Hybrid Diamond-Metal Structures from Diamondoids: Synthesis and Catalytic Applications
Final Report Abstract
This project aimed to explore the reactivity, and exploit the properties, of thermo-dynamically extremely stable and highly regular nm-sized diamondoids in combination with transition metal catalysis and sensor formation. We explored the preparation of hybrid materials that combine pure sp3 carbon and transition metals in uniquely ordered structures by innovative vapor deposition techniques and chemical methods inspired by the reactivity of transition metals. Progress has been made in the preparation of new hybrid materials endowed with interesting physical properties allowing high catalytic activity and direct separability. Ground-breaking results were achieved, in particular, with gas sensors based on highly sensitive nanodiamond materials (publications #3 and #5 noted above). In this context, the PIs’ groups developed functionalized nanodiamonds in that detect •NO2 and NH3 at ppb levels with low energy expenditure. To achieve such high sensitivity, palladium was deposited using current CVD-techniques from organometallic precursors on crystal assemblies of primary diamantane phosphines. The resulting porous nanomaterials are p-type semiconductors with a high specific surface area of up to 140 m2 g^–1. The adsorption of NO2 or NH3 on the diamondoid produces measurable variations in electrical resistance at levels below the threshold limit for human exposure, with the gas response being fully reversible at room temperature. Most remarkably, the diamondoid-based sensors demonstrate high stability under varying environmental conditions, even in the presence of water and oxygen. The team suggests that these gas sensors could be widely used in wireless air quality sensing networks. Further highlights from the Schreiner group are the synthetic efforts to developing diamondoid functionalizations that are broad and high-yielding. This includes a new Mukaiyama-like redox condensation reaction that enables SN1 reactions with a variety of nucleophiles for the functionalization of diamondoids as well as a large variety of other substrates. Furthermore, we also developed a rather general protocol for all-meta-substituted benzenes utilizing primary, secondary, but, in particular, tertiary alkyl substituents, including diamondoids. The two participating groups had complementary expert knowledge with the Hierso group having ample experience in a variety of physical techniques such as CVD utilizing organometallic precursors, while the Schreiner group being well versed in diamondoid chemistry. Furthermore, the addition of the Eduard Llobet group for gas-sensing measurements provided a most welcome asset to the entire team an formed the basis for continuing collaborations in this area.
Publications
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Nanodiamond-Palladium Core–Shell Organohybrid Synthesis: A Mild Vapor-Phase Procedure Enabling Nanolayering Metal onto Functionalized sp3-Carbon. Adv. Funct. Mat. 2018, 1705786/1–15
Maria A. Gunawan, Oana Moncea, Didier Poinsot, Mariem Keskes, Bruno Domenichini, Olivier Heintz, Rémi Chassagnon, Frédéric Herbst, Jeremy E. P. Dahl, Andrey A. Fokin, Peter R. Schreiner, and Jean-Cyrille Hierso
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Palladium-Catalyzed C2−H Arylation of Unprotected (N−H)-Indoles “On Water” Using Primary Diamantyl Phosphine Oxides as a Class of Primary Phosphine Oxide Ligands. ChemCatChem 2018, 10, 2915–2922
Oana Moncea, Didier Poinsot, Andrey A. Fokin, Peter. R. Schreiner, and Jean-Cyrille Hierso
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Diamondoid Nanostructures as sp3-Carbon-Based Gas Sensors. Angew. Chem. Int. Ed. 2019, 58, 9933–9938
Oana Moncea, Juan Casanova-Chafer, Didier Poinsot, Lukas Ochmann, Clève D. Mboyi, Eduard Llobet, Imen Makni, Molka El Atrous, Stéphane Brandès, Yoann Rousselin, Bruno Domenichini, Nicolas Nuns, Andrey A. Fokin, Peter R. Schreiner, and Jean-Cyrille Hierso
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Alkylphosphinites as Synthons for Stabilized Carbocations. Org. Lett. 2022, 24, 1460–1464
Lukas Ochmann, Mika L. Kessler, and Peter R. Schreiner
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All that metas – Synthesis of Dispersion Energy Donor-Substituted Benzenes. Org. Lett. 2022, 24
Lukas Ochmann, Michael Fuhrmann, Felix J. Gössl, Alexander Makaveev, and Peter R. Schreiner
