Zhang, Wuyong ; Zhan, Shaoqi ; Qin, Qing ; Heil, Tobias ; Liu, Xiyu ; Hwang, Jinyeon ; Ferber, Thimo H. ; Hofmann, Jan P. ; Oschatz, Martin (2022)
Electrochemical Generation of Catalytically Active Edge Sites in C₂N‐Type Carbon Materials for Artificial Nitrogen Fixation.
In: Small : nano micro, 2022, 18 (42)
doi: 10.26083/tuprints-00022888
Artikel, Zweitveröffentlichung, Verlagsversion
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Kurzbeschreibung (Abstract)
The electrochemical nitrogen reduction reaction (NRR) to ammonia (NH₃) is a potentially carbon‐neutral and decentralized supplement to the established Haber–Bosch process. Catalytic activation of the highly stable dinitrogen molecules remains a great challenge. Especially metal‐free nitrogen‐doped carbon catalysts do not often reach the desired selectivity and ammonia production rates due to their low concentration of NRR active sites and possible instability of heteroatoms under electrochemical potential, which can even contribute to false positive results. In this context, the electrochemical activation of nitrogen‐doped carbon electrocatalysts is an attractive, but not yet established method to create NRR catalytic sites. Herein, a metal‐free C₂N material (HAT‐700) is electrochemically etched prior to application in NRR to form active edge‐sites originating from the removal of terminal nitrile groups. Resulting activated metal‐free HAT‐700‐A shows remarkable catalytic activity in electrochemical nitrogen fixation with a maximum Faradaic efficiency of 11.4% and NH₃ yield of 5.86 µg mg⁻¹cat h⁻¹. Experimental results and theoretical calculations are combined, and it is proposed that carbon radicals formed during activation together with adjacent pyridinic nitrogen atoms play a crucial role in nitrogen adsorption and activation. The results demonstrate the possibility to create catalytically active sites on purpose by etching labile functional groups prior to NRR.
| Typ des Eintrags: | Artikel |
|---|---|
| Erschienen: | 2022 |
| Autor(en): | Zhang, Wuyong ; Zhan, Shaoqi ; Qin, Qing ; Heil, Tobias ; Liu, Xiyu ; Hwang, Jinyeon ; Ferber, Thimo H. ; Hofmann, Jan P. ; Oschatz, Martin |
| Art des Eintrags: | Zweitveröffentlichung |
| Titel: | Electrochemical Generation of Catalytically Active Edge Sites in C₂N‐Type Carbon Materials for Artificial Nitrogen Fixation |
| Sprache: | Englisch |
| Publikationsjahr: | 2022 |
| Ort: | Darmstadt |
| Publikationsdatum der Erstveröffentlichung: | 2022 |
| Verlag: | Wiley-VCH |
| Titel der Zeitschrift, Zeitung oder Schriftenreihe: | Small : nano micro |
| Jahrgang/Volume einer Zeitschrift: | 18 |
| (Heft-)Nummer: | 42 |
| Kollation: | 9 Seiten |
| DOI: | 10.26083/tuprints-00022888 |
| URL / URN: | https://tuprints.ulb.tu-darmstadt.de/22888 |
| Zugehörige Links: | |
| Herkunft: | Zweitveröffentlichung DeepGreen |
| Kurzbeschreibung (Abstract): | The electrochemical nitrogen reduction reaction (NRR) to ammonia (NH₃) is a potentially carbon‐neutral and decentralized supplement to the established Haber–Bosch process. Catalytic activation of the highly stable dinitrogen molecules remains a great challenge. Especially metal‐free nitrogen‐doped carbon catalysts do not often reach the desired selectivity and ammonia production rates due to their low concentration of NRR active sites and possible instability of heteroatoms under electrochemical potential, which can even contribute to false positive results. In this context, the electrochemical activation of nitrogen‐doped carbon electrocatalysts is an attractive, but not yet established method to create NRR catalytic sites. Herein, a metal‐free C₂N material (HAT‐700) is electrochemically etched prior to application in NRR to form active edge‐sites originating from the removal of terminal nitrile groups. Resulting activated metal‐free HAT‐700‐A shows remarkable catalytic activity in electrochemical nitrogen fixation with a maximum Faradaic efficiency of 11.4% and NH₃ yield of 5.86 µg mg⁻¹cat h⁻¹. Experimental results and theoretical calculations are combined, and it is proposed that carbon radicals formed during activation together with adjacent pyridinic nitrogen atoms play a crucial role in nitrogen adsorption and activation. The results demonstrate the possibility to create catalytically active sites on purpose by etching labile functional groups prior to NRR. |
| Freie Schlagworte: | activation, electrocatalysis, nitrogen fixation, nitrogen‐doped carbon |
| Status: | Verlagsversion |
| URN: | urn:nbn:de:tuda-tuprints-228887 |
| Sachgruppe der Dewey Dezimalklassifikatin (DDC): | 500 Naturwissenschaften und Mathematik > 540 Chemie 600 Technik, Medizin, angewandte Wissenschaften > 660 Technische Chemie |
| Fachbereich(e)/-gebiet(e): | 11 Fachbereich Material- und Geowissenschaften 11 Fachbereich Material- und Geowissenschaften > Materialwissenschaft 11 Fachbereich Material- und Geowissenschaften > Materialwissenschaft > Fachgebiet Oberflächenforschung |
| Hinterlegungsdatum: | 23 Dez 2022 13:55 |
| Letzte Änderung: | 28 Dez 2022 07:16 |
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| Suche nach Titel in: | TUfind oder in Google |
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- Electrochemical Generation of Catalytically Active Edge Sites in C₂N‐Type Carbon Materials for Artificial Nitrogen Fixation. (deposited 23 Dez 2022 13:55) [Gegenwärtig angezeigt]
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