We use micro particle image velocimetry (microPIV) and fluorescence microscopy techniques to characterize microscale segmented gas-liquid flow at low superficial velocities relevant for chemical reactions with residence times of up to several minutes. Different gas-liquid microfluidic channel networks of rectangular cross section are fabricated in poly(dimethylsiloxane) (PDMS) using soft lithography techniques. The recirculation motion in the liquid segments associated with gas-liquid flows as well as the symmetry characteristics of the recirculations are quantified for straight and meandering channel networks. Even minor surface roughness effects and the compressibility of the gas phase induce loss of symmetry and enhance mixing across the centerline in straight channels. Mixing is further accelerated in meandering channels by the periodic switching of recirculation patterns across the channel center. We demonstrate a new, piezoelectrically activated flow injection technique for determining residence time distributions (RTDs) of fluid elements in multiphase microfluidic systems. The results confirm a narrowed liquid phase RTD in segmented flows in comparison to their single-phase counterparts. The enhanced mixing and narrow RTD characteristics of segmented gas-liquid flows are applied to liquid mixing and in sol-gel synthesis of colloidal nanoparticles.
We demonstrate the design, fabrication, and operation of microfluidic chemical reactors for the synthesis of colloidal silica particles. Two reactor configurations are examined: laminar flow reactors and segmented flow reactors. We analyze particle sizes and size distributions and examine their change with varying linear flow velocity and mean residence time. Laminar flow reactors are affected by axial dispersion at high linear velocities, thus leading to wide particle size distributions under these conditions. Gas is used to create a segmented flow, consisting liquid plugs separated by inert gas bubbles. The internal recirculation created in the liquid plugs generates mixing, which eliminates the axial dispersion effects associated with laminar flow reactors and produces a narrow size distribution of silica nanoparticles.
A droplet-based microfluidic method for the preparation of anisotropic gold nanocrystal dispersions is presented. Gold nanoparticle seeds and growth reagents are dispensed into monodisperse picoliter droplets within a microchannel. Confinement within small droplets prevents contact between the growing nanocrystals and the microchannel walls. The critical factors in translating macroscale flask-based methods to a flow-based microfluidic method are highlighted and approaches are demonstrated to flexibly fine tune nanoparticle shapes into three broad classes: spheres/spheroids, rods, and extended sharp-edged structures, thus varying the optical resonances in the visible-near-infrared (NIR) spectral range.
Covalent organic frameworks (COFs) have recently emerged as a new class of crystalline porous materials with many potential applications. The development of facile and effective synthetic methods of COFs is highly desirable for their large-scale applications. Herein, we demonstrate the room temperature batch synthesis of three classical two-dimensional (2D) COFs with various types of linkage, namely, COF-LZU1 (imine-linked), TpPa-1 (enamine-linked), and N 3 -COF (azinelinked). These obtained COFs exhibit good crystallinity and high porosity comparable to their counterparts synthesized solvothermally at higher temperatures. The facile formation of these COFs under such mild synthetic conditions can be attributed to (1) high solubility of monomers and (2) the strong π−π stacking interactions between monomers and π-systems of oligomers during the initial and the subsequent error-correction crystallization process. Based on this conclusion, two new iminelinked COFs named NUS-14 and NUS-15 were successfully synthesized with good crystallinity under ambient conditions. Moreover, continuous flow synthesis has been demonstrated in COF-LZU1 with a production rate of 41 mg h −1 at an extremely high space-time yield (STY) of 703 kg m −3 day −1 . This study represents the first example of synthesizing COFs by continuous processes, which sheds light on the scaled-up synthesis of these promising materials.
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