Carbonizing Products of the Fe/Co Doped Polypyrrole as Efficient Electrocatalysts for Oxygen Reduction Reaction

doi:10.3724/SP.J.1077.2014.13275

Abstract

Abstract:

Polymerization reaction of pyrrole in the presence of Fe³⁺ and Co²⁺ was carried out to synthesize the metal -doped polypyrrole (PPy). The metal-doped PPy was then calcined at 700℃ to obtain the carbonized products. Finally, the carbonized products were heated to 900℃ to synthesize the catalysts PPY-M(M is Fe or Co). The structure of the catalysts was investigated by SEM and X-ray diffraction techniques. The oxygen reduction reaction (ORR) activities of the catalysts in acidic and alkaline media were tested by voltammetry. Results show that the catalyst PPY-Co presents the highest electrocatalytic activity for ORR. The ORR current density at rotation rate of 2000 r/min is 7.5 mA/mg@-0.3 V(vs SCE) in acidic solution and 5.7 mA/mg@-0.8 V(vs SCE) in alkaline solution, and the onset potential of ORR is 0.54 V(vs SCE) in acidic solution and -0.11V(vs SCE) in alkaline solution. It is of great significance for the study of carbonizing products of PPY as efficient catalysts for ORR because of their simple preparation and low cost.

Key words: polypyrrole, non-precious metal catalyst, oxygen reduction reaction, fuel cell

CLC Number:

TQ174

ZHANG Yu-Hui, YI Qing-Feng, LIU Xiao-Ping, XIANG Bai-Lin. Carbonizing Products of the Fe/Co Doped Polypyrrole as Efficient Electrocatalysts for Oxygen Reduction Reaction[J]. Journal of Inorganic Materials, 2014, 29(3): 269-274.

Figures/Tables 11

Table1 Mass percentage of metal in catalyst

Catalysts	PPY	PPY-Fe	PPY-Co	PPY-Fe-Co
Fe	0	4.6wt%	0	3.3wt%
Co	0	0	3.8wt%	2.7wt%

Fig. 1 SEM images of different catalysts

Fig. 2 XRD patterns of different catalysts

Fig. 3 Current-potential curves in N2-saturated and O2-satu rated 0.5 mol/L H2SO4. Scan rate at 20 mV/s

Fig. 4 Current-potential curves in N2-saturated and O2- saturated 1 mol/L NaOH. Scan rate at 20 mV/s

Fig. 5 RDE polarization curves of the samples in O2-saturated 0.5 mol/L H2SO4 at 2000 r/min and scan rate at 5 mV/s

Fig. 6 RDE polarization curves of the samples in O2-saturated 1mol/L NaOH at 2000 r/min and scan rate at 5 mV/s

Fig. 7 RDE polarization curves of the PPY-Co at different rotation rates in O2-saturated 0.5 mol/L H2SO4 (a) and O2-saturated 1 mol/L NaOH (b). Scan rate at 5 mV/s

Fig.8 Levich plots of various catalysts in 0.5 mol/L H2SO4 (a) and 1 mol/L NaOH (b)

Table 2 Electron-transfer number of ORR on various catalysts

Electrolyte	PPY	PPY-Fe	PPY-Co	PPY-Fe-Co
Acid	1.8	2.4	3.4	2.5
Alkaline	1.5	2.7	3.2	2.1

Fig. 9 Chronoamperograms of PPY-Co in O2-saturated 0.5 mol/L H2SO4 at 0.2 V (vs SCE) and in O2-saturated 1 mol/L NaOH at -0.2 V (vs SCE)

References 19

[1]	JU JIAN-FENG, WU DONG-HUI. Development of anode catalysts for direct methanol fuel cell. Chemical Industry and Engineering Progress, 2009, 28(4): 646-649.
[2]	ANTOINE O, BULTEL Y, OZIL P, et al. Catalyst gradient for cathode active layer of proton exchange membrane fuel cell. Electrochim. Acta, 2000, 45(27): 4493-4500.
[3]	JIANG S P, LIN Z G, TSEUNG A C. Homogeneous and heterogeneous catalytic reactions in cobalt oxide/graphite air electrodes. Electrochem Soc., 1990, 137(3): 759-764.
[4]	LADOUCEUR M, LALANDE G, GUAY D, et al. Pyrolyzed cobalt phthalocyanine as electrocatalyst for oxygen reduction. Electrochem Soc., 1993, 140(7): 1974-1981.
[5]	THOMAS S C, REN X, GOTTESFELD S, et al. Direct methanol fuel cells: progress in cell performance and cathode research. Electrochim. Acta, 2002, 47(22/23): 3741-3748.
[6]	ASINSKI J. A new fuel cell cathode catalyst. Nature, 1964, 201:1212-1213.
[7]	ZAGAL J H, BEDIOUI F, DODELET J P. N4-Macrocyclic Metal Complexes. New York : Springer, 2006: 45.
[8]	SI YU-JUN, CHEN CHANG-GUO, XIONG ZHONG-PING, et al. Development of new type of carbon supported non-noble metal TM-N/C catalysts for oxygen reduction reaction. Chinese Journal of Power Sources, 2010, 34(12):1314-1317.
[9]	WU G, MORE K L, JOHNSTON C M, et al. High-performance electrocatalysts for oxygen reduction derived from polyaniline iron, and cobalt. Science, 2011, 332(6028): 443-447.
[10]	PER RUCHOT C, CHEHIMI M M. Alysis of conducting polypyrrole-silica gel composites. Synthetic Metal, 2000, 113: 53-63.
[11]	OMAST OVA M, SIMON F. Surface characterizations of conductive poly(methyl methacrylate)/polypyrrole composites. J. Mater. Sci., 2000, 35(7): 1743-1749.
[12]	SU WENCHENG, IROH IUDE O. Morphology and structure of the passive interphase formed during aqueous electrodeposition of polypyrrole coatings on steel. Electrochimica Acta, l999, 44(26): 4655-4665.
[13]	YUASA M, YAMAGUCHI A, ITSUKI H, et al. Modifying carbon particles with polypyrrole for adsorption of cobalt ions as electrocatatytic site for oxygen reduction. Chemistry Materials, 2005, 17(17): 4278-4281.
[14]	BASHYAM R, ZELENAY P. A class of non-precious metal composite catalysts for fuel cells. Nature, 2006, 443(7): 63-66.
[15]	LIU G, LI XG, GANESAN P, et al. Development of non-precious metal oxygen-reduction catalysts for PEM fuel cells based on N-doped ordered porous carbon. Applied Catalysis B: Environmental, 2009, 93(1/2): 156-165.
[16]	MATSUBARA K, WAKI K. The effect of O-Functionalities for the electrochemical reduction of oxygen on MWCNTS in acid media. Solid State Lett. 2010, 13(8): 7-9.
[17]	LIMA F H B, DE CASTRO J F R, TICIANELLI EDSON A. Silver-cobalt bimetallic particles for oxygen reduction in alkaline media. Journal of Power Sources, 2006,161(2): 806-812.
[18]	LIDE D R. CRC Handbook of Chemistry and Physics. CRC Press, Boca Raton, 2001.
[19]	LOBYNTSEVA E, KALLIO T, ALEXEYEVA N, et al. Electrochemical synthesis of hydrogen peroxide: Rotating disk electrode and fuel cell studies. Electrochimica Acta, 2007, 52(25): 7262-7269.