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  Real-space identification of non-noble single atomic catalytic sites within metal-coordinated supramolecular networks

Schulze Lammers, B., Lopez Salas, N., Stein Siena, J., Mirhosseini, H., Yesilpinar, D., Heske, J., et al. (2022). Real-space identification of non-noble single atomic catalytic sites within metal-coordinated supramolecular networks. ACS Nano, 16(9), 14248-14296. doi:10.1021/acsnano.2c04439.

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 Creators:
Schulze Lammers, Bertram, Author
Lopez Salas, Nieves1, Author           
Stein Siena, Julya2, Author           
Mirhosseini, Hossein, Author
Yesilpinar, Damla, Author
Heske, Julian, Author
Kühne, Thomas D., Author
Fuchs, Harald, Author
Antonietti, Markus2, Author           
Mönig, Harry, Author
Affiliations:
1Nieves Lopez Salas, Kolloidchemie, Max Planck Institute of Colloids and Interfaces, Max Planck Society, ou_3029702              
2Markus Antonietti, Kolloidchemie, Max Planck Institute of Colloids and Interfaces, Max Planck Society, ou_1863321              

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Free keywords: single-atom surface catalysis; oxygen reduction reaction; ORR; cyclic voltammetry; metal-coordinated supramolecular network; on-surface synthesis; noncontact atomic force microscopy; density functional theory
 Abstract: With regard to the development of single atom catalysts (SACs), non-noble metal–organic layers combine a large functional variability with cost efficiency. Here, we characterize reacted layers of melamine and melem molecules on a Cu(111) surface by noncontact atomic force microscopy (nc-AFM), X-ray photoelectron spectroscopy (XPS) and ab initio simulations. Upon deposition on the substrate and subsequent heat treatments in ultrahigh vacuum (UHV), these precursors undergo a stepwise dehydrogenation. After full dehydrogenation of the amino groups, the molecular units lie flat and are strongly chemisorbed on the copper substrate. We observe a particularly extreme interaction of the dehydrogenated nitrogen atoms with single copper atoms located at intermolecular sites. In agreement with the nc-AFM measurements performed with an O-terminated copper tip on these triazine- and heptazine-based copper nitride structures, our ab initio simulations confirm a pronounced interaction of oxygen species at these N–Cu–N sites. To investigate the related functional properties of our samples regarding the oxygen reduction reaction (ORR), we developed an electrochemical setup for cyclic voltammetry experiments performed at ambient pressure within a drop of electrolyte in a controlled O2 or N2 environment. Both copper nitride structures show a robust activity in irreversibly catalyzing the reduction of oxygen. The activity is assigned to the intermolecular N–Cu–N sites of the triazine- and heptazine-based copper nitrides or corresponding oxygenated versions (N–CuO–N, N–CuO2–N). By combining nc-AFM characterization on the atomic scale with a direct electrochemical proof of performance, our work provides fundamental insights about active sites in a technologically highly relevant reaction.

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Language(s): eng - English
 Dates: 2022-09-022022
 Publication Status: Published in print
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 Identifiers: DOI: 10.1021/acsnano.2c04439
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Title: ACS Nano
  Other : ACS Nano
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 16 (9) Sequence Number: - Start / End Page: 14248 - 14296 Identifier: ISSN: 1936-0851