Chinese Journal of Catalysis ›› 2014, Vol. 35 ›› Issue (7): 1173-1188.DOI: 10.1016/S1872-2067(14)60066-8

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Facile preparation of modified carbon black-LaMnO3 hybrids and the effect of covalent coupling on the catalytic activity for oxygen reduction reaction

Jingjun Liu, Xuemin Jin, Weiwei Song, Feng Wang, Nan Wang, Ye Song   

  1. State Key Laboratory of Chemical Resource Engineering, Beijing Key Laboratory of Electrochemical Process and Technology for Materials, Beijing University of Chemical Technology, Beijing 100029, China
  • Received:2013-12-05 Revised:2014-02-28 Online:2014-06-28 Published:2014-06-28
  • Supported by:

    This work was supported by the National Natural Science Foundation of China (51272018, 51125007) and the National Key Technology R&D Program (2009BAE87B00).

Abstract:

Covalent coupling between LaMnO3 nanoparticles and carbon black to produce a composite catalyst for oxygen reduction reaction (ORR) was achieved by physical mixing of modified carbon and perovskite-type LaMnO3 nanoparticles, followed by sintering at different temperatures. Perovskite-type LaMnO3 nanoparticles were first synthesized via chemical precipitation, and the carbon support (Vulcan XC-72) was modified using graphitization, followed by HNO3 and ammonia treatments. The morphology and electronic states of the carbon black-LaMnO3 hybrid catalyst were characterized by scanning electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The loaded LaMnO3 particles featured rod-like, three bars-like, and bamboo rod-like structures and were homogeneously dispersed in the carbon matrix that featured a hollow spherical structure. At a sintering temperature of about 300℃, C-O-M (M=La, Mn) bonds formed at the interface between the carbon and LaMnO3 nanoparticles. Electrochemical measurements in 1 mol/L NaOH showed that the carbon-LaMnO3 hybrid prepared at a LaMnO3/GCB mass ratio of 2:3 displayed the highest electrocatalytic activity towards ORR among all the synthesized hybrid catalysts. The electrocatalytic activity was comparable with that obtained by commercial Pt/C catalyst (E-TEK). The average electron transfer number of ORR was ~3.81, and the corresponding yield of the hydrogen peroxide intermediatewas ~9.5%. The remarkably improved electrocatalytic activity towards ORR was likely because of the formation of covalent bonds (C-O-M) between the LaMnO3 nanoparticles and carbon that can effectively enhance the ORR kinetics. This information is important to understand the physical origin of the electrocatalytic activity of carbon-supported rare earth oxides as catalysts for ORR.

Key words: LaMnO3 particle, Carbon black, Electrocatalytic, Covalent coupling, Oxygen reduction reaction