Process Intensification of 2,2'-(4-Nitrophenyl) Dipyrromethane Synthesis with a SO3H-Functionalized Ionic Liquid Catalyst in Pickering-Emulsion-Based Packed-Bed Microreactors.

A stable water-in-oil Pickering emulsion was fabricated with SO3H-functionalized ionic liquid and surface-modified silica nanoparticles and used for 2,2'-(4-nitrophenyl) dipyrromethane synthesis in a packed-bed microreactor, exhibiting high reaction activity and product selectivity. The compartmentalized water droplets of the Pickering emulsion had an excellent ability to confine the ionic liquid against loss under continuous-flow conditions, and the excellent durability of the catalytic system without a significant decrease in the reaction efficiency and selectivity was achieved. Compared with the reaction performance of a liquid-liquid slug-flow microreactor and batch reactor, the Pickering-emulsion-based catalytic system showed a higher specific interfacial area between the catalytic and reactant phases, benefiting the synthesis of 2,2'-(4-nitrophenyl) dipyrromethane and resulting in a higher yield (90%). This work indicated that an increase in the contact of reactants with catalytic aqueous solution in a Pickering-emulsion-based packed-bed microreactor can greatly enhance the synthetic process of dipyrromethane, giving an excellent yield of products and a short reaction time. It was revealed that Pickering-emulsion-based packed-bed microreactors with the use of ionic liquids as catalysts for interfacial catalysis have great application potential in the process of intensification of organic synthesis.

Microfluidic, One-Batch Synthesis of Pd Nanocrystals on N-Doped Carbon in Surfactant-Free Deep Eutectic Solvents for Formic Acid Electrochemical Oxidation.

One of the grand challenges that impedes practical applications of nanomaterials is the lack of robust manufacturing methods that are scalable, cheap, and environmentally friendly. Herein, we address this challenge by developing a microfluidic approach that produces surfactant-free Pd nanocrystals (NCs) uniformly loaded on N-doped porous carbon in a one-batch process. The deep eutectic solvent (DES) prepared from choline chloride and ethylene glycol was employed as a novel synthesis solvent, and its extended hydrogen networks and abundant ionic species effectively stabilize Pd facets and confine nanocrystal sizes without using surfactants. The microreactors provide faster heat exchange and more uniform mass transport, which in combination with DES produced Pd NCs with better-defined shape and predominately exposed Pd (100) facet. Furthermore, we describe that the N-doped functional groups in porous carbon direct dense and uniform heterogeneous growth of Pd NCs in a one-batch process, thereby eliminating a separate catalyst deposition step that is often involved in conventional synthesis. The Pd NCs in the one-batch-produced Pd/C catalysts exhibited a size distribution of ∼13 ± 3.5 nm and a high ESCA of 46.0 m2/g and delivered 362 mA/mg for formic acid electrochemical oxidation with improved stability, demonstrating the unique potentials of microfluidic reactors and DES for the controllable and scalable synthesis of electrocatalyst materials for practical applications.

Continuous-Flow Microreactors for Polymer Synthesis: Engineering Principles and Applications.

Polymerization is widely involved in the fabrication of high-performance materials. With its advantages, microreactors are typically applied to reaction processes which are limited by transport properties of conventional batch reactors. As demonstrated in this review, numerous polymerization processes are suitable to be conducted in microreactors with showing excellent polymerization performance (e.g., precisely controllable molecular weights and structures of polymer products). However, distinctive differences between polymerization processes and small-molecular reaction systems can be easily expected since fluid physical properties vary significantly during the polymerization. Herein, we firstly clearly describe the engineering principles such as mass transport phenomena and energy dissipation related to polymerization processes in microreactors, and then give a great deal of application examples (classified as homogeneous polymerization, heterogeneous polymerization, and photopolymerization) through which readers indeed can further understand these relevant principles. Finally, the remaining challenges associated with the application of microreactor technology for polymerization processes and remarking conclusions are presented.

A Mechanistic Investigation of the Visible-Light Photocatalytic Trifluoromethylation of Heterocycles Using CF3 I in Flow.

