Chemical Insights into the Formation of Colloidal Iridium Nanoparticles from In Situ X-ray Total Scattering: Influence of Precursors and Cations on the Reaction Pathway
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Chemical Insights into the Formation of Colloidal Iridium Nanoparticles from In Situ X-ray Total Scattering : Influence of Precursors and Cations on the Reaction Pathway. / Mathiesen, Jette K.; Quinson, Jonathan; Blaseio, Sonja; Kjær, Emil T.S.; Dworzak, Alexandra; Cooper, Susan R.; Pedersen, Jack K.; Wang, Baiyu; Bizzotto, Francesco; Schröder, Johanna; Kinnibrugh, Tiffany L.; Simonsen, Søren B.; Theil Kuhn, Luise; Kirkensgaard, Jacob J.K.; Rossmeisl, Jan; Oezaslan, Mehtap; Arenz, Matthias; Jensen, Kirsten M.Ø.
I: Journal of the American Chemical Society, Bind 145, Nr. 3, 2023, s. 1769-1782.Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › fagfællebedømt
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TY - JOUR
T1 - Chemical Insights into the Formation of Colloidal Iridium Nanoparticles from In Situ X-ray Total Scattering
T2 - Influence of Precursors and Cations on the Reaction Pathway
AU - Mathiesen, Jette K.
AU - Quinson, Jonathan
AU - Blaseio, Sonja
AU - Kjær, Emil T.S.
AU - Dworzak, Alexandra
AU - Cooper, Susan R.
AU - Pedersen, Jack K.
AU - Wang, Baiyu
AU - Bizzotto, Francesco
AU - Schröder, Johanna
AU - Kinnibrugh, Tiffany L.
AU - Simonsen, Søren B.
AU - Theil Kuhn, Luise
AU - Kirkensgaard, Jacob J.K.
AU - Rossmeisl, Jan
AU - Oezaslan, Mehtap
AU - Arenz, Matthias
AU - Jensen, Kirsten M.Ø.
N1 - Funding Information: We are grateful for funding from the Villum Foundation through a Villum Young Investigator Grant (VKR00015416). Funding from the Danish Ministry of Higher Education and Science through the SMART Lighthouse is gratefully acknowledged. We acknowledge support from the Danish National Research Foundation Center for High Entropy Alloy Catalysis (DNRF 149). M.A. received funding from the Swiss National Science Foundation (SNSF) via the project no. 200021 184742. The Danish Research Council is acknowledged for covering travel expenses in relation to the synchrotron experiment (DanScatt). Funding Information: The authors would like to acknowledge the staff of beamline 11-ID-Bat Argonne National Laboratory (APS) for experimental assistance, in particular, O. J. Borkiewicz and C. Leighanne. Use of the Advanced Photon Source, an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science by Argonne National Laboratory, was supported by the U.S. DOE under contract no. DE-AC02-06CH11357 for the project GUP-65450 and GUP-73929. We gratefully thank Valerie Briois and Laurent Barthe for the technical support at the ROCK beamline, SOLEIL, France (Proposal ID 20190317). The work at the ROCK beamline was supported by a public grant overseen by the French National Research Agency (ANR) as part of the “Investissements d’Avenir” program (reference, ANR10-EQPX45). M.O. thanks the Ministerium für Bildung und Forschung (BMBF, ECatPEMFC, FKZ 03SF0539). We would like to thank Dr. Christopher Whitehead for fruitful discussion on kinetic modeling. Publisher Copyright: © 2023 American Chemical Society.
PY - 2023
Y1 - 2023
N2 - Iridium nanoparticles are important catalysts for several chemical and energy conversion reactions. Studies of iridium nanoparticles have also been a key for the development of kinetic models of nanomaterial formation. However, compared to other metals such as gold or platinum, knowledge on the nature of prenucleation species and structural insights into the resultant nanoparticles are missing, especially for nanoparticles obtained from IrxCly precursors investigated here. We use in situ X-ray total scattering (TS) experiments with pair distribution function (PDF) analysis to study a simple, surfactant-free synthesis of colloidal iridium nanoparticles. The reaction is performed in methanol at 50 °C with only a base and an iridium salt as precursor. From different precursor salts─IrCl3, IrCl4, H2IrCl6, or Na2IrCl6─colloidal nanoparticles as small as Ir∼55 are obtained as the final product. The nanoparticles do not show the bulk iridium face-centered cubic (fcc) structure but show decahedral and icosahedral structures. The formation route is highly dependent on the precursor salt used. Using IrCl3 or IrCl4, metallic iridium nanoparticles form rapidly from IrxClyn- complexes, whereas using H2IrCl6 or Na2IrCl6, the iridium nanoparticle formation follows a sudden growth after an induction period and the brief appearance of a crystalline phase. With H2IrCl6, the formation of different Irn (n = 55, 55, 85, and 116) nanoparticles depends on the nature of the cation in the base (LiOH, NaOH, KOH, or CsOH, respectively) and larger particles are obtained with larger cations. As the particles grow, the nanoparticle structure changes from partly icosahedral to decahedral. The results show that the synthesis of iridium nanoparticles from IrxCly is a valuable iridium nanoparticle model system, which can provide new compositional and structural insights into iridium nanoparticle formation and growth.
AB - Iridium nanoparticles are important catalysts for several chemical and energy conversion reactions. Studies of iridium nanoparticles have also been a key for the development of kinetic models of nanomaterial formation. However, compared to other metals such as gold or platinum, knowledge on the nature of prenucleation species and structural insights into the resultant nanoparticles are missing, especially for nanoparticles obtained from IrxCly precursors investigated here. We use in situ X-ray total scattering (TS) experiments with pair distribution function (PDF) analysis to study a simple, surfactant-free synthesis of colloidal iridium nanoparticles. The reaction is performed in methanol at 50 °C with only a base and an iridium salt as precursor. From different precursor salts─IrCl3, IrCl4, H2IrCl6, or Na2IrCl6─colloidal nanoparticles as small as Ir∼55 are obtained as the final product. The nanoparticles do not show the bulk iridium face-centered cubic (fcc) structure but show decahedral and icosahedral structures. The formation route is highly dependent on the precursor salt used. Using IrCl3 or IrCl4, metallic iridium nanoparticles form rapidly from IrxClyn- complexes, whereas using H2IrCl6 or Na2IrCl6, the iridium nanoparticle formation follows a sudden growth after an induction period and the brief appearance of a crystalline phase. With H2IrCl6, the formation of different Irn (n = 55, 55, 85, and 116) nanoparticles depends on the nature of the cation in the base (LiOH, NaOH, KOH, or CsOH, respectively) and larger particles are obtained with larger cations. As the particles grow, the nanoparticle structure changes from partly icosahedral to decahedral. The results show that the synthesis of iridium nanoparticles from IrxCly is a valuable iridium nanoparticle model system, which can provide new compositional and structural insights into iridium nanoparticle formation and growth.
U2 - 10.1021/jacs.2c10814
DO - 10.1021/jacs.2c10814
M3 - Journal article
C2 - 36631996
AN - SCOPUS:85146305229
VL - 145
SP - 1769
EP - 1782
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 3
ER -
ID: 337600164