Design, construction and application of photoelectrochemical flow reactors

This thesis examines the design, construction, and application of novel reactors that merge light, electricity, and flow chemistry into efficient, scalable platforms for producing fine chemicals and fuels. The research follows two primary trajectories. The first part focuses on electrophotocatalytic (EPC) transformations for organic synthesis. Chapter 2 introduces a flow reactor (f-EPC) that integrates photons and electrons to enable efficient C(sp³)–H heteroarylation and late-stage drug functionalization. Chapter 3 applies similar principles to C(sp²)–N coupling for amide formation; both methods leverage radical-polar crossover and hydrogen atom transfer to achieve high productivity. The second part transitions to modular flow photoelectrochemical cells (f-DSPEC and f-PEC) designed for solar fuel generation and chemical synthesis. In Chapter 4, engineering improvements in mass transport and microfluidic channels enhanced the f-DSPEC’s productivity and stability during benzyl alcohol oxidation. Chapter 5 details an f-PEC utilizing BiVO₄ photoanodes for water splitting. This system overcomes the limitations of traditional batch reactors and offers significant potential for scalable green manufacturing, though future work is required regarding material durability and gas separation. Ultimately, this thesis establishes fundamental design principles for photoelectrochemical flow reactors. By combining innovative reaction design with pragmatic engineering, this work provides a foundation for translating these technologies from laboratory demonstrations into industrial applications for sustainable chemical and fuel production.