Highly porous layered carbon nanocomposites from the self-assembly of a poly(amic acid) for efficient oxygen reduction reaction catalysis

Abstract

Porous layered carbon nanomaterials play important role in the efficient loading of electroactive substances for high performance energy conversion techniques. Herein, an intramolecular cyclization induced self-assembly (ICISA) strategy is proposed to prepare three-dimensional highly porous layered carbon nanostructures (LCs) for efficient loading of various transition metal nanoparticles for oxygen reduction reaction (ORR) catalysis. The amphiphilic alternating copolymer poly(amic acid) (PAA) is synthesized by the stepwise polymerization of hydrazine hydrate and pyromellitic dianhydride. Upon heating above 160 °C, the intramolecular cyclization reaction occurs, leading to the formation of rigid, crystalline and non-soluble polyimide segments in the backbone, which induces the self-assembly of the polymer to form dumbbell-shaped assemblies with a high solid content of 15%. After pyrolysis in a nitrogen atmosphere, LCs are obtained. Cobalt (Co), iron (Fe) and FeCo nanoparticles can be efficiently loaded, noted as Co@LCs, Fe@LCs and FeCo@LCs, respectively. The ORR catalytic performance of the catalysts is evaluated to give half wave potentials of 0.791, 0.787 and 0.812 V, and limit current densities of 4.92, 4.73 and 4.71 mA cm−2 for Co@LCs, Fe@LCs and FeCo@LCs, respectively. Overall, we propose an ICISA strategy to facilely prepare three-dimensional carbon nanomaterials with highly porous layered structure for efficient ORR catalysis.