Journal
ACS APPLIED MATERIALS & INTERFACES
Volume 13, Issue 1, Pages 688-695Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acsami.0c19212
Keywords
metal-organic framework; anion-exchange; copper(II); heterogeneous catalysis; C-C bond cleavage; lignin model
Funding
- University of Ottawa
- Canada Foundation for Innovation (CFI)
- Natural Sciences and Engineering Council of Canada (NSERC)
- Canada Research Chairs Program
- Conselho Nacional de Desenvolvimento Cientifico e Tecnologico (CNPq)-Brazil
- region Auvergne-Rhone-Alpes
- LIA Funcat
- Universite de Lyon/IDEX Lyon
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The research systematically studied the modulation of catalytic performance of a cationic framework, finding that the catalytic activity is highly anion-dependent and significantly increases when different anionic species are incorporated. The incorporation of viologen moieties within the linker tunes the electrophilicity of the active copper(II) sites, resulting in stronger interactions with the substrate and enhanced catalytic performance.
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, [Cu-2(L)(H2O)(2)](NO3)(2)center dot 5.5H(2)O (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.
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