Designing catalysts for water splitting based on electronic structure considerations Academic Article uri icon


  • Abstract The disproportionation of H2O into solar fuels H2 and O2, or water splitting, is a promising strategy for clean energy harvesting and storage but requires the concerted action of absorption of photons, separation of excitons, charge diffusion to catalytic sites and catalysis of redox processes. It is increasingly evident that the rational design of photocatalysts for efficient water splitting must employ hybrid systems, where the different components perform light harvesting, charge separation and catalysis in tandem. In this topical review, we report on the recent development of a new class of hybrid photocatalysts that employs M x V2O5 (M = p-block cation) nanowires in order to engineer efficient charge transfer from the photoactive chalcogenide quantum dots (QDs) to the water-splitting and hydrogen evolving catalysts. Herein, we summarize the oxygen-mediated lone pair mechanism used to modulate the energy level and orbital character of mid-gap states in the M x V2O5 nanowires. The electronic structure of M x V2O5 is discussed in terms of density functional theory and hard x-ray photoelectron spectroscopy (HAXPES) measurements. The principles of HAXPES are explained within the context of its unique sensitivity to metal 5(6)s orbitals and ability to non-destructively study buried interface alignments of quantum dot decorated nanowires i.e., M x V2O5/CdX (X = S, Se, Te). We illustrate with examples how the M x V2O5/CdX band alignments can be rationally engineered for ultra-fast charge-transfer of photogenerated holes from the quantum dot to the nanowires; thereby suppressing anodic photo-corrosion in the CdX QDs and enabling efficacious hydrogen evolution.

published proceedings


altmetric score

  • 9.85

author list (cited authors)

  • Razek, S. A., Popeil, M. R., Wangoh, L., Rana, J., Suwandaratne, N., Andrews, J. L., ... Piper, L.

citation count

  • 24

complete list of authors

  • Razek, Sara Abdel||Popeil, Melissa R||Wangoh, Linda||Rana, Jatinkumar||Suwandaratne, Nuwanthi||Andrews, Justin L||Watson, David F||Banerjee, Sarbajit||Piper, Louis FJ

publication date

  • June 2020