Synergistic Effects in N,O-Comodified Carbon Nanotubes Boost Highly Selective Electrochemical Oxygen Reduction to H2
Shuhui Xu1, Ruihu Lu2, Kai Sun1
1State Key Laboratory of Chemical Resource Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing, 100029, China.
Abstract:
Electrochemical 2-electron oxygen reduction reaction (ORR) is a promising route for renewable and on-site H2 O2 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%) H2 O2 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 H2 O2 productivity of 264.8 mol kgcat -1 h-1 .
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