Photocatalytic radical trifluoromethylation strategies have impacted the synthesis of trifluoromethyl-containing molecules. However, mechanistic aspects concerning such transformations remain poorly understood. Here, we describe in detail the mechanism of the visible-light photocatalytic trifluoromethylation of N-methylpyrrole with gaseous CF3 I in flow. The use of continuous-flow microreactor technology allowed for the determination of different important parameters with high precision (e.g., photon flux, quantum yield, reaction rate constants) and for the handling of CF3 I in a convenient manner. Our data indicates that the reaction occurs through a reductive quenching mechanism and that there is no radical chain process present.

Accelerated gas-liquid visible light photoredox catalysis with continuous-flow photochemical microreactors.

In this protocol, we describe the construction and use of an operationally simple photochemical microreactor for gas-liquid photoredox catalysis using visible light. The general procedure includes details on how to set up the microreactor appropriately with inlets for gaseous reagents and organic starting materials, and it includes examples of how to use it to achieve continuous-flow preparation of disulfides or trifluoromethylated heterocycles and thiols. The reported photomicroreactors are modular, inexpensive and can be prepared rapidly from commercially available parts within 1 h even by nonspecialists. Interestingly, typical reaction times of gas-liquid visible light photocatalytic reactions performed in microflow are lower (in the minute range) than comparable reactions performed as a batch process (in the hour range). This can be attributed to the improved irradiation efficiency of the reaction mixture and the enhanced gas-liquid mass transfer in the segmented gas-liquid flow regime.

Liquid phase oxidation chemistry in continuous-flow microreactors.

Continuous-flow liquid phase oxidation chemistry in microreactors receives a lot of attention as the reactor provides enhanced heat and mass transfer characteristics, safe use of hazardous oxidants, high interfacial areas, and scale-up potential. In this review, an up-to-date overview of both technological and chemical aspects of liquid phase oxidation chemistry in continuous-flow microreactors is given. A description of mass and heat transfer phenomena is provided and fundamental principles are deduced which can be used to make a judicious choice for a suitable reactor. In addition, the safety aspects of continuous-flow technology are discussed. Next, oxidation chemistry in flow is discussed, including the use of oxygen, hydrogen peroxide, ozone and other oxidants in flow. Finally, the scale-up potential for continuous-flow reactors is described.

An experimental study on the numbering-up of microchannels for liquid mixing.

The numbering-up of zigzag-form microchannels for liquid mixing was experimentally investigated in a multichannel micromixer including 8 parallel channels, based on the Villermaux-Dushman reaction system, with an appropriate sulphuric acid concentration. The results showed that the micromixing performance in such micromixers could reach the same quality as in a single microchannel, when flat constructal distributors with bifurcation configurations were used. The mixing performance did not depend on whether a vertical or horizontal micromixer position was selected. Surprisingly, the channel blockage somewhat increased the micromixing performance in the multichannel micromixer due to the fluid redistribution effect of the constructal distributors. This effect could also be confirmed by CFD simulations. However, the channel blockage resulted in a higher pressure drop and thus higher specific energy dissipation in the multichannel micromixer. The local pressure drop caused by fluid splitting and re-combination in the numbering-up technique could be neglected at low Reynolds numbers, but it became larger with increasing flow rates. The operational zone for the mixing process in multichannel micromixers was sub-divided into two parts according to the specific energy dissipation and the mixing mechanisms.

Photochemical transformations accelerated in continuous-flow reactors: basic concepts and applications.

Continuous-flow photochemistry is used increasingly by researchers in academia and industry to facilitate photochemical processes and their subsequent scale-up. However, without detailed knowledge concerning the engineering aspects of photochemistry, it can be quite challenging to develop a suitable photochemical microreactor for a given reaction. In this review, we provide an up-to-date overview of both technological and chemical aspects associated with photochemical processes in microreactors. Important design considerations, such as light sources, material selection, and solvent constraints are discussed. In addition, a detailed description of photon and mass-transfer phenomena in microreactors is made and fundamental principles are deduced for making a judicious choice for a suitable photomicroreactor. The advantages of microreactor technology for photochemistry are described for UV and visible-light driven photochemical processes and are compared with their batch counterparts. In addition, different scale-up strategies and limitations of continuous-flow microreactors are discussed.