Automated self-optimization, intensification, and scale-up of photocatalysis in flow.

The optimization, intensification, and scale-up of photochemical processes constitute a particular challenge in a manufacturing environment geared primarily toward thermal chemistry. In this work, we present a versatile flow-based robotic platform to address these challenges through the integration of readily available hardware and custom software. Our open-source platform combines a liquid handler, syringe pumps, a tunable continuous-flow photoreactor, inexpensive Internet of Things devices, and an in-line benchtop nuclear magnetic resonance spectrometer to enable automated, data-rich optimization with a closed-loop Bayesian optimization strategy. A user-friendly graphical interface allows chemists without programming or machine learning expertise to easily monitor, analyze, and improve photocatalytic reactions with respect to both continuous and discrete variables. The system's effectiveness was demonstrated by increasing overall reaction yields and improving space-time yields compared with those of previously reported processes.

Membrane-based TBADT recovery as a strategy to increase the sustainability of continuous-flow photocatalytic HAT transformations.

Photocatalytic hydrogen atom transfer (HAT) processes have been the object of numerous studies showcasing the potential of the homogeneous photocatalyst tetrabutylammonium decatungstate (TBADT) for the functionalization of C(sp3)-H bonds. However, to translate these studies into large-scale industrial processes, careful considerations of catalyst loading, cost, and removal are required. This work presents organic solvent nanofiltration (OSN) as an answer to reduce TBADT consumption, increase its turnover number and lower its concentration in the product solution, thus enabling large-scale photocatalytic HAT-based transformations. The operating parameters for a suitable membrane for TBADT recovery in acetonitrile were optimized. Continuous photocatalytic C(sp3)-H alkylation and amination reactions were carried out with in-line TBADT recovery via two OSN steps. Promisingly, the observed product yields for the reactions with in-line catalyst recycling are comparable to those of reactions performed with pristine TBADT, therefore highlighting that not only catalyst recovery (>99%, TON > 8400) is a possibility, but also that it does not happen at the expense of reaction performance.

Tailoring the Surface Chemistry of Anion Exchange Membranes with Zwitterions: Toward Antifouling RED Membranes.

Fouling is a pressing issue for harvesting salinity gradient energy with reverse electrodialysis (RED). In this work, antifouling membranes were fabricated by surface modification of a commercial anion exchange membrane with zwitterionic layers. Either zwitterionic monomers or zwitterionic brushes were applied on the surface. Zwitterionic monomers were grafted to the surface by deposition of a polydopamine layer followed by an aza-Michael reaction with sulfobetaine. Zwitterionic brushes were grafted on the surface by deposition of polydopamine modified with a surface initiator for subsequent atom transfer radical polymerization to obtain polysulfobetaine. As expected, the zwitterionic layers did increase the membrane hydrophilicity. The antifouling behavior of the membranes in RED was evaluated using artificial river and seawater and sodium dodecylbenzenesulfonate as the model foulant. The zwitterionic monomers are effective in delaying the fouling onset, but the further build-up of the fouling layer is hardly affected, resulting in similar power density losses as for the unmodified membranes. Membranes modified with zwitterionic brushes show a high potential for application in RED as they not only delay the onset of fouling but they also slow down the growth of the fouling layer, thus retaining higher power density outputs.