Revealing the Formation Mechanism of Alloyed Pd-Ru Nanoparticles: A Conversion Measurement Approach Utilizing a Microflow Reactor.

The synthesis of alloyed nanoparticles has been studied extensively; however, the formation mechanisms involved remain unclear. Here, we reveal the detailed formation mechanism of alloyed nanoparticles in a Pd-Ru system, using a semibatch polyol method in which the simultaneous rapid reduction of both precursors was assumed to be the critical mechanism. We employed a microflow reactor to realize rapid heating and cooling. A significant difference in the reaction rate between the two precursors was observed. Pd was reduced within seconds, but the reduction of Ru was 2 orders of magnitude slower than that of Pd and was not as rapid as previously assumed. Further investigation of the semibatch method was performed to trace changes in the particle sizes and composition. Through quantitative and multilateral evidence, we concluded that the formation of low-crystallinity seeds, followed by solid-state diffusion, is the governing mechanism for the formation of alloyed Pd-Ru nanoparticles.

Contactless mass transfer for intra-droplet extraction.

This study demonstrates the possibility of "contactless" mass transfer between two aqueous slugs (droplets) separated by an oil slug in Taylor flow inside milli-channels. Separation of the alternating aqueous slugs at the outlet was performed by switching a couple of solenoid valves at branched outlets according to signals obtained by an optical sensor at the branch. Transfer of bromothymol blue (BTB) from acidic to basic aqueous slugs was performed for demonstration. In some cases, aqueous slugs separated by oil, merged catching on each other due to the velocity difference. Interfacial tension which was affected by the solute concentration was responsible for the velocity difference. Position-specific mass transfer activity at the rear end of the aqueous slugs was found on the course of the experiment. A meandering channel decreased the velocity difference and enhanced mass transfer. Almost complete (93%) transfer of BTB was achieved within a short residence time of several minutes under optimized conditions. The presented system opens a way for advanced separation using minimum amounts of the oil phase and allows concentrating the solute by altering relative lengths of the sender and receiver slugs.

5-Hydroxymethylfurfural Synthesis from Monosaccharides by a Biphasic Reaction-Extraction System Using a Microreactor and Extractor.

5-Hydroxymethylfurfural (HMF) was synthesized from monosaccharides by a biphasic reaction system using a microreactor. The biphasic reaction system realized an immediate extraction and stabilization of product HMF, which further degrades under the reaction conditions. Segmented flow was utilized for an efficient reaction-extraction tool. The effect of extraction ability was evaluated based on the extraction phase/reaction phase partition coefficient of HMF. A Lewis acid catalyst was introduced to overcome the obstacle of the reaction, which was clarified as the isomerization of glucose to fructose, and improved the HMF yield to 85 mol % under the condition of T = 180 °C and τ = 47 min. The recovery of the product HMF was also examined using a constructed microextraction system, and HMF was selectively recovered from the extraction phase.

Control of extremely fast competitive consecutive reactions using micromixing. Selective Friedel-Crafts aminoalkylation.

Friedel-Crafts reactions of aromatic and heteroaromatic compounds with an N-acyliminium ion pool were studied. The reaction of 1,3,5-trimethylbenzene in a batch reactor gave rise to the selective formation of a monoalkylation product (69%). Presumably, the second alkylation is slower than the first alkylation because of the protonation of the monoalkylation product that decreases its reactivity. The reaction of 1,3,5-trimethoxybenzene, however, gave rise to the formation of both monoalkylation (37%) and dialkylation (32%) products. Disguised chemical selectivity due to faster reaction than mixing seems to be responsible for the lack of selectivity. The use of micromixing was found to be quite effective to solve this problem to increase the selectivity. The monoalkylation product was obtained in 92% yield together with a small amount of the dialkylation product (4%). The reaction with various aromatic and heteroaromatic compounds revealed that the low mono/dialkylation selectivity was observed only for highly reactive aromatics. In such cases, the use of micromixing was quite effective to improve the selectivity. On the basis of micromixing, the selective sequential dialkylation using two different N-acyliminium ions was achieved. CFD simulations using a laminar flow and finite-rate model are consistent with the experimental observations and clearly indicate the importance of mixing.