Chapter 16: Photochemistry in Supercritical Fluids
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Published:27 Jan 2016
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Special Collection: 2016 ebook collection
D. R. Worrall, in Singlet Oxygen: Applications in Biosciences and Nanosciences, ed. S. Nonell, C. Flors, S. Nonell, and C. Flors, The Royal Society of Chemistry, 2016, ch. 16, pp. 323-334.
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In this chapter, the generation and subsequent decay of singlet oxygen in a range of supercritical fluids is reviewed. Factors including the solvent radial distribution function and local density augmentation around the solute, which are a function of proximity to the critical point, are considered. Specific solvent effects, such as electronic-to-vibrational energy transfer and spin–orbit coupling, are also examined. In addition, the application of supercritical fluids as solvents for singlet oxygen-mediated oxidations, which is an attractive proposition based on the long singlet-oxygen lifetimes in these systems and low fluid viscosity, are discussed. These include batch and continuous-flow approaches, and also biphasic systems to facilitate photosensitizer separation and recycling.