Imposed dynamic irradiation to intensify photocatalytic reactions

Dynamic irradiation is a potent option to influence the interaction between photochemical reactions and mass transport to design high performant and efficient photochemical processes. To systematically investigate the impact of this parameter, the photocatalytic reduction of nitrobenzene was conducted as a test reaction. Dynamic irradiation was realized through provoked secondary flow patterns, multiple spatially distributed light emitting diodes (LEDs) and electrical pulsation of LEDs. A combined experimental and theoretical approach revealed significant potential to enhance photochemical processes. The reaction rate was accelerated by more than 70% and even more important the photonic efficiency was increased by more than a factor of 4. This renders imposed dynamic irradiation an innovative and powerful tool to intensify photoreactions on the avenue to large scale sustainable photochemical processes.

Photooxidation of Cyclohexane by Visible and Near-UV Light Catalyzed by Tetraethylammonium Tetrachloroferrate

Tetraethylammonium tetrachloroferrate catalyzes the photooxidation of cyclohexane heterogeneously, exhibiting significant photocatalysis even in the visible portion of the spectrum. The photoproducts, cyclohexanol and cyclohexanone, initially develop at constant rates, implying that the ketone and the alcohol are both primary products. The yield is improved by the inclusion of 1% acetic acid in the cyclohexane. With small amounts of catalyst, the reaction rate increases with the amount of catalyst employed, but then passes through a maximum and decreases, due to increased reflection of the incident light. The reaction rate also passes through a maximum as the percentage of dioxygen above the sample is increased. This behavior is due to quenching by oxygen, which at the same time is a reactant. Under one set of reaction conditions, the photonic efficiency at 365 nm was 0.018 mol/Einstein. Compared to TiO2 as a catalyst, Et4N[FeCl4] generates lower yields at wavelengths below about 380 nm, but higher yields at longer wavelengths. Selectivity for cyclohexanol is considerably greater with Et4N[FeCl4], and oxidation does not proceed past cyclohexanone.