Chen, Z, Mitchell, S, Vorobyeva, E et al. (11 more authors) (2017) Stabilization of Single Metal Atoms on Graphitic Carbon Nitride. Advanced Functional Materials, 27 (8). 1605785. ISSN 1616-301X
Abstract
Graphitic carbon nitride (g‐C3N4) exhibits unique properties as a support for single‐atom heterogeneous catalysts (SAHCs). Understanding how the synthesis method, carrier properties, and metal identity impact the isolation of metal centers is essential to guide their design. This study compares the effectiveness of direct and postsynthetic routes to prepare SAHCs by incorporating palladium, silver, iridium, platinum, or gold in g‐C3N4 of distinct morphology (bulk, mesoporous and exfoliated). The speciation (single atoms, dimers, clusters, or nanoparticles), distribution, and oxidation state of the supported metals are characterized by multiple techniques including extensive use of aberration‐corrected electron microscopy. SAHCs are most readily attained via direct approaches applying copolymerizable metal precursors and employing high surface area carriers. In contrast, although post‐synthetic routes enable improved control over the metal loading, nanoparticle formation is more prevalent. Comparison of the carrier morphologies also points toward the involvement of defects in stabilizing single atoms. The distinct metal dispersions are rationalized by density functional theory and kinetic Monte Carlo simulations, highlighting the interplay between the adsorption energetics and diffusion kinetics. Evaluation in the continuous three‐phase semihydrogenation of 1‐hexyne identifies controlling the metal–carrier interaction and exposing the metal sites at the surface layer as key challenges in designing efficient SAHCs.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2017 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim. This is the peer reviewed version of the following article: Chen, Z., Mitchell, S., Vorobyeva, E., Leary, R., Hauert, R., Furnival, T., Ramasse, Q., et al. (2017). Stabilization of Single Metal Atoms on Graphitic Carbon Nitride. Advanced Functional Materials, 27 (8), 1605785, which has been published in final form at https://doi.org/10.1002/adfm.201605785. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving. Uploaded in accordance with the publisher's self-archiving policy. |
Keywords: | aberration‐corrected scanning transmission electron microscopy; carbon nitride; density functional theory; kinetic Monte Carlo simulations; single‐atom heterogeneous catalysts |
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: | 20 Mar 2018 12:09 |
Last Modified: | 20 Mar 2018 12:09 |
Status: | Published |
Publisher: | Wiley |
Identification Number: | 10.1002/adfm.201605785 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:128726 |