Metal-organic frameworks as catalyst supports : influence of defects on metal nanoparticle formation

Miguel Rivera-Torrente , Matthias Filez , Rifan Hardian (1) , Emily Reynolds , Beatriz Seoane (2) , Marie-Vanessa Coulet (1) , Freddy Oropeza palacio , Jan Hofmann , Roland Fischer , Andrew Goodwin (3) , Philip Llewellyn (1) , Bert Weckhuysen

1 MADIREL - Matériaux divisés, interfaces, réactivité, électrochimie
2 LPTENS - Laboratoire de Physique Théorique de l'ENS [École Normale Supérieure]
3 Inorganic Chemistry Laboratory [Oxford]

Because of their high tunability and surface area, metal-organic frameworks (MOFs) show great promise as supports for metal nanoparticles. Depending on the synthesis route, MOFs may contain defects. Here, we show that highly crystalline MIL-100(Fe) and disordered Basolite® F300, with identical iron 1,3,5-benzenetricarboxylate composition, exhibit very divergent properties when used as a support for Pd nanoparticle deposition. While MIL-100(Fe) shows a regular MTN-zeotype crystal structure with two types of cages, Basolite® F300 lacks long-range order beyond 8 Å and has a single-pore system. The medium-range configurational linker-node disorder in Basolite® F300 results in a reduced number of Lewis acid sites, yielding more hydrophobic surface properties compared to hydrophilic MIL-100(Fe). The hydrophilic/hydrophobic nature of MIL-100(Fe) and Basolite® F300 impacts the amount of Pd and particle size distribution of Pd nanoparticles deposited during colloidal synthesis and dry impregnation methods, respectively. It is suggested that polar (apolar) solvents/precursors attractively interact with hydrophilic (hydrophobic) MOF surfaces, allowing tools at hand to increase the level of control over, for example, the nanoparticle size distribution.

Domaines: Matériaux; Catalyse

Miguel Rivera-Torrente, Matthias Filez, Rifan Hardian, Emily Reynolds, Beatriz Seoane, et al.. Metal-organic frameworks as catalyst supports : influence of defects on metal nanoparticle formation. ChemistryOpen, 2018, ⟨10.1002/chem.201800694⟩. ⟨hal-01789561⟩