Nickel Nanocluster-Stabilized Unsaturated Ni–N3 Atomic Sites for Efficient CO2-to-CO Electrolysis at Industrial-Level Current

  • Unsaturated Ni single-atom catalysts (SACs), Ni-Nx (x=1,2,3), have been investigated to break the conventional Ni-N4 structural limitation and provide more unoccupied 3d orbitals for CO2 reduction reaction (CO2RR) intermediates adsorption, but their intrinsically low structural stability has seriously hindered their applications. Here, we developed a strategy by integrating Ni nanoclusters to stabilize unsaturated Ni-N3 atomic sites for efficient CO2 electroreduction to CO at industrial-level current. Density Functional Theory (DFT) calculations revealed that the incorporation of Ni nanocluster effectively stabilizes the unsaturated Ni-N3 atomic sites and modulates their electronic structure to enhance the adsorption of the key intermediate *COOH during CO2RR. Guided by these insights, we prepared an optimal composite catalyst, Ni6@Ni-N3, which features a Ni6N6 nanocluster surrounded by six Ni-N3 single atoms sites, through low-temperature pyrolysis. The morphology and coordinativeUnsaturated Ni single-atom catalysts (SACs), Ni-Nx (x=1,2,3), have been investigated to break the conventional Ni-N4 structural limitation and provide more unoccupied 3d orbitals for CO2 reduction reaction (CO2RR) intermediates adsorption, but their intrinsically low structural stability has seriously hindered their applications. Here, we developed a strategy by integrating Ni nanoclusters to stabilize unsaturated Ni-N3 atomic sites for efficient CO2 electroreduction to CO at industrial-level current. Density Functional Theory (DFT) calculations revealed that the incorporation of Ni nanocluster effectively stabilizes the unsaturated Ni-N3 atomic sites and modulates their electronic structure to enhance the adsorption of the key intermediate *COOH during CO2RR. Guided by these insights, we prepared an optimal composite catalyst, Ni6@Ni-N3, which features a Ni6N6 nanocluster surrounded by six Ni-N3 single atoms sites, through low-temperature pyrolysis. The morphology and coordinative structure of Ni6@Ni-N3 were confirmed by an aberration-corrected transmission electron microscope (AC-TEM) and X-ray absorption spectroscopy (XAS). As a result, Ni6@Ni-N3 demonstrated a remarkably high CO Faradaic efficiency (FECO) of 99.7 % and a turnover frequency (TOF) of 83984.2 h−1 at 500 mA cm−2 under −1.15 VRHE, much better than those of Ni-N4 with a lower FECO of 86 % at 100 mA cm−2 and a TOF of 39309.9 h−1under identical potential. XAS analyses of Ni6@Ni-N3 before and after long-term CO2RR testing confirmed the excellent stability of its coordinative environment. This work highlights a generalizable approach for stabilizing unsaturated single-atom catalysts, paving the way for their application in high-performance CO2RR.zeige mehrzeige weniger

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Autor*innen:Wuyi Zhang, Asad MehmoodORCiD, Ghulam Ali, Hui Liu, Liyuan Chai, Jun Wu, Min Liu
Dokumenttyp:Zeitschriftenartikel
Veröffentlichungsform:Verlagsliteratur
Sprache:Englisch
Titel des übergeordneten Werkes (Englisch):Angewandte Chemie - International Edition
Jahr der Erstveröffentlichung:2025
Organisationseinheit der BAM:3 Gefahrgutumschließungen; Energiespeicher
3 Gefahrgutumschließungen; Energiespeicher / 3.6 Elektrochemische Energiematerialien
Verlag:Wiley-VCH
Verlagsort:Weinheim
Jahrgang/Band:64
Ausgabe/Heft:13
Aufsatznummer:e202424552
Erste Seite:1
Letzte Seite:10
DDC-Klassifikation:Technik, Medizin, angewandte Wissenschaften / Ingenieurwissenschaften / Angewandte Physik
Freie Schlagwörter:CO2 electrolysis; Electrochemical CO2 conversion; Single atom catalysts
Themenfelder/Aktivitätsfelder der BAM:Energie
Energie / Elektrische Energiespeicher und -umwandlung
DOI:10.1002/anie.202424552
ISSN:1521-3773
Verfügbarkeit des Dokuments:Datei im Netzwerk der BAM verfügbar ("Closed Access")
Datum der Freischaltung:10.04.2025
Referierte Publikation:Ja
Datum der Eintragung als referierte Publikation:10.04.2024
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