Büchele, S, Yakimov, A, Collins, SM orcid.org/0000-0002-5151-6360 et al. (11 more authors) (2022) Elucidation of Metal Local Environments in Single‐Atom Catalysts Based on Carbon Nitrides. Small, 18 (33). 2202080. p. 2202080. ISSN 1613-6810
Abstract
The ability to tailor the properties of metal centers in single-atom heterogeneous catalysts depends on the availability of advanced approaches for characterization of their structure. Except for specific host materials with well-defined metal adsorption sites, determining the local atomic environment remains a crucial challenge, often relying heavily on simulations. This article reports an advanced analysis of platinum atoms stabilized on poly(triazine imide), a nanocrystalline form of carbon nitride. The approach discriminates the distribution of surface coordination sites in the host, the evolution of metal coordination at different stages during the synthesis of the material, and the potential locations of metal atoms within the lattice. Consistent with density functional theory predictions, simultaneous high-resolution imaging in high-angle annular dark field and bright field modes experimentally confirms the preferred localization of platinum in-plane in the corners of the triangular cavities. X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS), and dynamic nuclear polarization enhanced 15N nuclear magnetic resonance (DNP-NMR) spectroscopies coupled with density functional theory (DFT) simulations reveal that the predominant metal species comprise Pt(II) bound to three nitrogen atoms and one chlorine atom inside the coordination sites. The findings, which narrow the gap between experimental and theoretical elucidation, contribute to the improved structural understanding and provide a benchmark for exploring the speciation of single-atom catalysts based on carbon nitrides.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2022 The Authors. Small published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution-NonCommercial License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes. |
Keywords: | carbon nitrides, characterization, metal coordination sites, metal speciation, single-atom catalysis |
Dates: |
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Institution: | The University of Leeds |
Academic Units: | The University of Leeds > Faculty of Engineering & Physical Sciences (Leeds) > School of Chemical & Process Engineering (Leeds) |
Depositing User: | Symplectic Publications |
Date Deposited: | 13 Jun 2022 13:24 |
Last Modified: | 18 Feb 2025 14:14 |
Status: | Published |
Publisher: | Wiley |
Identification Number: | 10.1002/smll.202202080 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:187822 |