Anion-Dependent Catalytic C-C Bond Cleavage of a Lignin Model within a Cationic Metal-Organic Framework
| Autor: | R. Tom Baker, Glenn A. Facey, Muralee Murugesu, Fernanda Gomes de Mendonça, Floris Chevallier, Christophe Bucher, Walace D. do Pim, Gabriel Brunet |
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| Přispěvatelé: | Université d'Ottawa [Ontario] (uOttawa), Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS) |
| Rok vydání: | 2020 |
| Předmět: |
Materials science
010405 organic chemistry Cationic polymerization Substrate (chemistry) Viologen [CHIM.CATA]Chemical Sciences/Catalysis 010402 general chemistry Heterogeneous catalysis 01 natural sciences Combinatorial chemistry 0104 chemical sciences Catalysis Electrophile medicine [CHIM]Chemical Sciences General Materials Science Metal-organic framework ComputingMilieux_MISCELLANEOUS Bond cleavage medicine.drug |
| Zdroj: | ACS Applied Materials & Interfaces ACS Applied Materials & Interfaces, Washington, D.C. : American Chemical Society, 2021, 13 (1), pp.688-695. ⟨10.1021/acsami.0c19212⟩ ACS Applied Materials & Interfaces, 2021, 13 (1), pp.688-695. ⟨10.1021/acsami.0c19212⟩ |
| ISSN: | 1944-8252 1944-8244 |
| DOI: | 10.1021/acsami.0c19212⟩ |
| Popis: | The development of heterogeneous catalysts capable of selectively converting lignin model compounds into products of added value offers an exciting avenue to explore in the production of renewable chemical feedstocks. The use of metal-organic frameworks (MOFs) in such chemical transformations relies largely on the presence of accessible open metal sites found within highly porous networks that simultaneously allow for fast transport and strong interactions with desired substrates. Here, we present the first systematic study on the modulation of catalytic performance of a cationic framework, [Cu2(L)(H2O)2](NO3)2·5.5H2O (L = 1,1'-bis(3,5-dicarboxylatophenyl)-4,4'-bipyridinium), achieved through the exchange of anionic guests. Remarkably, the catalytic activity proves to be highly anion-dependent, with a nearly 10-fold increase toward the aerobic C-C bond cleavage of a lignin model compound when different anionic species are incorporated within the MOF. Moreover, we demonstrate that the cationic nature of the MOF, imparted by the incorporation of viologen moieties within the linker, tunes the electrophilicity of the active copper(II) sites, resulting in stronger interactions with the substrate. As such, the copper-based framework exhibits enhanced catalytic performance when compared to its neutral counterpart, emphasizing the appeal of charged frameworks for use as green heterogeneous catalysts. |
| Databáze: | OpenAIRE |
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