Electrochemically mediated atom transfer radical polymerization of acrylonitrile and poly(acrylonitrile-b-butyl acrylate) copolymer as a precursor for N-doped mesoporous carbons. (20th September 2018)

• Record Type: Journal Article
• Authors: Trevisanello, Enrico; De Bon, Francesco; Daniel, Giorgia; Lorandi, Francesca; Durante, Christian; Isse, Abdirisak Ahmed; Gennaro, Armando
• Is Part Of: Electrochimica acta. Volume 285(2018)
• Page Start: 344
• Page End: 354
• Publication Date: 2018-09-20
• Subjects: eATRP -- Polyacrylonitrile -- Copolymer templated nanocarbons -- Porous carbon -- ORR catalysts; Electrochemistry -- Periodicals; Electrochemistry, Industrial -- Periodicals; 541.37
• DOI: 10.1016/j.electacta.2018.07.209
• Languages: English
• ISSNs: 0013-4686

Abstract

Abstract: The synthesis of polyacrylonitrile (PAN) with precisely defined morphology is essential to obtain a polymer precursor for the preparation of high-value carbon-based materials. PAN homopolymers with very narrow molecular weight distribution were prepared by electrochemically mediated atom transfer radical polymerization ( e ATRP) of acrylonitrile. The redox properties of the Cu complexes used as e ATRP catalysts were first investigated. Convenient polymerization conditions were identified by varying the applied potential, initiator nature, monomer and catalyst loading, and targeted molecular weight (MW). PAN with high MW, 9.1×10 4 g mol -1, was obtained in only 3 h. A shorter PAN was extended with butyl acrylate to prepare a well-defined PAN- b -PBA copolymer, which was subjected to annealing and pyrolysis. The obtained copolymer-templated nitrogen-enriched nanocarbon was characterized by BET, TEM and Raman spectroscopy. The material showed an exceptionally high nitrogen content, together with a remarkable activity toward O2 reduction and 40% selectivity for H2 O2 production. Graphical abstract: Image 1 Highlights: Rapid synthesis of low-dispersity, high-MW PAN via e ATRP. Well-defined PAN (co)polymers via electrochemically mediated ATRP. PAN- b -PBA copolymer as precursor for porous carbons with high nitrogen content. PAN-based copolymer templated nanocarbons as catalyst for ORR. High selectivity for H2 O2 generation from pyrolyzed PAN-based copolymer.