Visible-light sensitization and photoenergy storage in quantum dot/polyoxometalate systems

Abstract Recently, the process by which energy is transferred from photoexcited semiconductor nanocrystals, called quantum dots (QDs), to other semiconductors has attracted much attention and has potential application in solar energy conversion (i.e., QD-sensitized solar cells). Sensitization of wide band gap polyoxometalates (POMs) to visible light by using CuInS₂ QDs dispersed in an organic solution is demonstrated herein. Photoluminescence quenching and lifetime studies revealed efficient electron transfer from the CuInS₂ QDs to POMs, such as SiW₁₂O₄₀ and W₁₀O₃₂, that were hybridized with a cationic surfactant. CuInS₂ QDs function as an antenna that absorbs visible light and supplies electrons to the POMs to enable certain photocatalytic reactions, including noble-metal-ion reduction. The photoenergy storage capabilities of the QD-POM system, in which electrons photogenerated in QDs by visible-light excitation are trapped and accommodated by POMs to form reduced POM, are also demonstrated. Electrons stored in the POM can be later discharged through reductive reactions, such as oxygen reduction, in the dark. Enhanced capabilities: CuInS₂ quantum dots (QDs) are used to sensitize polyoxometalates (POMs) with wide band gaps. Visible-light-induced photocatalytic reactions proceed through the formation of one-electron-reduced POMs, which also show photoenergy-storing properties (see figure).