes(Poly-FePc/MWCNTs) composites were sythetized by an efficient and facile microwave method. The ultraviolet-visible(UV-Vis) spectroscopy and transmission electron microscopy(TEM) results showed that the iron-phthalocyanine polymers had uniformly loaded onto the MWCNTs. The oxygen reduction reaction activity of Poly-FePc/MWCNTs was measured by linear sweep voltammetry(LSV) and electrochemical impedance spectrometry(EIS), the results demonstrated that FePPc/MWCNTs exhibited the best oxygen reduction catalytic activity. Finally, the relationship between the electrocatalytic activity and molecular structures of Poly-FePc/MWCNTs was revealed by X-ray photoelectron spectroscopy(XPS) and X-ray absorption fine spectroscopy(XAFS). The results showed that if Fe-N₄ in FePPc/MWCNTs presents a square planar structure, it could improve the synergistic effect between the iron-phthalocyanine polymers and the MWCNTs. As a consequence, it can accelerate the electrons transfer and enhance the oxygen reduction catalytic activity of the composite.

Key words: X-ray absorption fine spectroscopy(XAFS), Microwave method, Iron phthalocyanine polymer, Multi-walled carbon nanotube, Oxygen reduction

中图分类号:

O646

TrendMD:

李志盼, 彭迎祥, 杨士锋, 张瑞, 李凯, 左霞. 聚合酞菁铁/多壁碳纳米管复合材料的制备及氧还原催化性能. 高等学校化学学报, 2015, 36(10): 2016.

LI Zhipan, PENG Yingxiang, YANG Shifeng, ZHANG Rui, LI Kai, ZUO Xia. Preparation and Oxygen Reduction Catalytic Performance of Iron-phthalocyanine Polymer/Multi-walled Carbon Nanotubes Composites^†. Chem. J. Chinese Universities, 2015, 36(10): 2016.

图/表 10

Synthetic route of Poly-FePc/MWCNTs

Fig.1 UV-Vis spectra of Poly-FePc/MWCNTsa. FePPc/MWCNTs; b. HFePPc/MWCNTs;c. BAFePPc/MWCNTs; d. BBFePPc/MWCNTs.

Fig.2 TEM images of Poly-FePc/MWCNTs(A) FePPc/MWCNTs; (B) HFePPc/MWCNTs; (C) BAFePPc/MWCNTs; (D) BBFePPc/MWCNTs.

Fig.3 LSV curves of Poly-FePc/MWCNTs in O2 saturated 0.5 mol/L H2SO4 at a scan rate of 5 mV/sa. FePPc/MWCNTs; b. HFePPc/MWCNTs;c. BAFePPc/MWCNTs; d. BBFePPc/MWCNTs.

Fig.4 EIS of Poly-FePc/MWCNTs in 0.1 mol/L KCl containing 0.05 mol/L K3[Fe(CN)6]/K4[Fe(CN)6]a. FePPc/MWCNTs; b. HFePPc/MWCNTs; c. BAFePPc/MWCNTs; d. BBFePPc/MWCNTs.

Fig.5 Full survey(A) and Fe2p(B) XPS spectra of Poly-FePc/MWCNTsa. FePPc/MWCNTs; b. HFePPc/MWCNTs; c. BAFePPc/MWCNTs; d. BBFePPc/MWCNTs.

Fig.6 XPS peak-differentation spectra for Fe2p doublet in Poly-FePc/MWCNTs(A) FePPc/MWCNTs; (B) HFePPc/MWCNTs; (C) BAFePPc/MWCNTs; (D) BBFePPc/MWCNTs.

Table 1 Results of the Fe2p quadrature component spectra

Sample	Component of F $e 2 p 32$ (%)		Component of F $e 2 p 12$ (%)
Sample	709.2 eV-Fe(Ⅱ)	711.2 eV-Fe(Ⅲ)	722.8 eV-Fe(Ⅱ)	724.8 eV-Fe(Ⅲ)
FePPc/MWCNTs	32.489	43.931	4.975	18.604
HFePPc/MWCNTs	40.588	35.861	8.941	14.610
BAFePPc/MWCNTs	35.968	32.686	14.305	17.041
BBFePPc/MWCNTs	36.356	26.138	15.555	21.951

Table 1 Results of the Fe2p quadrature component spectra

Sample	Component of F $e 2 p 32$ (%)		Component of F $e 2 p 12$ (%)
Sample	709.2 eV-Fe(Ⅱ)	711.2 eV-Fe(Ⅲ)	722.8 eV-Fe(Ⅱ)	724.8 eV-Fe(Ⅲ)
FePPc/MWCNTs	32.489	43.931	4.975	18.604
HFePPc/MWCNTs	40.588	35.861	8.941	14.610
BAFePPc/MWCNTs	35.968	32.686	14.305	17.041
BBFePPc/MWCNTs	36.356	26.138	15.555	21.951

Fig.7 XANES spectra of Poly-FePc/MWCNTsa. FePPc/MWCNTs; b. HFePPc/MWCNTs;c. BAFePPc/MWCNTs; d. BBFePPc/MWCNTs.

Fig.8 Fe K-edge Fourier transform EXAFS spectra of Poly-FePc/MWCNTsa. FePPc/MWCNTs; b. HFePPc/MWCNTs;c. BAFePPc/MWCNTs; d. BBFePPc/MWCNTs.

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