Nanodiamond‐Palladium Core–Shell Organohybrid Synthesis: A Mild Vapor‐Phase Procedure Enabling Nanolayering Metal onto Functionalized sp3‐Carbon |
| |
Authors: | Maria A Gunawan Oana Moncea Didier Poinsot Mariem Keskes Bruno Domenichini Olivier Heintz Rémi Chassagnon Frédéric Herbst Robert M K Carlson Jeremy E P Dahl Andrey A Fokin Peter R Schreiner Jean‐Cyrille Hierso |
| |
Affiliation: | 1. Institut de Chimie Moléculaire de l'Université de Bourgogne (ICMUB), UMR‐CNRS 6302, Université de Bourgogne Franche‐Comté (UBFC), Dijon, France;2. Institut für Organische Chemie, Justus‐Liebig‐Universit?t, Giessen, Germany;3. Laboratoire Interdisciplinaire Carnot de Bourgogne (ICB), UMR‐CNRS 6303, Université de Bourgogne Franche‐Comté (UBFC), Dijon, France;4. Stanford Institute for Materials and Energy Sciences, Stanford, CA, USA;5. Department of Organic Chemistry, Kiev Polytechnic Institute, Kiev, Ukraine;6. Institut Universitaire de France (IUF), Paris Cedex 5, France |
| |
Abstract: | A novel approach for the bottom‐up construction of hybrid organic–inorganic nanocomposites with an intimate arrangement between sp3‐carbon 3D molecular‐size nanodiamonds (diamondoids) and a coated palladium surface as nanolayer is reported. The construction process is conducted stepwisely from the gas phase, using first controlled vapor‐phase self‐assembly of tailor‐made functionalized diamantane derivatives, followed by low‐temperature (45 °C) chemical vapor deposition of an organometallic complex in a reducing H2 atmosphere over the self‐assembled diamondoid scaffold. The use of self‐assemblies of primary diamantane phosphine and phosphine oxide, which are produced with high structural uniformity and reproducibility, yields new hybrid diamondoid‐palladium materials incorporating Pd? O? PH? diamantane bonding motifs. Additional investigations provide evidence for a very challenging issue in the intimate construction of sp3‐C/metal scaffolds. Scanning electron microscopy and transmission electron microscopy microscopies combined with X‐ray photoelectron spectroscopy surface analysis and EDX bulk analysis confirm the formation of diamondoid‐palladium organohybrids with unique surface layering. The vapor phase‐controlled mild synthetic process allows excellent control over nanocomposite formation and morphology from molecular‐level modifications. As such, this bottom‐up composite building process bridges scales from the molecular (functionalized diamondoids) over nanoscopic (self‐assemblies) to microscopic regime (hybrids), in the challenging association of transition metals with an electronically saturated sp3‐carbon organic host material. |
| |
Keywords: | diamondoids nanocomposite nanodiamonds nanolayers palladium self‐assembly sp3‐C hybrid materials |
|
|