Metal-Free Electrocatalysts for the Selective 2 e- Oxygen Reduction Reaction: A Never-Ending Story?

Chemistry. 2023 Jul 26;29(42):e202301036. doi: 10.1002/chem.202301036. Epub 2023 Jun 16.

Abstract

Hydrogen peroxide (H2 O2 ) electrosynthesis via the 2e- Oxygen Reduction Reaction (ORR) represents a highly challenging, environmentally friendly and cost-effective alternative to the current anthraquinone-based technology. Various lightweight element hetero-doped carbon nanostructures are promising and cheap metal-free electrocatalysts for H2 O2 synthesis, particularly those containing O-functionalities. The exact role of O-containing functional groups as electroactive sites for the process remains debated if not highly controversial. Herein, we have reported on the covalent exohedral functionalization of the outer surface of extra-pure multi-walled carbon nanotubes (MWCNTs) with discrete O-functional groups as a unique approach to prepare selective electrocatalysts for the process. This kind of decoration has added fundamental tiles to the puzzling structure/reactivity relationship of O-containing carbon-based catalysts for ORR, clearing doubts on the controversial role of hydroxyl/phenol groups as key functionalities for the design of more performing 2e- ORR electrocatalysts.

Keywords: 2e− oxygen reduction reaction; carbon nanomaterials functionalization; electrocatalyst surface chemical engineering; hydrogen peroxide production; metal-free electrocatalysts.