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Coupling photochemistry with flow microreactors enables novel synthesis strategies with higher efficiencies compared to batch systems. Improving the reproducibility and understanding of the photochemical reaction mechanisms requires quantitative tools such as chemical actinometry. However, the choice of actinometric systems which can be applied in microreactors is limited, due to their short optical pathlength in combination with a large received photon flux. Furthermore, actinometers for the characterization of reactions driven by visible light between 500 and 600 nm (e.g. photosensitized oxidations) are largely missing. In this paper, we propose a new visible-light actinometer which can be applied in flow microreactors between 480 and 620 nm. This actinometric system is based on the photoisomerization reaction of a diarylethene derivative from its closed to the open form. The experimental protocol for actinometric measurements is facile and characterized by excellent reproducibility and we also present an analytical estimation to calculate the photon flux. Furthermore, we propose an experimental methodology to determine the average pathlength in microreactors using actinometric measurements. In the context of a growing research interest on using flow microreactors for photochemical reactions, the proposed visible-light actinometer facilitates the determination of the received photon flux and average pathlength in confined geometries.

Photochemical activation routes are gaining the attention of the scientific community since they can offer an alternative to the traditional chemical industry that mainly utilizes thermochemical activation of molecules. Photoreactions are fast and selective, which would potentially reduce the downstream costs significantly if the process is optimized properly. With the transition towards green chemistry, the traditional batch photoreactor operation is becoming abundant in this field. Process intensification efforts led to micro- and mesostructured flow photoreactors. In this work, we are reviewing structured photoreactors by elaborating on the bottleneck of this field: the development of an efficient scale-up strategy. In line with this, micro- and mesostructured bench-scale photoreactors were evaluated based on a new benchmark called photochemical space time yield (mol·day−1·kW−1), which takes into account the energy efficiency of the photoreactors. It was manifested that along with the selection of the photoreactor dimensions and an appropriate light source, optimization of the process conditions, such as the residence time and the concentration of the photoactive molecule is also crucial for an efficient photoreactor operation. In this paper, we are aiming to give a comprehensive understanding for scale-up strategies by benchmarking selected photoreactors and by discussing transport phenomena in several other photoreactors.

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