Ligand-free Au nanoclusters/g-C3N4 ultra-thin nanosheets composite photocatalysts for efficient visible-light-driven photocatalytic H2 generation

In this paper, we report the synthesis of ligand-free Au nanoclusters (NCs)/g-C3N4 ultra-thin nanosheets (NSs) composite via a facile wet-impregnation method with post-annealing. On the one hand, post-annealing was used for the exfoliation of multi-layered g-C3N4 to obtain ultra-thin NSs; on the other hand, after Au25(Cys)18 NCs were loaded, post-annealing was further adopted to remove the ligands to obtain clean surface on Au NCs. It is demonstrated that the loaded Au NCs were aggregating resistant by post-annealing. Constructing heterojunctions with appropriate inter-band structures between the ligand-free Au NCs and the ultra-thin g-C3N4 NSs, along with the mono-distribution of the Au NCs and their intimate contact with g-C3N4 NSs ensured the smooth interfacial charge transfer. As a result, the composite photocatalysts exhibited efficient visible-light-induced photocatalytic H2 generation, mainly due to the local electric field enhancement induced by excitation of Au NCs under visible light and the improved charge separation in g-C3N4. This work provides a general strategy for the synthesis of noble metal NCs based composites with clean surface as the efficient photocatalysts for solar energy conversion. A stepwise post-annealing strategy is exploited to prepare g-C3N4 ultra-thin nanosheets modified with highly dispersed ligand-free Au nanoclusters for efficient photocatalytic hydrogen production.