RESUMO
Metal-organic frameworks (MOFs) are porous 3-dimensional crystalline structures that have shown promise for a variety of applications including adsorption, catalysis, and sensing. Modern warfare has placed chemical warfare agent (CWA) destruction at the forefront of chemical applications for MOFs. However, experiments involving CWAs can only be performed by a small number of highly trained individuals as they are extremely dangerous and available only to certain laboratories. As such, it is imperative that suitable chemical simulants and reaction conditions are determined for CWAs of interest. In this work, we determine the reaction rate for heterogeneous catalytic hydrolysis of eight commonly used G-agent simulants with zirconium-based MOFs. Of the simulants tested, only dimethyl chlorophosphate (DMCP), diisopropylfluorophosphate (DFP), and dimethyl p-nitrophenylphosphate (DMNP) exhibit the ability to be catalytically hydrolyzed in a manner similar to the G-agents by the MOFs studied. Two different base-catalyzed reaction mechanisms are proposed for the hydrolysis reaction on the different MOF secondary building units, and the effect of pH and buffer properties is determined using an N-ethylmorpholine (NEM) buffer at pH 8-10 and a 3-(cyclohexylamino)-1-propanesulofinic acid (CAPS) buffer at pH 10-11.
RESUMO
Paper spray mass spectrometry has been shown to successfully analyze chemical warfare agent (CWA) simulants. However, due to the volatility differences between the simulants and real G-series (i.e., sarin, soman) CWAs, analysis from an untreated paper substrate proved difficult. To extend the analytical lifetime of these G-agents, metal-organic frameworks (MOFs) were successfully integrated onto the paper spray substrates to increase adsorption and desorption. In this study, several MOFs and nanoparticles were tested to extend the analytical lifetimes of sarin, soman, and cyclosarin on paper spray substrates. It was found that the addition of either UiO-66 or HKUST-1 to the paper substrate increased the analytical lifetime of the G-agents from less than 5 min detectability to at least 50 min.
RESUMO
Metal-organic frameworks (MOFs) are versatile materials highly regarded for their porous nature. Depending on the synthetic method, various guest molecules may remain in the pores or can be systematically loaded for various reasons. Herein, we present a study that explores the effect of guest molecules on the adsorption and reactivity of the MOF in both the gas phase and solution. The differences between guest molecule interactions and the subsequent effects on their activity are described for each system. Interestingly, different effects are observed and described in detail for each class of guest molecules studied. We determine that there is a strong effect of alcohols with the secondary building unit of UiO MOFs, while Lewis bases have an effect on the reactivity of the -NH2 group in UiO-66-NH2 and adsorption by the coordinatively unsaturated copper sites in HKUST-1. These effects must be considered when determining synthesis and activation methods of MOFs toward various applications.
RESUMO
A fullerene-based photosensitizer is incorporated postsynthetically into a Zr6 -based MOF, NU-1000, for enhanced singlet oxygen production. The structural organic linkers in the MOF platform also act as photosensitizers which contribute to the overall generation of singlet oxygen from the material under UV irradiation. The singlet oxygen generated by the MOF/fullerene material is shown to oxidize sulfur mustard selectively to the less toxic bis(2-chloroethyl)sulfoxide with a half-life of only 11â min.
RESUMO
Recently, polymer-metal-organic frameworks (polyMOFs) were reported as a new class of hybrid porous materials that combine advantages of both organic polymers and crystalline MOFs. Herein, we report a bridging coligand strategy to prepare new types of polyMOFs, demonstrating that polyMOFs are compatible with additional MOF architectures besides that of the earlier reported IRMOF-1 type polyMOF. Gas sorption studies revealed that these polyMOF materials exhibited relatively high CO2 sorption but very low N2 sorption, making them promising materials for CO2/N2 separations. Moreover, these polyMOFs demonstrated exceptional water stability attributed to the hydrophobicity of polymer ligands as well as the cross-linking of the polymer chains within the MOF.
