Self‐Assembled Au/CdSe Nanocrystal Clusters for Plasmon‐Mediated Photocatalytic Hydrogen Evolution

Plasmon-mediated photocatalytic systems generally suffer from poor efficiency due to weak absorption overlap and thus limited energy transfer between the plasmonic metal and the semiconductor. Herein, a near-ideal plasmon-mediated photocatalyst system is developed. Au/CdSe nanocrystal clusters (NCs) are successfully fabricated through a facile emulsion-based self-assembly approach, containing Au nanoparticles (NPs) of size 2.8, 4.6, 7.2, or 9.0 nm and CdSe quantum dots (QDs) of size ≈3.3 nm. Under visible-light irradiation, the Au/CdSe NCs with 7.2 nm Au NPs afford very stable operation and a remarkable H2 -evolution rate of 73 mmol gCdSe-1 h-1 (10× higher than bare CdSe NCs). Plasmon resonance energy transfer from the Au NPs to the CdSe QDs, which enhances charge-carrier generation in the semiconductor and suppresses bulk recombination, is responsible for the outstanding photocatalytic performance. The approach used here to fabricate the Au/CdSe NCs is suitable for the construction of other plasmon-mediated photocatalysts.