Highly Efficient Photoelectrochemical Hydrogen Production Using Nontoxic CuIn1.5Se3 Quantum Dots with ZnS/SiO2 Double Overlayers

Quantum dots (QDs) are a promising material for photoelectrochemical (PEC) hydrogen (H₂) production because of their attractive optical properties including high optical absorption coefficient, band-gap tunability, and potential multiple exciton generation. To date, QDs containing toxic elements such as Cd or Pb have been mainly investigated for PEC H₂ production, which cannot be utilized in practice because of the environmental issue. Here, we demonstrate a highly efficient type II heterojunction photoanode of nontoxic CuIn_1.5Se₃ (CISe) QDs and a mesoporous TiO₂ film. In addition, ZnS/SiO₂ double overlayers are deposited on the photoanodes to passivate surface defect sites on the CISe QDs, leading to the enhancement of both photocurrent density and photostability. Due to a combination of a wide light absorption range of the CISe QDs and the reduced interfacial charge recombination by the overlayers, a remarkable photocurrent density of 8.5 mA cm^-2 (at 0.5 V_RHE) is obtained under 1 sun illumination, which is a record for the PEC sulfite oxidation based on nontoxic QD photoanodes.