Abstract
Metal-organic frameworks (MOFs); also known as porous coordination polymers (PCP) are a class of porous crystalline materials constructed by connecting metal clusters via organic linkers. The possibility of functionalization leads to virtually infinite MOF designs using generic modular methods. Functionalized MOFs can exhibit interesting physical and chemical properties including accelerated adsorption kinetics and catalysis. Although there are discrete methods to synthesize well-defined nanoscale MOFs, rapid and flexible methods are not available for continuous, one-pot synthesis and post-synthetic modification (functionalization) of MOFs. Here, we show a continuous, scalable nanodroplet-based microfluidic route that not only facilitates the synthesis of MOFs at a nanoscale, but also offers flexibility for direct functionalization with desired functional groups (e.g., -COCH3, fluorescein isothiocyanate; FITC). In addition, the presented route of continuous manufacturing of functionalized nanosized MOFs takes significantly less time compared to state-of-the-art batch methods currently available (1 hr vs. several days). We envisage our approach to be a breakthrough method for synthesizing complex functionalized nanomaterials (metal, metal oxides, quantum dots and MOFs) that are not accessible by direct batch processing and expand the range of a new class of functionalized MOF-based functional nanomaterials.
Highlights
Biological systems for imaging, delivery and therapeutic use, and (iv) functionalization with fluorescent dyes enables fluorescence labeling of nanoparticles for bio-sensing applications[25]
The nucleation and growth of colloidal nanoparticles are sensitive to experimental conditions, large scale production of nanoMOFs with controlled morphology is nearly impossible by linearly increasing the volume of the reaction solution in batch synthesis methods
To characterize the crystal structure of as synthesized and functionalized UIO-66-NH2 analogs, approximately 5 mg each of UIO-66-NH2 and its functionalized analogs synthesized through both batch and microfluidic methods was characterized with powder X-ray diffraction (PXRD)
Summary
To address the challenges of conventional synthesis methods, various droplet-based microfluidic devices have been presented during the past few years[29,30,31,39,44,45,46]. These devices offer a number of advantages over conventional batch type reactors. The droplet-based microfluidic technique we developed can be exploited as a generic, low-cost, fast, and scalable method for the one-pot synthesis and PSM of MOFs. Our droplet chip works on the principle of flow focusing geometry (Fig. 2c). Salient points Automation, control and integration Simultaneous synthesis and post-synthetic modification Scalability Reproducibility Time required Compositional control
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