The Still Elusive Role of Lightweight Doping in Carbon-Based Electrocatalysts for the Selective Oxygen Reduction Reaction to Hydrogen Peroxide

The two-electron electrocatalytic oxygen reduction reaction (ORR) to hydrogen peroxide (H2O2) is a valuable alternative to the more conventional and energy-intensive anthraquinone process. From a circularity viewpoint, metal-free catalysts constitute a sustainable alternative for the process. In particular, lightweight hetero-doped C-materials are cost-effective and easily scalable samples that replace - more and more frequently - the use of critical raw elements in the preparation of highly performing (electro)catalysts. Anyhow, their large-scale exploitation in industrial processes still suffers from technical limits of samples upscale and reproducibility other than a still moderate comprehension of their action mechanism in the process. This concept article offers a comprehensive and exhaustive "journey" through the most representative lightweight hetero-doped C-based electrocatalysts and their performance in the 2e- ORR process. It provides an interpretation of phenomena at the triple-phase interface of solid catalyst, liquid electrolyte and gaseous oxygen based on the doping-driven generation of ideal electronic microenvironments at the catalyst surface.The concept offers a comprehensive "journey" through the most representative lightweight hetero-doped C-based electrocatalysts and their performance in the 2e- ORR process. It aims at providing a rationale in the role of doping with respect to the generation of ideal electronic microenvironments at the catalysts surface for the selective process to occur. image