We designed photoelectrochemical cells to achieve efficient oxidation of rhodamine B (RhB) without the need for photocatalyst or supporting electrolyte. RhB, the metal anode/cathode, and O₂ formed an energy-relay structure, enabling the efficient formation of O ₂ ^– species under ultraviolet illumination. In a single-compartment cell (S cell) containing a titanium (Ti) anode, Ti cathode, and 10 mg·mL^–1 RhB in water, the zero-order rate constant of the photoelectrochemical oxidation (k_PEC) of RhB was 0.049 mg·L^–1·min^–1, while those of the photochemical and electrochemical oxidations of RhB were nearly zero. k_PEC remained almost the same when 0.5 mol·L^–1 Na₂SO₄ was included in the reactive solution, regardless of the increase in the photocurrent of the S cell. The k_PEC of the illuminated anode compartment in the two-compartment cell, including a Ti anode, Ti cathode, and 10 mg·mL^–1 RhB in water, was higher than that of the S cell. These results support a simple, eco-friendly, and energysaving method to realize the efficient degradation of RhB.

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