Modulation and templating are two synthetic techniques that have garnered significant attention over the last several years for the preparation of hierarchically porous metal–organic frameworks (HP‐MOFs). In this study, by using fatty acids with different lengths and concentrations as dual‐functional modulators/templates, we were able to obtain HP‐MOFs with tunable mesopores that exhibit different pore diameters and locations. We found that the length and concentration of the fatty acids can determine if micelle formation occurs, which in turn dictates the porosity of the resulting HP‐MOFs. The HP‐MOFs with different mesopores differed in their performance in gas uptake and dye adsorption, and the structure–performance relationships were ascribed to the pore diameters and locations. This approach could provide a potentially universal method to efficiently introduce hierarchal mesopores into existing microporous MOF adsorbents with tunable properties.
Exfoliation of layered inorganic nanomaterials into single-layered sheets has been widely interested in materials chemistry and composite fabrication. Here, we report the exfoliation of layered zirconium phosphate nanoplatelets by using small molecule intercalating agents in ionic liquids, which opens a new platform for fabricating single-layered inorganic materials from synthetic layered compounds.
Nanocomposites with exfoliated 2D
materials are highly sought after
due to resulting material enhancement of barrier and increased modulus
among others. In the past, this was achieved by using polyols that
were effective but caused a significant drop in the glass transition
temperature of the nanocomposite. In this contribution, α-zirconium
phosphate (ZrP) nanoplatelets were covalently modified to allow for
dispersion in solvents with varying hydrophobicity and poly(methyl
methacrylate) (PMMA) for the first time. The nanoplatelets were prepared
by using a polyetheramine surfactant to achieve exfoliation, followed
by modification with epoxides. Combinations of different epoxides
were shown capable of tuning the functionality and hydrophobicity
of the exfoliated ZrP in organic media. After grafting glycidyl methacrylate
and cyclohexene oxide to the surface of ZrP, an in situ free radical polymerization of MMA allowed for high concentrations
of self-assembled exfoliated ZrP in a PMMA matrix.
Alkyl ligands with an amine or thiol headgroup have been
chosen
to investigate their effectiveness in preventing copper nanowire (Cu
NW) oxidation in hydrothermal and hygrothermal environments. Ligand
desorption has been found to be the key reason for Cu NWs to oxidize
in a wet environment. Alkylamines interact with Cu NWs through weak
coordination bonding, which would desorb easily, rendering Cu NWs
prone to oxidation. Adding excess alkylamines in the aqueous solution
can suppress the Cu NW oxidation, and keep the Cu NWs oxidation-free
upon solution processing and long-term storage. In contrast, alkylthiols
can strongly bind on Cu NW surfaces through thiolate bonding, which
provides better oxidation protection than alkylamines even in hydrothermal
and hygrothermal environments. Furthermore, it has been found that
for the alkyl chains containing 12 carbons or longer, the alkyl chain
length would have little effect on the oxidation-resistant properties
of Cu NWs when the ligands are strongly bound to Cu NW surfaces. In
addition to oxidation resistance, a shorter alkyl chain length is
found to favor current transport between Cu NWs for potential applications
in transparent flexible electronics and autonomous vehicles.
Modulation and templating are two synthetic techniques that have garnered significant attention over the last several years for the preparation of hierarchically porous metal-organic frameworks (HP-MOFs). In this study,byusing fatty acids with different lengths and concentrations as dualfunctional modulators/templates,w ew ere able to obtain HP-MOFs with tunable mesopores that exhibit different pore diameters and locations.W ef ound that the length and concentration of the fatty acids can determine if micelle formation occurs,w hichi nt urn dictates the porosity of the resulting HP-MOFs.The HP-MOFs with different mesopores differed in their performance in gas uptake and dye adsorption, and the structure-performance relationships were ascribed to the pore diameters and locations.This approach could provide ap otentially universal method to efficiently introduce hierarchal mesopores into existing microporous MOF adsorbents with tunable properties.
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