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  • Accepted Manuscript: Immobilization of molecular catalysts on solid supports via atomic layer deposition for chemical synthesis in sustainable solvents
Title: Immobilization of molecular catalysts on solid supports via atomic layer deposition for chemical synthesis in sustainable solvents
Homogeneous molecular catalysts are valued for their reaction specificity but face challenges in manufacturing scale-up due to complexities in final product separation, catalyst recovery, and instability in the presence of water. Heterogenizing these molecular catalysts, by attachment to a solid support, could transform the practical utility of molecular catalysts, simplify catalyst separation and recovery, and prevent catalyst decomposition by impeding bimolecular catalyst interactions. Previous strategies to heterogenize molecular catalysts via ligand-first binding to supports have suffered from reduced catalytic activity and leaching (loss) of catalyst, especially in environmentally friendly solvents like water. Herein, we describe an approach in which molecular catalysts are first attached to a metal oxide support through acidic ligands and then “encapsulated” with a metal oxide layer via atomic layer deposition (ALD) to prevent molecular detachment from the surface. For this initial report, which is based upon the well-studied Suzuki carbon–carbon cross-coupling reaction, we demonstrate the ability to achieve catalytic performance using a non-noble metal molecular catalyst in high aqueous content solvents. The catalyst chosen exhibits limited catalytic reactivity under homogeneous conditions due to extremely short catalyst lifetimes, but when heterogenized and immobilized with an optimal ALD layer thickness product yields >90% can be obtained in primarily more » aqueous solutions. Catalyst characterization before and after ALD application and catalytic reaction is achieved with infrared, electron paramagnetic resonance, and X-ray spectroscopies. « less
Authors:
; ; ; ; ; ; ; ; ; ; ;
Award ID(s):
1954809 1954850
Publication Date:
NSF-PAR ID:
10328103
Journal Name:
Green Chemistry
Volume:
23
Issue:
23
Page Range or eLocation-ID:
9523 to 9533
ISSN:
1463-9262
Sponsoring Org:
National Science Foundation
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