Uncovering Dynamic Edge‐Sites in Atomic Co−N−C Electrocatalyst for Selective Hydrogen Peroxide Production

Understanding the nature of single‐atom catalytic sites and identifying their spectroscopic fingerprints are essential prerequisites for the rational design of target catalysts. Here, we apply correlated in situ X‐ray absorption and infrared spectroscopy to probe the edge‐site‐specific chemistry of...

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Published inAngewandte Chemie International Edition Vol. 62; no. 27; pp. e202304754 - n/a
Main Authors Hu, Jinwen, Shang, Wenzhe, Xin, Cuncun, Guo, Jingya, Cheng, Xusheng, Zhang, Songlin, Song, Suchan, Liu, Wei, Ju, Feng, Hou, Jungang, Shi, Yantao
Format Journal Article
LanguageEnglish
Published Germany Wiley Subscription Services, Inc 03.07.2023
EditionInternational ed. in English
Subjects
Active sites
Adsorption
Carbon dioxide
Catalysts
Chemical reduction
Cobalt
Edge-Site
Electrocatalysts
Hydrogen peroxide
In Situ
Infrared spectroscopy
Oxygen Reduction
Oxygen reduction reactions
Valence
X-Ray Absorption Spectroscopy
X-Ray Absorption Spectroscopy
Edge-Site
In Situ
Oxygen Reduction
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Summary:Understanding the nature of single‐atom catalytic sites and identifying their spectroscopic fingerprints are essential prerequisites for the rational design of target catalysts. Here, we apply correlated in situ X‐ray absorption and infrared spectroscopy to probe the edge‐site‐specific chemistry of Co−N−C electrocatalyst during the oxygen reduction reaction (ORR) operation. The unique edge‐hosted architecture affords single‐atom Co site remarkable structural flexibility with adapted dynamic oxo adsorption and valence state shuttling between Co(2−δ)+ and Co2+, in contrast to the rigid in‐plane embedded Co1−Nx counterpart. Theoretical calculations demonstrate that the synergistic interplay of in situ reconstructed Co1−N2‐oxo with peripheral oxygen groups gives a rise to the near‐optimal adsorption of *OOH intermediate and substantially increases the activation barrier for its dissociation, accounting for a robust acidic ORR activity and 2e− selectivity for H2O2 production. A correlated in situ X‐ray absorption and infrared spectroscopy study provides insight into the dynamics of the edge‐sites in atomic Co−N−C electrocatalyst during the oxygen reduction reaction. Observation of adapted dynamic oxo adsorption and valence state shuttling between Co(2−δ)+ and Co2+ manifests the structural flexibility of unique edge‐hosted atomic Co sites, in contrast to the rigid in‐plane embedded Co1−Nx counterpart.
Bibliography:These authors contributed equally to this work.
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ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202304754