High pressure decomposition of a sandwich compound
Year: 2023
Authors: Fanetti S.; Romi S.; Berretti E.; Hanfland M.; Mijit E.; Alabarse F.; Dalladay-Simpson P.; Gorelli F.; Bini R.; Santoro M.
Autors Affiliation: CNR, CNR ICCOM, Ist Chim Composti OrganoMetall, Via Madonna Piano 10, I-50019 Sesto Fiorentino, FI, Italy; LENS, European Lab Nonlinear Spect, Via Nello Carrara 1, I-50019 Sesto Fiorentino, FI, Italy; CNR, Ist Nazl Ott, CNR INO, Via Nello Carrara, I-50019 Sesto Fiorentino, FI, Italy; European Synchrotron Radiat Facil, 71 Ave Martyrs,CS40220, F-38043 Grenoble 9, France; Elettra Sincrotrone Trieste SCpA, AREA Sci Pk, I-34149 Basovizza, TS, Italy; Ctr High Pressure Sci & Technol Adv Res, Shanghai 201203, Peoples R China; Univ Firenze, Dipartimento Chim Ugo Schiff, Via Lastruccia 3, I-50019 Sesto Fiorentino, FI, Italy.
Abstract: While it is widely recognized that purely organic molecular systems with multiple bonds undergo chemical condensation at sufficiently high pressures (from tenths to tens of GPa), the fate of organometallics at extreme conditions remains largely underexplored. We have investigated the high pressure (up to 41 GPa) chemical transformations in a simple molecular system known as nickelocene, (C5H5)2Ni, which serves as a representative example of a class of organometallics called sandwich compounds. Nickelocene decomposed above 13 GPa, at room temperature, while lower pressure thresholds have been observed at higher temperatures (295-573 K). The products were identified as nanocomposite materials, primarily composed of disordered, nickel-rich nanoparticles segregated within an extended, amorphous matrix of hydrogenated carbon (a-C:H). The investigation was conducted by means of diamond anvil cells in combination with optical spectroscopies and microscopy, synchrotron x-ray absorption spectroscopy and diffraction, as well as transmission electron microscopy. Our findings have the potential to stimulate further research into the high-pressure chemical reactivity of organometallics and open up new synthesis routes for the production of metal-based nanoparticles, which find a wide range of applications.
Journal/Review: JOURNAL OF CHEMICAL PHYSICS
Volume: 159 (13) Pages from: 134502-1 to: 134502 -11
More Information: We thank LENS for hosting the research. We acknowledge Joao Elias F. S. Rodrigues for his help during the XAS measurements at the BM23 beamline of ESRF. We then acknowledge the European Synchrotron Radiation Facility and Elettra Sincrotrone Trieste for providing access to the ID15B and Xpress beam-lines, respectively, and for financial support under the Proposal Nos. CH-5992 (ESRF) and 20220094 (Elettra). We thank the Fondazione Ente Cassa di Risparmio di Firenze for the strong support through the SALUS Grant. We also thank “Ente Cassa di Risparmio di Firenze,” Grant No. 2013.0878, and Regione Toscana POR FESR 2014-2020 for the project FELIX (Fotonica ed Elettronica Integrate per lŽIndustria), Grant No. 6455 and the Italian MIUR funding Fondo Investimenti (art. 1 comma 1072 legge 205/2017) -Realizzazione, acquisto, ammodernamento, a manutenzione straordinaria delle infrastrutture di ricerca e dei relativi immobili -CNR Progetto N. 40. Acquisto di un microscopio HRTEM ad ultra-alta risoluzione per la caratterizzazione di materiali per la filiera dellŽidrogeno, lŽenergia e la sostenibilita.KeyWords: High pressure engineering; High resolution transmission electron microscopy; Metal nanoparticles; Nanocomposites; Synthesis (chemical); X ray absorption spectroscopy; nickeloceneDOI: 10.1063/5.0167748Connecting to view paper tab on IsiWeb: Click here