The doping engineering and crystal structure of rod-like Au8Ag17 nanoclusters.

Alloy nanoclusters protected by ligands were widely studied due to the synergistic effect of metal atoms, and they exhibit enhanced properties in different fields, such as bio-imaging and catalysis. Herein, we obtained Au8Ag17(PPh3)10Cl10 nanoclusters via one-step simple synthesis. The atomically precise crystal structure was determined by x-ray crystallography. It is found that the rod-like Au8Ag17 nanoclusters were composed of two Au4Ag9 icosahedrons via sharing the same Ag atom. Two Au atoms occupy the center of icosahedrons, and the other six Au atoms are all at the neck sites. Four kinds of Cl-Ag connecting modes were observed in Au8Ag17 nanoclusters. Moreover, the ultraviolet-visible absorption spectrum shows that the prominent absorption peaks of Au8Ag17 nanoclusters are at ∼395 and 483 nm. This work provides a feasible strategy to synthesize alloy nanoclusters with precise composition via doping engineering.

Synthesis and Optical Properties of Unique Pt1Ag24 Nanoclusters with Mixed Exterior Motif Structures.

The atomic arrangement of metal nanoclusters plays a significant role in the structure-property correlation. Herein, we present a novel Pt1Ag24(SR)16(PPh3)3 nanocluster with a unique structure, different from two reported Pt1Ag24 nanoclusters. The nanocluster was prepared via one-pot synthesis and solvent extraction. It has a centered icosahedral Pt1Ag12 kernel and an open shell composed of three Ag2(SR)3(PPh3) staple motifs and a unique trefoil-like Ag6(SR)7 motif. The three kinds of Pt1Ag24 nanoclusters have the same kernel but different shell configurations. The fine-tuning of structures is necessary and significant for the investigation of the relationship of structures and properties. The different UV-vis absorption spectra indicate that the optical properties of three Pt1Ag24 nanoclusters mainly depend on the exterior shell configuration and the metal-ligand interface. This work provides insights toward growth mechanism and the structure-property correlation of metal nanoclusters.

[AuAg26(SR)18S]- Nanocluster: Open Shell Structure and High Faradaic Efficiency in Electrochemical Reduction of CO2 to CO.

For atomically precise metal nanoclusters, distinctive molecular architectures and promising applications are urgently required to be intensively explored. Herein, we have first reported the open shell structure of the [AuAg26(S-Adm)18S]- nanocluster and its application in the electrochemical reduction of CO2. The X-ray crystal structure of the AuAg26 nanocluster is composed of a AuAg12 icosahedron kernel and a Ag14(SR)18S open shell. The shell includes a Ag6(SR)3S, a Ag5(SR)6, and three Ag(SR)3 motifs. It is the first time twisty propeller-like Ag5(SR)6 and trefoil-like Ag6(SR)3S motifs in metal nanoclusters have been observed. Due to the novel open shell configuration of Ag14(SR)18S, four triangular facets of the kernel are exposed. The AuAg26 nanocluster shows excellent catalytic activity in the electrochemical reduction of CO2 to CO. The Faradaic efficiency of CO is up to 98.4% under -0.97 V. The electrochemical in situ infrared study and DFT calculations demonstrate that the open shell structure of the AuAg26 nanocluster is beneficial to the forming of intermediate COOH* in the electrochemical reduction of CO2 to CO.

The synthesis and structure of the [PdAu13(PPh3)3(SR)7]+ nanocluster.

Metal alloy nanoclusters have attracted increasing attention due to the synergistic effect of the foreign atoms. For the first time the synthesis and crystal structure of the [PdAu13(PPh3)3(SR)7]+ nanocluster is reported. The crystal structure of the nanocluster was determined by single crystal X-ray diffraction. The [PdAu13(PPh3)3(SR)7]+ nanocluster has a concave polyhedron Au9Pd kernel, which looks like a girl dancing ballet. The structure shows that [PdAu13(PPh3)3(SR)7]+ has an open shell. Meanwhile, we also carried out ultraviolet-visible (Uv-vis) absorption spectroscopy and fluorescence spectroscopy to study the optical properties of the [PdAu13(PPh3)3(SR)7]+ nanocluster.

Structure of the Au23-x Agx (S-Adm)15 Nanocluster and Its Application for Photocatalytic Degradation of Organic Pollutants.

Ligands play an important role in determining the atomic arrangement within the metal nanoclusters. Here, we report a new nanocluster [Au23-x Agx (S-Adm)15 ] protected by bulky adamantanethiol ligands which was obtained through a one-pot synthesis. The total structure of [Au23-x Agx (S-Adm)15 ] comprises an Au13-x Agx icosahedral core, three Au3 (SR)4 units, and one AgS3 staple motif in contrast to the 15-atom bipyramidal core previously seen in [Au23-x Agx (SR)16 ]. UV/Vis spectroscopy indicates that the HOMO-LUMO gap of [Au23-x Agx (S-Adm)15 ] is 1.5 eV. DFT calculations reveal that [Au19 Ag4 (S-Adm)15 ] is the most stable structure among all structural possibilities. Benefitting from Ag doping, [Au23-x Agx (S-Adm)15 ] exhibits drastically improved photocatalytic activity for the degradation of rhodamine B (RhB) and phenol under visible-light irradiation compared to Au23 nanoclusters.

Cluster-to-cluster transformation among Au6, Au8 and Au11 nanoclusters.

We present the cluster-to-cluster transformations among three gold nanoclusters, [Au6(dppp)4]2+ (Au6), [Au8(dppp)4Cl2]2+ (Au8) and [Au11(dppp)5]3+ (Au11). The conversion process follows a rule that states that the transformation of a small cluster to a large cluster is achieved through an oxidation process with an oxidizing agent (H2O2) or with heating, while the conversion of a large cluster to a small one occurs through a reduction process with a reducing agent (NaBH4). All the reactions were monitored using UV-Vis spectroscopy and ESI-MS. This work may provide an alternative approach to the synthesis of novel gold nanoclusters and a further understanding of the structural transformation relationship of gold nanoclusters.