Heppe, Nils ; Gallenkamp, Charlotte ; Paul, Stephen ; Segura‐Salas, Nicole ; Rhein, Niklas von ; Kaiser, Bernhard ; Jaegermann, Wolfram ; Jafari, Atefeh ; Sergueev, Ilya ; Krewald, Vera ; Kramm, Ulrike I. (2023)
Substituent Effects in Iron Porphyrin Catalysts for the Hydrogen Evolution Reaction.
In: Chemistry - A European Journal, 2023, 29 (10)
doi: 10.26083/tuprints-00023704
Artikel, Zweitveröffentlichung, Verlagsversion
 | Es ist eine neuere Version dieses Eintrags verfügbar. |
Kurzbeschreibung (Abstract)
For a future hydrogen economy, non‐precious metal catalysts for the water splitting reactions are needed that can be implemented on a global scale. Metal‐nitrogen‐carbon (MNC) catalysts with active sites constituting a metal center with fourfold coordination of nitrogen (MN4) show promising performance, but an optimization rooted in structure‐property relationships has been hampered by their low structural definition. Porphyrin model complexes are studied to transfer insights from well‐defined molecules to MNC systems. This work combines experiment and theory to evaluate the influence of porphyrin substituents on the electronic and electrocatalytic properties of MN4 centers with respect to the hydrogen evolution reaction (HER) in aqueous electrolyte. We found that the choice of substituent affects their utilization on the carbon support and their electrocatalytic performance. We propose an HER mechanism for supported iron porphyrin complexes involving a [FeII(P⋅)]− radical anion intermediate, in which a porphinic nitrogen atom acts as an internal base. While this work focuses on the HER, the limited influence of a simultaneous interaction with the support and an aqueous electrolyte will likely be transferrable to other catalytic applications.
| Typ des Eintrags: | Artikel |
|---|---|
| Erschienen: | 2023 |
| Autor(en): | Heppe, Nils ; Gallenkamp, Charlotte ; Paul, Stephen ; Segura‐Salas, Nicole ; Rhein, Niklas von ; Kaiser, Bernhard ; Jaegermann, Wolfram ; Jafari, Atefeh ; Sergueev, Ilya ; Krewald, Vera ; Kramm, Ulrike I. |
| Art des Eintrags: | Zweitveröffentlichung |
| Titel: | Substituent Effects in Iron Porphyrin Catalysts for the Hydrogen Evolution Reaction |
| Sprache: | Englisch |
| Publikationsjahr: | 27 November 2023 |
| Ort: | Darmstadt |
| Publikationsdatum der Erstveröffentlichung: | 2023 |
| Ort der Erstveröffentlichung: | Weinheim |
| Verlag: | Wiley-VCH |
| Titel der Zeitschrift, Zeitung oder Schriftenreihe: | Chemistry - A European Journal |
| Jahrgang/Volume einer Zeitschrift: | 29 |
| (Heft-)Nummer: | 10 |
| Kollation: | 16 Seiten |
| DOI: | 10.26083/tuprints-00023704 |
| URL / URN: | https://tuprints.ulb.tu-darmstadt.de/23704 |
| Zugehörige Links: | |
| Herkunft: | Zweitveröffentlichung DeepGreen |
| Kurzbeschreibung (Abstract): | For a future hydrogen economy, non‐precious metal catalysts for the water splitting reactions are needed that can be implemented on a global scale. Metal‐nitrogen‐carbon (MNC) catalysts with active sites constituting a metal center with fourfold coordination of nitrogen (MN4) show promising performance, but an optimization rooted in structure‐property relationships has been hampered by their low structural definition. Porphyrin model complexes are studied to transfer insights from well‐defined molecules to MNC systems. This work combines experiment and theory to evaluate the influence of porphyrin substituents on the electronic and electrocatalytic properties of MN4 centers with respect to the hydrogen evolution reaction (HER) in aqueous electrolyte. We found that the choice of substituent affects their utilization on the carbon support and their electrocatalytic performance. We propose an HER mechanism for supported iron porphyrin complexes involving a [FeII(P⋅)]− radical anion intermediate, in which a porphinic nitrogen atom acts as an internal base. While this work focuses on the HER, the limited influence of a simultaneous interaction with the support and an aqueous electrolyte will likely be transferrable to other catalytic applications. |
| Freie Schlagworte: | density functional theory, electrochemistry, heterogeneous catalysis, hydrogen, molecular electrochemistry, renewable resources |
| ID-Nummer: | e202202465 |
| Status: | Verlagsversion |
| URN: | urn:nbn:de:tuda-tuprints-237042 |
| Zusätzliche Informationen: | A previous version of this manuscript has been deposited on a preprint server (https://10.26434/chemrxiv-2022-x76g3). |
| Sachgruppe der Dewey Dezimalklassifikatin (DDC): | 500 Naturwissenschaften und Mathematik > 540 Chemie |
| Fachbereich(e)/-gebiet(e): | 11 Fachbereich Material- und Geowissenschaften 11 Fachbereich Material- und Geowissenschaften > Materialwissenschaft 07 Fachbereich Chemie > Eduard Zintl-Institut > Fachgebiet Anorganische Chemie > Fachgruppe Katalysatoren und Elektrokatalysatoren 11 Fachbereich Material- und Geowissenschaften > Materialwissenschaft > Fachgebiet Oberflächenforschung 07 Fachbereich Chemie 07 Fachbereich Chemie > Eduard Zintl-Institut > Fachgebiet Anorganische Chemie 07 Fachbereich Chemie > Theoretische Chemie (am 07.02.2024 umbenannt in Quantenchemie) |
| Hinterlegungsdatum: | 27 Nov 2023 13:51 |
| Letzte Änderung: | 28 Nov 2023 06:43 |
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