Preparation and Oxygen Reduction Catalytic Performance of Iron-phthalocyanine Polymer/Multi-walled Carbon Nanotubes Composites†

doi:10.7503/cjcu20150121

Abstract

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

CLC Number:

O646

TrendMD:

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^†[J]. Chem. J. Chinese Universities, 2015, 36(10): 2016.

Figures/Tables 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.

References 38

[1]	Dresselhaus M. S., Thomas I. L., Nature, 2001, 414(6861), 332—337
[2]	Steele B. C. H., Heinzel A., Nature, 2001, 414(6861), 345—352
[3]	Stamenkovic' V., Schmidt T. J., Ross P. N., Markovic' N. M., J. Phys. Chem. B, 2002, 106(46), 11970—11979
[4]	Chen W. X., Han G., Lee J. Y., Liu Z. L., Chem. J. Chinese Universities, 2003, 24(12), 2285—2287
	(陈卫祥, 韩贵, LEE Jim Yang, 刘昭林. 高等学校化学学报,2003, 24(12), 2285—2287)
[5]	Wu G., More K. L., Johnston C. M., Zelenay P., Science, 2011, 332(6028), 443—447
[6]	Zhao X., Yin M., Ma L., Liang L., Liu C. P., Liao J. H., Lu T. H., Xing W., Energy Environ. Sci., 2011, 4(8), 2736—2753
[7]	Zhong H., Zhang H., Liu G., Liang Y., Hu J., Yi B., Electrochem. Commun., 2006, 8(5), 707—712
[8]	Su D. S., Sun G., Angew. Chem. Int. Ed., 2011, 50(49), 11570—11572
[9]	Chen Z., Higgins D., Yu A., Zhang L., Zhang J., Energy Environ. Sci., 2011, 4(9), 3167—3192
[10]	Zhang L., Zhang J., Wilkinson D. P., Wang H., J. Power Sources, 2006, 156(2), 171—182
[11]	Bezerra C. W. B., Zhang L., Lee K., Liu H., Marques A. L. B., Marques E. P., Wang H., Zhang J., Electrochim. Acta, 2008, 53(15), 4937—4951
[12]	Baker R., Wilkinson D. P., Zhang J., Electrochim. Acta, 2009, 54(11), 3098—3102
[13]	Zagal J. H., Griveau S., Silva J. F., Nyokong T., Bedioui F., Coord. Chem. Rev., 2010, 254(23), 2755—2791
[14]	Dong G., Huang M., Guan L., Phys. Chem. Chem. Phys., 2012, 14(8), 2557—2559
[15]	Orellana W., Chem. Phys. Lett., 2012, 541, 81—84
[16]	Rakov E. G., Russ. Chem. Rev., 2001, 70(10), 827—863
[17]	Baughman R. H., Zakhidov A. A., de Heer W. A., Science, 2002, 297(5582), 787—792
[18]	Akinbulu I. A., Nyokong T., New J. Chem., 2010, 34(12), 2875—2886
[19]	Morozan A., Campidelli S., Filoramo A., Jousselme B., Palacin S., Carbon, 2011, 49(14), 4839—4847
[20]	Yuan Y., Zhao B., Jeon Y., Zhong S., Zhou S., Kim S., Bioresour. Technol., 2011, 102(10), 5849—5854
[21]	Zhang Y., Mo G., Li X., Ye J., J. Power Sources, 2012, 197, 93—96
[22]	Mouahid E. O., Coutanceau C., Belgsir E. M., Crouigneau P., Léger J. M., Lamy C., J. Electroanal. Chem., 1997, 426(1), 117—123
[23]	Xu G., Li Z., Wang S., Yu X., J. Power Sources, 2010, 195(15), 4731—4735
[24]	Kip B. J., Duivenvoorden F. B. M., Koningsberger D. C., Prins R., J. Catal., 1987, 105, 26—38
[25]	Stöhr J., Hermsmeier B. D., Samant M. G., Weller D., Rev. Lett., 1992, 69(52), 2307—2310
[26]	Banerjee S., Hemraj-Benny T., Balasubramanian M., Fischer D. A., Misewich J. A., Wong S. S., Chem. Commun., 2004, 7, 772—773
[27]	Yeh Y. C., Chen H. M., Liu R. S., Asakura K., Lo M. Y., Peng Y. M., Chan T. S., Lee J. F., Chem. Mater., 2009, 21(17), 4030—4036
[28]	Cartier C., Momenteau M., Dartyge E., Fontaine A., Tourillon G., Michalowicz A., Verdaguer M., J. Chem. Soc., Dalton Trans., 1992, 4, 609—618
[29]	Kandaz M., Bilgiçli A. T., Altındal A., Synth. Met., 2010, 160(1), 52—60
[30]	Sosnik A., Gotelli G., Abraham G. A., Prog. Polym. Sci., 2011, 36(8), 1050—1078
[31]	Nas A., Fandaklı S., Kantekin H., Demirbaᶊ A., Durmuᶊ M., Dyes Pigm., 2012, 95(1), 8—17
[32]	Alvaro M., Carbonell E., Espl M., Garcia H., Appl. Catal., 2005, 57(1), 37—42
[33]	Peng Y. X., Cui L. F., Yang S. F., Fu J. J., Zheng L. R., Liao Y., Li K., Zuo X., Xia D. G., Electrochim. Acta, 2015, 154, 102—109
[34]	Bhargava G., Gouzman I., Chun C., Ramanarayanan T., Bernasek S., Appl. Surf. Sci., 2007, 253(9), 4322—4329
[35]	Niu W. H., Li L. G., Liu X. J., Wang N., Liu J., Zhou W. J., Tang Z. H., Chen S. W., J. Am. Chem. Soc., 2015, 137, 5555—5562
[36]	Peng Y. X., Li Z. P., Xia D. G., Zheng L. R., Liao Y., Li K., Zuo X., J. Power Sources, 2015 , 291, 20—28
[37]	Shui J. L., Karan N. K., Balasubramanian M., Li S. Y., Liu D. J., J. Am. Chem. Soc., 2012, 134, 16654—16661
[38]	Choi H. J., Kwag G., Kim S., J. Electroanal. Chem., 2001, 508(1), 105—114