Abstract
The high overpotentials for oxygen reduction reaction (ORR) create an extremely negative impact on the energy efficiency of the air-based battery systems. To overcome this problem, binuclear ball-type metallophthalocyanines containing methoxy substituents (M2Pc2(EP)4, M = Fe(II), Co(II) and Zn(II)) were wrapped with polystyrene sodium sulfonate (PSS) modified graphene oxide (GO), using a facilely “solvothermal π-π assembly” method to prepare M2Pc2(EP)4/PSS-Gr composites. Compared with the commercial Pt/C catalysts, the M2Pc2(EP)4/PSS-Gr composites enhanced the catalytic activity of oxygen reduction reaction. The π electron conjugated structure of the MN4-type phthalocyanine macrocyclic system strongly influenced the one-step four-electron electrocatalytic process of the M2Pc2(EP)4/PSS-Gr composites. Moreover, the π-π interactions between the M2Pc2(EP)4 and PSS-Gr dramatically enhanced the π electron density in the conjugated structure and oxygen could be reduced more easily. The electrocatalytic activity test was displayed in the order of Fe2Pc2(FP)4/PSS-Gr > Co2Pc2(EP)4/PSS-Gr > Zn2Pc2(EP)4/PSS-Gr. The results indicated that the catalytic performance of M2Pc2Rn could be enhanced by the modification of π electron conjugated structure of M2Pc2(EP)4 and carbon materials.
Highlights
With the exhausting of traditional energy sources and increasing concerns of environmental pollution, it is urgent to explore and utilize clean energy
Composites of binuclear ball-type metallophthalocyanines with methoxy substituents (M2Pc2(EP)4, M = Fe(II), Co(II) and Zn(II)) were loaded on the surface of polystyrene sodium sulfonate (PSS)-Graphene (PSS-Gr), to enhance the catalytic activity and stability for oxygen reduction reaction (ORR) based on the π electron conjugated structure of the MN4-type phthalocyanine macrocyclic system, and the π-π supramolecular interaction between MPc nanoparticles and graphene
The results indicated that the electrocatalytic activity of Fe2Pc2(EP)4/PSS-Gr was enhanced by the π-π supramolecular interaction between Fe2Pc2(EP)4 compounds and PSS-Gr, which enhance the π
Summary
With the exhausting of traditional energy sources and increasing concerns of environmental pollution, it is urgent to explore and utilize clean energy. Pt and its alloys contribute significantly in decreasing the overpotential of oxygen reduction reaction (ORR) because of their high catalytic activity, they are limited in the scarcity of reserves, high price and lack of excellent methanol resistance [5] To overcome this problem, extensive efforts have been implemented to study low-cost, non-precious metal substitute catalysts for Pt/C catalysts [6,7]. Composites of binuclear ball-type metallophthalocyanines with methoxy substituents (M2Pc2(EP), M = Fe(II), Co(II) and Zn(II)) were loaded on the surface of PSS-Graphene (PSS-Gr), to enhance the catalytic activity and stability for ORR based on the π electron conjugated structure of the MN4-type phthalocyanine macrocyclic system, and the π-π supramolecular interaction between MPc nanoparticles and graphene
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