We utilise 3D design and 3D printing techniques to fabricate a number of miniaturised fluidic 'reactionware' devices for chemical syntheses in just a few hours, using inexpensive materials producing reliable and robust reactors. Both two and three inlet reactors could be assembled, as well as one-inlet devices with reactant 'silos' allowing the introduction of reactants during the fabrication process of the device. To demonstrate the utility and versatility of these devices organic (reductive amination and alkylation reactions), inorganic (large polyoxometalate synthesis) and materials (gold nanoparticle synthesis) processes were efficiently carried out in the printed devices.

A ‘dial-a-molecule’ platform for algorithm driven organic synthesis using real-time feedback, via in-line flow NMR spectroscopy, is demonstrated.

The employment of continuous-flow platforms for synthetic chemistry is becoming increasingly popular in research and industrial environments. Integrating analytics in-line enables obtaining a large amount of information in real-time about the reaction progress, catalytic activity and stability, etc. Furthermore, it is possible to influence the reaction progress and selectivity via manual or automated feedback optimisation, thus constituting a dial-a-molecule approach employing digital synthesis. This contribution gives an overview of the most significant contributions in the field to date.

SummaryWe present a study in which the versatility of 3D-printing is combined with the processing advantages of flow chemistry for the synthesis of organic compounds. Robust and inexpensive 3D-printed reactionware devices are easily connected using standard fittings resulting in complex, custom-made flow systems, including multiple reactors in a series with in-line, real-time analysis using an ATR-IR flow cell. As a proof of concept, we utilized two types of organic reactions, imine syntheses and imine reductions, to show how different reactor configurations and substrates give different products.

The development of simple, cost-effective and sustainable methods to transform CO2 into feedstock chemicals is essential to reduce the dependence on fossil fuels of the chemical industry. Here, we report the selective and efficient catalytic hydrogenation of CO2 to formic acid (FA) using a synergistic combination of an ionic liquid (IL) with basic anions and relatively simple catalysts derived from the precursor [Ru3(CO)12]. Very high values of TON (17000) and TOF have been observed and FA solutions with concentrations of up to 1.2 M have been produced. In this system, the imidazolium based IL associated with the acetate anion acts as precursor for the formation of the catalytically active Ru-H species, catalyst stabilizer and as an acid buffer, shifting the equilibrium towards free formic acid. Moreover, the IL acts as an entropic driver (via augmentation of the number of microstates), lowering the entropic contribution imposed by the IL surrounding the catalytically active sites. The favorable thermodynamic conditions enable the reaction to proceed efficiently at low pressure pressures, and furthermore the immobilization of the IL onto a solid support facilitates the separation of FA at the end of the reaction.