Understanding the mechanism of plasmon-driven water splitting: hot electron injection and a near field enhancement effect

Utilizing plasmon-generated hot carriers to drive chemical reactions has currently become an active area of research in solar photocatalysis at the nanoscale. However, the mechanism underlying exact transfer and the generation dynamics of hot carriers, and the strategies used to further improve the quantum efficiency of the photocatalytic reaction still deserve further investigation. In this work, we perform a nonadiabatic excited-state dynamics study to depict the correlation between the reaction rate of plasmon-driven water splitting (PDWS) and the sizes of gold particles, the incident light frequency and intensity, and the near-field spatial distribution. Four model systems, H2O and Au20@H2O separately interacting with the laser field and the near field generated by the Au nanoparticle (NP) with a few nanometers in size, have been investigated. Our simulated results clearly unveil the mechanism of PDWS and hot-electron injection in a Schottky-free junction: the electrons populated on the antibonding orbitals of H2O are mandatory to drive the OH bond breaking and the strong orbital hybridization between Au20 and H2O creates the conditions for direct electron injection. We further find that the linear dependence of the reaction rate and the field amplitude only holds at a relatively weak field and it breaks down when the second OH bond begins to dissociate and field-induced water fragmentation occurs at a very intensive field, and that with the guarantee of electron injection, the water splitting rate increases with an increase in the NP size. This study will be helpful for further improving the efficiency of photochemical reactions involving plasmon-generated hot carriers and expanding the applications of hot carriers in a variety of chemical reactions.