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The Tetrapyrollic Motif in Nitrogen Doped Carbons and M-N-C Electrocatalysts as Active Site in the Outer-Sphere Mechanism of the Alkaline Oxygen Reduction Reaction
- Development and fundamental understanding of precious-group-metal-free electrocatalysts is hampered by limitations in the quantification of the intrinsic activity of different catalytic sites and understanding the different reaction mechanisms. Comparing isomorphic nitrogen-doped carbons, Zn-N-Cs and Fe-N-Cs with the common tetrapyrrolic motif, a catalyst-independent outer-sphere rate-determining step in the alkaline oxygen reduction reaction is observed. Density functional theory (DFT) simulations on tetrapyrrolic model structures indicate the highest occupied molecular orbital (HOMO) level as a good descriptor for the catalytic activity. Contour plots suggest that the electron transfer occurs directly from the tetrapyrrolic coordination site, rather than from the metal center. Metal-free tetrapyrrolic N4 sites are discovered to be highly active oxygen reduction reaction (ORR) active sites in alkaline that reach turnover frequencies (TOF) of 0.33 and 1.84 s−1 at 0.80 and 0.75 VRHE inDevelopment and fundamental understanding of precious-group-metal-free electrocatalysts is hampered by limitations in the quantification of the intrinsic activity of different catalytic sites and understanding the different reaction mechanisms. Comparing isomorphic nitrogen-doped carbons, Zn-N-Cs and Fe-N-Cs with the common tetrapyrrolic motif, a catalyst-independent outer-sphere rate-determining step in the alkaline oxygen reduction reaction is observed. Density functional theory (DFT) simulations on tetrapyrrolic model structures indicate the highest occupied molecular orbital (HOMO) level as a good descriptor for the catalytic activity. Contour plots suggest that the electron transfer occurs directly from the tetrapyrrolic coordination site, rather than from the metal center. Metal-free tetrapyrrolic N4 sites are discovered to be highly active oxygen reduction reaction (ORR) active sites in alkaline that reach turnover frequencies (TOF) of 0.33 and 1.84 s−1 at 0.80 and 0.75 VRHE in the order of magnitude of tetrapyrrolic Fe–N4 sites in the acidic ORR. While Zn-coordination lowers the HOMO level and therefore the catalytic activity, Fe-coordination lifts the HOMO level resulting in TOF values of 0.4 and 4 s−1 for tetrapyrrolic Fe–N4 sites at 0.90 and 0.85 VRHE, respectively. At higher mass activities, the peroxide reduction becomes rate-limiting, where highest peroxide production rates are observed for the nitrogen-doped carbon.…
Autor*innen: | D. Menga, Jian Liang Low, Ana Guilherme Buzanich, B. Paulus, Tim-Patrick Fellinger |
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Dokumenttyp: | Zeitschriftenartikel |
Veröffentlichungsform: | Verlagsliteratur |
Sprache: | Englisch |
Titel des übergeordneten Werkes (Englisch): | Advanced Energy Materials |
Jahr der Erstveröffentlichung: | 2024 |
Organisationseinheit der BAM: | 3 Gefahrgutumschließungen; Energiespeicher |
3 Gefahrgutumschließungen; Energiespeicher / 3.6 Elektrochemische Energiematerialien | |
6 Materialchemie | |
6 Materialchemie / 6.3 Strukturanalytik | |
Veröffentlichende Institution: | Bundesanstalt für Materialforschung und -prüfung (BAM) |
Verlag: | Wiley-VCH |
Jahrgang/Band: | 2024 |
Aufsatznummer: | 2400482 |
Erste Seite: | 1 |
Letzte Seite: | 8 |
DDC-Klassifikation: | Technik, Medizin, angewandte Wissenschaften / Ingenieurwissenschaften / Angewandte Physik |
Freie Schlagwörter: | Alkaline Oxygen; Carbons; Motif; Nitrogen; Tetrapyrollic |
Themenfelder/Aktivitätsfelder der BAM: | Energie |
Energie / Wasserstoff | |
DOI: | https://doi.org/10.1002/aenm.202400482 |
URN: | urn:nbn:de:kobv:b43-606239 |
Verfügbarkeit des Dokuments: | Datei für die Öffentlichkeit verfügbar ("Open Access") |
Lizenz (Deutsch): | Creative Commons - CC BY - Namensnennung 4.0 International |
Datum der Freischaltung: | 16.07.2024 |
Referierte Publikation: | Nein |
Schriftenreihen ohne Nummerierung: | Wissenschaftliche Artikel der BAM |