Show simple item record

dc.contributor.authorSun, Xiaohui
dc.contributor.authorWang, Riming
dc.contributor.authorOuld-Chikh, Samy
dc.contributor.authorOsadchii, Dmitrii
dc.contributor.authorLi, Guanna
dc.contributor.authorAguilar, Antonio
dc.contributor.authorHazemann, Jean-louis
dc.contributor.authorKapteijn, Freek
dc.contributor.authorGascon, Jorge
dc.date.accessioned2019-10-07T08:01:49Z
dc.date.available2019-10-07T08:01:49Z
dc.date.issued2019-09-25
dc.identifier.citationSun, X., Wang, R., Ould-Chikh, S., Osadchii, D., Li, G., Aguilar, A., … Gascon, J. (2019). Structure-activity relationships in metal organic framework derived mesoporous nitrogen-doped carbon containing atomically dispersed iron sites for CO2 electrochemical reduction. Journal of Catalysis, 378, 320–330. doi:10.1016/j.jcat.2019.09.013
dc.identifier.doi10.1016/j.jcat.2019.09.013
dc.identifier.urihttp://hdl.handle.net/10754/656926
dc.description.abstractMesoporous nitrogen-doped carbon nanoparticles with atomically dispersed iron sites (named mesoNC-Fe) are synthesized via high-temperature pyrolysis of an Fe containing ZIF-8 MOF. Hydrolysis of tetramethyl orthosilicate (TMOS) in the MOF framework prior to pyrolysis plays an essential role in maintaining a high surface area during the formation of the carbon structure, impeding the formation of iron (oxide) nanoparticles. To gain inside on the nature of the resulting atomically dispersed Fe moieties, HERFD-XANES, EXAFS and valence-to-core X-ray emission spectroscopies have been used. The experimental spectra (both XAS and XES) combined with theoretical calculations suggest that iron has a coordination sphere including a porphyrinic environment and OH/H2O moieties responsible for the high activity in CO2 electroreduction. DFT calculations demonstrate that CO formation is favored in these structures because the free energy barriers of *COOH formation are decreased and the adsorption of *H is impeded. The combination of such a unique coordination environment with a high surface area in the carbon structure of mesoNC-Fe makes more active sites accessible during catalysis and promotes CO2 electroreduction.
dc.description.sponsorshipWe thank Alma I. Olivos Suarez for help in the design of the graphical abstract. Mauro Rovezzi is kindly thanked for the extraction of the X-ray emission spectra. Guanna Li thanks the NWO veni grant (no. 016.Veni.172.034). NWO surfsara is acknowledged for providing access to the supercomputer facilities.
dc.publisherElsevier BV
dc.relation.urlhttps://linkinghub.elsevier.com/retrieve/pii/S0021951719304439
dc.rightsNOTICE: this is the author’s version of a work that was accepted for publication in Journal of Catalysis. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in Journal of Catalysis, [[Volume], [Issue], (2019-09-25)] DOI: 10.1016/j.jcat.2019.09.013 . © 2019. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/
dc.subjectCO2
dc.subjectCO
dc.subjectElectroreduction
dc.subjectAtomically dispersed sites
dc.subjectIron
dc.titleStructure-activity relationships in metal organic framework derived mesoporous nitrogen-doped carbon containing atomically dispersed iron sites for CO2 electrochemical reduction
dc.typeArticle
dc.contributor.departmentChemical Engineering Program
dc.contributor.departmentKAUST Catalysis Center (KCC)
dc.contributor.departmentPhysical Science and Engineering (PSE) Division
dc.identifier.journalJournal of Catalysis
dc.eprint.versionPost-print
dc.contributor.institutionCatalysis Engineering, Department of Chemical Engineering, Delft University of Technology, Van der Maasweg 9, 2629 HZ Delft, the Netherlands
dc.contributor.institutionInst. Néel, UPR 2940 CNRS – Univ. Grenoble Alpes, F-38000 Grenoble, France
kaust.personOuld-Chikh, Samy
kaust.personGascon, Jorge
refterms.dateFOA2019-10-07T10:14:14Z
dc.date.published-online2019-09-25
dc.date.published-print2019-10


Files in this item

Thumbnail
Name:
Sun et al.pdf
Size:
2.238Mb
Format:
PDF
Description:
Accepted manuscript

This item appears in the following Collection(s)

Show simple item record