Graphene Bridge for Photocatalytic Hydrogen Evolution with Gold Nanocluster Co-Catalysts.

Herein, the UV light photocatalytic activity of an Au101NC-AlSrTiO3-rGO nanocomposite comprising 1 wt% rGO, 0.05 wt% Au101(PPh3)21Cl5 (Au101NC), and AlSrTiO3 evaluated for H2 production. The synthesis of Au101NC-AlSrTiO3-rGO nanocomposite followed two distinct routes: (1) Au101NC was first mixed with AlSrTiO3 followed by the addition of rGO (Au101NC-AlSrTiO3:rGO) and (2) Au101NC was first mixed with rGO followed by the addition of AlSrTiO3 (Au101NC-rGO:AlSrTiO3). Both prepared samples were annealed in air at 210 °C for 15 min. Inductively coupled plasma mass spectrometry and high-resolution scanning transmission electron microscopy showed that the Au101NC adhered almost exclusively to the rGO in the nanocomposite and maintained a size less than 2 nm. Under UV light irradiation, the Au101NC-AlSrTiO3:rGO nanocomposite produced H2 at a rate 12 times greater than Au101NC-AlSrTiO3 and 64 times greater than AlSrTiO3. The enhanced photocatalytic activity is attributed to the small particle size and high loading of Au101NC, which is achieved by non-covalent binding to rGO. These results show that significant improvements can be made to AlSrTiO3-based photocatalysts that use cluster co-catalysts by the addition of rGO as an electron mediator to achieve high cluster loading and limited agglomeration of the clusters.

Au101-rGO nanocomposite: immobilization of phosphine-protected gold nanoclusters on reduced graphene oxide without aggregation.

Graphene supported transition metal clusters are of great interest for potential applications, such as catalysis, due to their unique properties. In this work, a simple approach to deposit Au101(PPh3)21Cl5 (Au101NC) on reduced graphene oxide (rGO) via an ex situ method is presented. Reduction of graphene oxide at native pH (pH ≈ 2) to rGO was performed under aqueous hydrothermal conditions. Decoration of rGO sheets with controlled content of 5 wt% Au was accomplished using only pre-synthesised Au101NC and rGO as precursors and methanol as solvent. High resolution scanning transmission electron microscopy indicated that the cluster size did not change upon deposition with an average diameter of 1.4 ± 0.4 nm. It was determined that the rGO reduction method was crucial to avoid agglomeration, with rGO reduced at pH ≈ 11 resulting in agglomeration. X-ray photoelectron spectroscopy was used to confirm the deposition of Au101NCs and show the presence of triphenyl phosphine ligands, which together with attenuated total reflectance Fourier transform infrared spectroscopy, advocates that the deposition of Au101NCs onto the surface of rGO was facilitated via non-covalent interactions with the phenyl groups of the ligands. Inductively coupled plasma mass spectrometry and thermogravimetric analysis were used to determine the gold loading and both agree with a gold loading of ca. 4.8-5 wt%. The presented simple and mild strategy demonstrates that good compatibility between size-specific phosphine protected gold clusters and rGO can prevent aggregation of the metal clusters. This work contributes towards producing an agglomeration-free synthesis of size-specific ligated gold clusters on rGO that could have wide range of applications.