Controlling Cubic versus Octahedral Morphology in Plasmonic Aluminum Nanoparticle Synthesis with Titanocene Catalysts: A Systematic Study

IF 11.3 1区化学 Q1 CHEMISTRY, PHYSICAL

ACS Catalysis Pub Date : 2024-12-02 DOI:10.1021/acscatal.4c06286

Jaekwan Kim, Christian R. Jacobson, Naomi J. Halas, Ian A. Tonks

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Abstract

Ti precatalysts containing the titanocene moiety (Cp₂Ti–, Cp = cyclopentadienyl) can, under certain conditions, selectively produce cubic Al nanocrystals through the dehydrocoupling of alane amine adducts such as AlH₃·NMe₂Et. A systematic study of reaction conditions reveals that cubic Al nanoparticle formation occurs at a higher temperature (e.g., 65 °C) and/or higher catalyst-concentration conditions (e.g., 0.5 mol % [Ti]). Kinetic studies reveal that under these conditions nanoparticle formation and alane consumption are much faster, and cubic nanoparticle formation takes place under kinetically controlled conditions. On the other hand, employing a wide suite of TiX₄ (X = anionic ligand)-type precatalysts yielded only octahedral-shaped aluminum nanoparticles regardless of conditions. Finally, we report the synthesis of a hydride-bridged Ti–Al heterobimetallic compound from the reaction of Cp₂TiCl₂ with AlH₃·NMe₂Et and characterized it to show that it is a reaction intermediate in the Ti-catalyzed aluminum nanoparticle synthesis.

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来源期刊

ACS Catalysis CHEMISTRY, PHYSICAL-

CiteScore

20.80

自引率

6.20%

发文量

1253

审稿时长

1.5 months

期刊介绍： ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.