16 research outputs found
On-Surface Synthesis of Highly Oriented Thin Metal-Organic Framework Films through Vapor-Assisted Conversion
Virmani E, Rotter JM, Maehringer A, et al. On-Surface Synthesis of Highly Oriented Thin Metal-Organic Framework Films through Vapor-Assisted Conversion. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY. 2018;140(14):4812-4819.Controlled on-surface film growth of porous and crystalline frameworks is a central prerequisite for incorporating these materials into functional platforms and operational devices. Here, we present the synthesis of thin zirconium-based metal organic framework (MOF) films by vapor-assisted conversion (VAC). We established protocols adequate for the growth of UiO-66, UiO-66(NH2), UiO-67, and UiO-68(NH2) as well as the porous interpenetrated Zr-organic framework, PPPP-PIZOF-1, as highly oriented thin films. Through the VAC approach, precursors in a cast solution layer on a bare gold surface are reacting to form a porous continuous MOF film, oriented along the [111] crystal axis, by exposure to a solvent vapor at elevated temperature of 100 degrees C and 3 h reaction time. It was found that the concentration of dicarboxylic acid, the modulator, the droplet volume, and the reaction time are vital parameters to be controlled for obtaining oriented MOF films. Using VAC for the MOF film growth on gold surfaces modified with thiol SAMs and on a bare silicon surface yielded oriented MOF films, rendering the VAC process robust toward chemical surface variations. Ethanol sorption experiments show that a substantial part of the material pores is accessible. Thereby, the practical VAC method is an important addition to the toolbox of synthesis methods for thin MOF films. We expect that the VAC approach will open new horizons in the formation of highly defined functional thin MOF films for numerous applications
Characterization of a single reporter-gene potency assay for T-cell-dependent bispecific molecules
Expanding the Group of Porous Interpenetrated Zr-Organic Frameworks (PIZOFs) with Linkers of Different Lengths
A Zr-based MOF of
the PIZOF type, which consists of two independent
and mutually interpenetrating UiO-type frameworks with [Zr<sub>6</sub>O<sub>4</sub>(OH)<sub>4</sub>(O<sub>2</sub>C)<sub>12</sub>] nodes,
does not only form with a PEPEP dicarboxylic acid (P = phenylene,
E = ethynylene). Also dicarboxylic acids with the shorter PPPP and
PEPP spacers were found to give PIZOFs, denoted PPPP-PIZOF and PEPP-PIZOF,
respectively. Reducing the spacer length even further to a PEEP segment
caused a switchover to the formation of a UiO framework. The hysteresis
in the Ar sorption curve of PEPP-PIZOF-1 and the slightly too large
amount of combustion residue from PPPP-PIZOF-1 suggest structural
defects. These hint at a mismatch between the requirement of the optimal
linker length for PIZOF formation and the lengths of the PEPP and
PPPP dicarboxylates. Nevertheless, these dicarboxylates prefer the
formation of a PIZOF over the formation of a UiO structure. PEPEP-PIZOF-2,
PPPP-PIZOF-1, and PEPP-PIZOF-1 are stable in air up to 325, 350, and
300 °C, respectively, and have BET surface areas of 2350, 2020,
and 1650 m<sup>2</sup> g<sup>–1</sup>, respectively. PEPEP-PIZOFs,
even those with very hydrophilic oligo(ethylene glycol) side chains
on the linkers, are very stable in water and also during drying from
a water-wetted state. On the contrary, PEPP-PIZOF-1 and PPPP-PIZOF-1
that had been exposed to water required exchange of water for ethanol
before drying to mostly preserve the framework. The results emphasize
the importance of differentiating between framework damage caused
through hydrolysis in water and through drying from a water-wetted
state. The sensitivity of PEPP-PIZOF-1 and PPPP-PIZOF-1 against drying
from a water-wetted state may be the consequence of defects. The drying
stability of water-wetted PEPEP-PIZOFs lets us suggest that reversible
bending of the linkers contributes to the stability of the PEPEP-PIZOFs