N,F-Codoped Carbon Nanocages: An Efficient Electrocatalyst for Hydrogen Peroxide Electroproduction in Alkaline and Acidic Solutions

Abstract

Exploiting efficient electrocatalysts for hydrogen peroxide (H2O2) electroproduction by oxygen reduction reaction (ORR) is highly desired in practical application. Herein, nitrogen- and fluoride-codoped carbon nanocages (NF-Cs) are successfully synthesized through a simple and scalable template method. With the aid of a porous structure, a large surface area, and the introduction of N and F atoms, NF-Cs show excellent electrocatalytic performance for H2O2 electroproduction in alkaline solution (pH 13) with a faradaic efficiency of 89.6% at very positive applied potential (0.74 V). In acid solution (pH 0.35), the faradaic efficiency of H2O2 electroproduction stably maintains at 85%–88% in the range of 0.4–0.72 V potential. The experimental and theoretical results reveal that the strong synergistic effect between the doped N and F atoms facilitate the H2O2 electroproduction through 2e ORR. That is, the doped N atoms promote O2 molecule adsorption on the catalyst surface, and the F atoms facilitate the desorption of the *OOH intermediate, which is the key factor for the NF-Cs efficiently catalyzing H2O2 electroproduction. These results provide beneficial references for reasonably designing effective carbon-based electrocatalysts for H2O2 electroproduction.

Design Strategies of Non‐Noble Metal‐Based Electrocatalysts for Two‐Electron Oxygen Reduction to Hydrogen Peroxide

“…The doped N atom promotes oxygen adsorption on the catalyst surface, thus improving the catalytic performance for the ORR. Meanwhile, the doped F atom facilitates the desorption of the *OOH intermediate, leading to a high H 2 O 2 selectivity [79] . The N, F‐codoped carbons present catalytic performance for H 2 O 2 generation in both acid and alkaline electrolytes with a high faradaic efficiency (88 %, pH 0.35, 0.72 V; 89.6 %, pH 13, 0.74 V) and excellent stability.…”

Recent Progress of Single‐atom Catalysts in the Electrocatalytic Reduction of Oxygen to Hydrogen Peroxide

“…Non-noble metal-based SACs have also exhibited apparent ORR activity towards H 2 O 2 production. Carbon derivatives are generally used as the supporting matrices [5,16,[67][68][69][70][71][72]. For instance, graphene and carbon nanotubes doped with O, N, F, B, etc have been used rather extensively, into which a range of transition metal atoms (e. g., Co, Ni, Fe, Mn, Cu, etc.)…”

H2O2 production on a carbon cathode loaded with a nickel carbonate catalyst and on an oxide photoanode without an external bias

“…As for noble-metal-free cathodes, there are several reports on the use of carbon-based materials modied with inexpensive metal compounds mainly at basic pH. [38][39][40][41] However, efficiencies for the H 2 O 2 production with these cathodes were low at near-neutral pH, and an ion-exchange membrane was essential when the pH values of the anodic and cathodic electrolyte solutions were different. 21,22 Recently, we reported that a carbon cathode modied with a biomass-derived W-based electrocatalyst exhibited a relatively high cathodic current for the reductive H 2 O 2 production in a nearneutral KHCO 3 aqueous solution in a two-compartment cell, but the FE(H 2 O 2 ) and the partial current density for H 2 O 2 production were not enough.…”