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

Tuci, Giulia;Rossin, Andrea;Giambastiani, Giuliano
2024

Abstract

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.
2024
Istituto di Chimica dei Composti OrganoMetallici - ICCOM -
Active sites and action mechanism
C-based nanomaterials
Metal-free electrocatalysts
lighweight doping and co-doping
two-electron oxygen reduction reaction
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Descrizione: "This is the peer reviewed version of the following article: G. Tuci, A. Rossin, Z. Saki, L. Caporaso, Y. Liu, G. Centi, G. Giambastiani, ChemSusChem 2024, e202400660, which has been published in final form at https://doi.org/10.1002/cssc.202400660. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. This article may not be enhanced, enriched or otherwise transformed into a derivative work, without express permission from Wiley or by statutory rights under applicable legislation. Copyright notices must not be removed, obscured or modified. The article must be linked to Wiley’s versino of record on Wiley Online Library and any embedding, framing or otherwise making available the article or pages thereof by third parties from platforms, services and websites other than Wiley Online Library must be prohibited."
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/20.500.14243/491602
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