Langmuir and Langmuir–Blodgett Monolayers from 20 nm Sized Crystals of the Metal–Organic Framework MIL-101(Cr)

HighlightsWhat are the main findings?A metal–organic Framework (MOF) MIL-101(Cr) with crystal sizes around 20 nm was synthesized and the results were compared to a 300 nm crystal-sized commercially available material.What are the implications of the main findings?Smaller-sized MIL-101(Cr) crystals form a stable insoluble monolayer at the air–water interface with denser, more homogeneous water coverage and packing upon compression, and no visible micrometer-sized aggregates.Langmuir-Blodgett monolayers from the 20 nm MOF show six times lower surface roughness.Metal–Organic Frameworks (MOFs) have diverse applications due to their tunable porosity, large surface area, and diverse chemical functionalities. Among them, one of the most researched MOFs is MIL-101(Cr), which, in addition, is very stable in water. We have used a commercially available substance with approximately 300 nm large crystals for the preparation of a sensing nano-thin layer for the emerging water contaminant PFOS, due to its high selectivity towards this compound. Here, we have synthesized 20 nm sized crystals of MIL-101(Cr), which are among the smallest reported, and compared them to the same material with 300 nm sized crystals. The material was characterized by TEM and XPS. It was possible to prepare insoluble monolayers at the air–water interface (Langmuir films), which were characterized with film compression isotherms, Brewster angle microscopy, and surface potential measurements. The Langmuir–Blodgett (LB) method was used to deposit monolayers on Si wafers and 434 MHz Surface Acoustic Wave resonator simultaneously. The LB layers were very stable over time. The smaller-sized MIL-101 (Cr) crystals exhibit denser, more homogeneous water coverage and packing upon compression, with no observable 10–100 µm aggregates. LB monolayers from the 20 nm particles have approximately six times lower surface roughness. The LB monolayer is far from being smooth, but this will allow excellent access to the MOF pores by the tested analyte in a chemical sensing application. The lack of research on depositing presynthesized MOFs using probably the best method for nanoarchitectonics—the LB method—is addressed. The 20 nm sized MOF crystals are the smallest deposited by this method so far.