Synergistic Effects in N,O-Comodified Carbon Nanotubes Boost Highly Selective Electrochemical Oxygen Reduction to H(2) O(2)

N、O共修饰碳纳米管的协同效应促进高选择性电化学氧还原生成H(2)O(2)

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Abstract

Electrochemical 2-electron oxygen reduction reaction (ORR) is a promising route for renewable and on-site H(2) O(2) production. Oxygen-rich carbon nanotubes have been demonstrated their high selectivity (≈80%), yet tailoring the composition and structure of carbon nanotubes to further enhance the selectivity and widen working voltage range remains a challenge. Herein, combining formamide condensation coating and mild temperature calcination, a nitrogen and oxygen comodified carbon nanotubes (N,O-CNTs) electrocatalyst is synthesized, which shows excellent selective (>95%) H(2) O(2) selectivity in a wide voltage range (from 0 to 0.65 V versus reversible hydrogen electrode). It is significantly superior to the corresponding selectivity values of CNTs (≈50% in 0-0.65 V vs RHE) and O-CNTs (≈80% in 0.3-0.65 V vs RHE). Density functional theory calculations revealed that the C neighbouring to N is the active site. Introducing O-related species can strengthen the adsorption of intermediates *OOH, while N-doping can weaken the adsorption of in situ generated *O and optimize the *OOH adsorption energy, thus improving the 2-electron pathway. With optimized N,O-CNTs catalysts, a Janus electrode is designed by adjusting the asymmetric wettability to achieve H(2) O(2) productivity of 264.8 mol kg(cat) (-1) h(-1) .

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