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dc.contributor.authorChen, Zen
dc.contributor.authorVorobyeva, Een
dc.contributor.authorMitchell, Sen
dc.contributor.authorFako, Een
dc.contributor.authorLópez, Nen
dc.contributor.authorCollins, Seanen
dc.contributor.authorLeary, RKen
dc.contributor.authorMidgley, Paulen
dc.contributor.authorHauert, Ren
dc.contributor.authorPérez-Ramírez, Jen
dc.date.accessioned2019-02-08T15:35:31Z
dc.date.available2019-02-08T15:35:31Z
dc.date.issued2018-09-01en
dc.identifier.issn2095-5138
dc.identifier.urihttps://www.repository.cam.ac.uk/handle/1810/289026
dc.description.abstractCarbon 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.
dc.description.sponsorshipEuropean Research Council (291522-3DIMAGE) ETH Zurich Swiss National Science Foundation (200021-169679) Spanish Ministerio de Economía y Competitividad (CTQ2015-68770-R)
dc.publisherOUP
dc.titleSingle-atom heterogeneous catalysts based on distinct carbon nitride scaffoldsen
dc.typeArticle
prism.endingPage652
prism.issueIdentifier5en
prism.publicationDate2018en
prism.publicationNameNational Science Reviewen
prism.startingPage642
prism.volume5en
dc.identifier.doi10.17863/CAM.36288
dcterms.dateAccepted2018-04-10en
rioxxterms.versionofrecord10.1093/nsr/nwy048en
rioxxterms.versionAM*
rioxxterms.licenseref.urihttp://www.rioxx.net/licenses/all-rights-reserveden
rioxxterms.licenseref.startdate2018-09-01en
dc.contributor.orcidCollins, Sean [0000-0002-5151-6360]
dc.contributor.orcidMidgley, Paul [0000-0002-6817-458X]
dc.identifier.eissn2053-714X
rioxxterms.typeJournal Article/Reviewen
pubs.funder-project-idEuropean Research Council (291522)
rioxxterms.freetoread.startdate2019-04-17


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