Coulomb Barrier for Sequential Two-Electron Transfer in a Nanoengineered Photocatalyst

Multielectron photocatalysis requires sequential, multiple charge transfer from the light absorber to the catalytic site. As a result, many-body effects induced by charge accumulation play a fundamental role in these reactions, especially when photocatalysts are miniaturized to the nanoscale. Here, we study sequential two-electron transfer in a state-of-the-art nanophotocatalyst, CdSe@CdS dot-in-rod (DIR) decorated with Pt tips, using pump-pump-probe transient absorption spectroscopy. Following the first electron transfer (ET) from DIR to the Pt tip, the second ET needs to not only compete with Auger recombination of a positively charged exciton but also experience a large Coulomb barrier exerted by two holes. As a result, both the ET rate and efficiency decrease by an order of magnitude. Analysis using a dissociation-limited long-range charge transfer model reveals that the Coulomb barrier of the second ET is similar to 60 meV higher than that of the first one. This study not only uncovers the mechanism and efficiency bottleneck of a real multielectron photocatalyst but also provides general guidelines for the design of multielectron photocatalytic systems.