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Electrochemical Generation of Catalytically Active Edge Sites in C₂N‐Type Carbon Materials for Artificial Nitrogen Fixation

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
Article, Secondary publication, Publisher's Version

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Item Type: Article
Type of entry: Secondary publication
Title: Electrochemical Generation of Catalytically Active Edge Sites in C₂N‐Type Carbon Materials for Artificial Nitrogen Fixation
Language: English
Date: 2022
Place of Publication: Darmstadt
Year of primary publication: 2022
Publisher: Wiley-VCH
Journal or Publication Title: Small : nano micro
Volume of the journal: 18
Issue Number: 42
Collation: 9 Seiten
DOI: 10.26083/tuprints-00022888
Corresponding Links:
Origin: Secondary publication DeepGreen
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.

Uncontrolled Keywords: activation, electrocatalysis, nitrogen fixation, nitrogen‐doped carbon
Status: Publisher's Version
URN: urn:nbn:de:tuda-tuprints-228887
Classification DDC: 500 Science and mathematics > 540 Chemistry
600 Technology, medicine, applied sciences > 660 Chemical engineering
Divisions: 11 Department of Materials and Earth Sciences > Material Science > Surface Science
Date Deposited: 23 Dec 2022 13:55
Last Modified: 05 Jan 2023 07:22
SWORD Depositor: Deep Green
URI: https://tuprints.ulb.tu-darmstadt.de/id/eprint/22888
PPN: 503274879
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