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Nitro-functionalized metal–organic frameworks (MOFs), such as Al-MIL-53-NO 2 , have been widely used in quantitative hydrogen sulfide (H 2 S) detection based on the “turn-on” effect, where fluorescence enhancements were observed upon contact with H 2 S. This was believed to be caused by the fact that the electron-withdrawing –NO 2 groups in the initial non-luminescent MOFs were reduced to electron-donating –NH 2 groups in the sensing process. However, since most H 2 S detection is conducted in a suspension system consisting of MOFs and solvents, it is still unclear whether these –NH 2 groups are on MOFs or in the liquid. Using Al-MIL-53-NO 2 as a model MOF, this work aims to answer this question. Specifically, the supernatant and undissolved particles separated from the Al-MIL-53-NO 2 suspensions after being exposed to H 2 S were analyzed systematically. The results showed that it is the free BDC-NH 2 (2-aminobenzene-1,4-dicarboxylic acid) in the solution rather than the formation of Al-MIL-53-NH 2 that really caused the fluorescence enhancement. In particular, the formed BDC-NH 2 was reduced from the shedded BDC-NO 2 (2-nitrobenzene-1,4-dicarboxylic acid) during the decomposition of Al-MIL-53-NO 2 , which was attacked by OH − in the NaHS solution. We anticipate that this work will offer new ways of tracing fluorophores for MOF-based sensing applications in aqueous systems. 

The synthesis of metal–organic frameworks (MOFs) by using traditional wet-chemistry methods generally requires very long durations and still suffers from non-uniform heat and mass transfer within the bulk precursor solutions. Towards addressing these issues, a microdroplet-based spray method has been developed. In a typical spray process, an MOF's precursor solution is first atomized into microdroplets. These droplets serve as microreactors to ensure homogeneous mixing, fast evaporation, and rapid nucleation and crystal growth to form MOF particles. However, the fundamental MOF formation mechanisms by using this strategy have not been fully understood. In this work, the role of the operating pressure in the synthesis of a representative MOF ( i.e. , Cu(TPA)·(DMF); TPA: terephthalic acid, DMF: dimethylformamide) was systematically investigated. Detailed characterization showed that the pressure variations significantly affected both the morphologies and crystalline structures of Cu(TPA)·(DMF). Numerical simulations revealed that the morphology changes are mainly attributed to the variations in supersaturation ratios, which are caused by different microdroplet evaporation rates due to the regulation of operating pressure, while the crystalline structure variations are closely related to the dissociation of DMF molecules at lower operating pressures. Besides, the dissociation of DMF molecules decreased the surface area of the MOF crystals, but gave rise to massive coordinatively unsaturated metal sites, which greatly enhanced the interaction of CO 2 with the MOF crystal and thus led to improved CO 2 adsorption capacity and selectivity. The outcome of this work would contribute to the fundamental understanding of MOF synthesis using the microdroplet-based spray method. 

A new colloid-assisted approach is introduced to synthesize metal–organic framework (MOF) nanoparticles. Polystyrene latex (PS) nanocolloids were used as model colloids, which provide active surface sites for the controlled, in situ growth of MOF nanoparticles. Interactions among the colloid surfaces, ligands, and metal ions were studied systematically to map out the possible formation pathways of the MOF nanoparticles.