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Synthesis of trifluoromethylstyrene compounds via gas-liquid photoredox catalysis in continuous-flow microreactors

Final Report Summary - PHOTOFLOW (Synthesis of trifluoromethylstyrene compounds via gas-liquid photoredox catalysis in continuous-flow microreactors)

The whole project was divided into six work packages. This project was started at March 1, 2014 and ended at February 29, 2016. It has been implemented strictly according to the grant agreement. Work Packages 1-6 have been totally finished. The main research results of this project can be concluded as follows:
(1) Novel microreactors with high energy utilization efficiencies have been developed for photochemical transformations and corresponding kinetic studies, in which the mixing and mass transfer limitations are eliminated.
(2) Photochemical processes such as phtocatalytic oxidation of thiophenol to phenyl disulfide and trifluoromethylation have been thoroughly investigated and process optimization was conducted in photomicroreactors.
(3) The attenuation effect on photochemical processes should be taken into account even these processes are conducted in photomicroreactors.
(4) Empirical correlations have been developed to predict the residence time (reaction time) in capillary microreactors for gas-liquid two-phase reaction systems.
(5) Kinetic parameters for photochemical processes in photomicroreactors are correlated to power input for light sources and photocatalyst loading.
(6) Protocols for measuring important parameters in photochemical transformations such as quantum yield and photon flux in microreactors have been developed.
(7) Reaction mechanisms have been proposed for both phtocatalytic oxidation of thiols and trifluoromethylation of heterocycles according to their reaction kinetic characteristics.
(8) A new numbering-up strategy has been proposed for improving the throughput of microreactors for photochemical processes.
(9) Transport phenomena associated with photochemical processes conducted in microreactors have been described in details, resulting in the publication of two book chapters.
(10) More than 10 papers have been published in famous international journals such as Nature Protocols, AIChE Journal, Chemical Society Reviews, Chemistry – A European Journal, Reaction Chemistry & Engineering, and so on. High citations imply the high quality of these research results and huge attention from both academic and industrial areas.

The expenditure on this project was reasonable according to the research plan. The production of this project reaches the objectives proposed in the proposal. The researcher has learned relevant knowledge in the fields of microreactor technology, flow chemistry and organic synthesis; and he improved his research, management and collaboration skills through training activities with the help of his host (scientist in charge). In particular, novel microreactors for photochemical transformations and relevant reaction kinetic studies developed by the researcher and his host have attracted more and more academics. This kind of smart and compact photomicroreactors may become a strong tool to conduct photochemical transformations for academic researches, and both chemistry and chemical engineering consortiums would pay great attention on relevant research results. Through the publication of high-quality papers, this project has been well known by international researchers. Meanwhile, the researcher and his host widely presented the work related to this project in international conferences. The researcher has successfully supervised several master / bachelor students, which is very useful for knowledge transfer. In fact, the implementation of this project has obviously increased the competitive power in relevant research fields such as microreactor technology, reaction engineering, flow chemistry and photochemistry, according to the feedback of this project (eg. citations and invited speeches). Currently, the researcher has become an associate professor in Shanghai Jiao Tong University in China (new working email address: y.su@sjtu.edu.cn). All in all, this project was very successful according to its overall targets.