Abstract

Exploring metal-free, highly active and durable electrocatalysts with tunable selectivity toward oxygen reduction reaction (ORR) still remains a standing challenge. Herein, porous carbon nanotubes derived from a self-supporting hyper-cross-linked polymer with tailored selectivity for efficient ORR are reported. The sulfur-containing tubular polymer provides a versatile platform to fabricate diverse heteroatom doped porous carbon nanotubes. Attributed to the porous tubular morphology, abundant dopants and defects, the N-doped porous carbon nanotubes through pyrolysis under Ar-NH3 show excellent 4e− ORR performance with a half-wave potential (E1/2) of 0.85 V. It also has superior stability and methanol tolerance. Meanwhile, the O, S co-doped porous carbon nanotubes through oxygen plasma treatment show enhanced 2e− ORR performance with a selectivity up to 85.4%, which is probably ascribed to the more C=O and COOH species introduced in the carbon matrix. This work not only provides a useful strategy to design and prepare efficient ORR catalysts, but also paves the avenue for the facile tailoring of selectivity in ORR process.

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