Single-atom heterogeneous catalysts based on distinct carbon nitride scaffolds
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Authors
Chen, Z
Vorobyeva, E
Mitchell, S
Fako, E
López, N
Leary, RK
Hauert, R
Pérez-Ramírez, J
Publication Date
2018-09-01Journal Title
National Science Review
ISSN
2095-5138
Publisher
OUP
Volume
5
Issue
5
Pages
642-652
Type
Article
This Version
AM
Metadata
Show full item recordCitation
Chen, Z., Vorobyeva, E., Mitchell, S., Fako, E., López, N., Collins, S., Leary, R., et al. (2018). Single-atom heterogeneous catalysts based on distinct carbon nitride scaffolds. National Science Review, 5 (5), 642-652. https://doi.org/10.1093/nsr/nwy048
Abstract
Carbon nitrides integrating macroheterocycles offer unique potential as hosts for stabilizing metal atoms due to their rich electronic structure. To date, only graphitic heptazine-based polymers have been studied. Here, we demonstrate that palladium atoms can be effectively isolated on other carbon nitride scaffolds including linear melem oligomers and poly(triazine/heptazine imides). Increased metal uptake was linked to the larger cavity size and the presence of chloride ions in the polyimide structures. Changing the host structure leads to significant variation of the average oxidation state of the metal, which can be tuned by exchange of the ionic species as evidenced by X-ray photoelectron spectroscopy
and supported by density functional theory. Evaluation in the semi
-hydrogenation of 2-methyl-3-butyn-2-ol reveals an inverse correlation between the activity and the degree of oxidation of palladium, with
oligomers exhibiting the highest activity. These findings provide new mechanistic insights into the influence of the carbon nitride structure
on metal stabilization.
Sponsorship
European Research Council (291522-3DIMAGE)
ETH Zurich
Swiss National Science Foundation (200021-169679)
Spanish Ministerio de Economía y Competitividad (CTQ2015-68770-R)
Funder references
European Research Council (291522)
Identifiers
External DOI: https://doi.org/10.1093/nsr/nwy048
This record's URL: https://www.repository.cam.ac.uk/handle/1810/289026
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