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 CuIn1.5Se3 (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 VRHE) is obtained under 1 sun illumination, which is a record for the PEC sulfite oxidation based on nontoxic QD photoanodes.