Two-Dimensional Polyphosphazene Nanosheet-Derived N,P Doubly Doped Carbon Nanotubes for Electrocatalytic Oxygen Reduction

Two-dimensional (2D) covalent organic polymers (COPs) featuring large surface areas and exposed active sites are desirable in the modification of electrode materials for electrochemical reactions. However, the rigid and planar conformation of 2D COPs limits the wrap of one-dimensional electrodes. Herein, we have proposed a molecular strategy to regulate in situ encapsulation of carbon nanotubes (CNTs) with 2D polyphosphazene. The stoichiometric control over the nucleophilic substitution reaction between hexachlorocyclophosphazene and amines allows for the oriented evolution around the surface of CNTs. The formed COP sheath is an ultrathin and uniform coating without granular deposition. Upon carbonization, the well-defined core/shell CNT composite was converted into the N,P-codoped carbon, exhibiting outstanding electrocatalytic oxygen reduction performance with a diffusion-limiting current density of 5.4 mA cm–2 and an electron transfer number of 3.97. The improved electrocatalytic activity originates from a high content of active N,P-containing catalytic sites uniformly distributed on porous carbon. This study provides a viable strategy to develop functional composite materials by modulating the flexibility of 2D COPs for 1D substrates, contributing to broad applicability.