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Single Au Atom Doping of Silver Nanoclusters.

ABSTRACT: Ag₂₉ nanoclusters capped with lipoic acid (LA) can be doped with Au. The doped clusters show enhanced stability and increased luminescence efficiency. We attribute the higher quantum yield to an increase in the rate of radiative decay. With mass spectrometry, the Au-doped clusters were found to consist predominantly of Au₁Ag₂₈(LA)₁₂^3-. The clusters were characterized using X-ray absorption spectroscopy at the Au L₃-edge. Both the extended absorption fine structure (EXAFS) and the near edge structure (XANES) in combination with electronic structure calculations confirm that the Au dopant is preferentially located in the center of the cluster. A useful XANES spectrum can be recorded for lower concentrations, or in shorter time, than the more commonly used EXAFS. This makes XANES a valuable tool for structural characterization.

SUBMITTER: van der Linden M

PROVIDER: S-EPMC6328285 | biostudies-literature | 2018 Dec

REPOSITORIES: biostudies-literature

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Single Au Atom Doping of Silver Nanoclusters.

van der Linden Marte M van Bunningen Arnoldus J AJ Amidani Lucia L Bransen Maarten M Elnaggar Hebatalla H Glatzel Pieter P Meijerink Andries A de Groot Frank M F FMF

ACS nano 20181203 12

Ag29 nanoclusters capped with lipoic acid (LA) can be doped with Au. The doped clusters show enhanced stability and increased luminescence efficiency. We attribute the higher quantum yield to an increase in the rate of radiative decay. With mass spectrometry, the Au-doped clusters were found to consist predominantly of Au1Ag28(LA)123-. The clusters were characterized using X-ray absorption spectroscopy at the Au L3-edge. Both the ...[more]

PMID: 30458110

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Project description:Dopants in gold nanoclusters have been proved to mediate the intrinsic electronic properties of homo-clusters. In this work, we report the precise synthesis of atomically precise Au8Ag3(PPh3)7Cl3 alloy nanoclusters with multiple Ag dopants for the first time. Their structure was resolved by single-crystal X-ray crystallography. Au8Ag3(PPh3)7Cl3 nanoclusters possessed a similar structure topology to the well-known Au11(PPh3)7Cl3 nanoclusters. It is observed that the three Ag atoms were fixed at the cluster surface and bound selectively with the chlorine ligands in a C3-axis manner. The alloy nanoclusters exhibited a closed-shell electronic structure (i.e., 8(Au 6s1) + 3(Ag 5s1) - 3(Cl) = 8e), as evidenced by electrospray ionization-mass spectrometry (ESI-MS). The photothermodynamic stability of alloy clusters was remarkably improved (e.g., full decomposition after 7 days under sunlight irradiation vs. 3 days for Au11(PPh3)7Cl3 clusters). DFT calculations indicated that the Ag dopants in a C3-axis manner could obviously delocalize the electrons of Au to the orbitals of P atoms and then mediate the electronic property of the clusters. Shrinkage of the HOMO-LUMO gap to 1.67 eV of Au8Ag3(PPh3)7Cl3 was observed as compared with that of homo-nanoclusters of Au11(PPh3)7Cl3 (2.06 eV). The electrochemical gap of Au8Ag3(PPh3)7Cl3 alloy nanoclusters was 1.272 V, which was higher than that of Au11(PPh3)7Cl3 nanoclusters, which indicated higher electrochemical stability, as evidenced by the differential pulse voltammetry (DPV) method. Au8Ag3(PPh3)7Cl3 clusters exhibited three specific photoluminescence peaks at 405, 434 and 454 nm. AuAg alloy clusters exhibited twofold greater activity than homo gold clusters in the photooxidation of benzylamine, which was mainly due to the unique electronic properties of the alloy clusters. Controllable heteroatom doping engineering is a powerful method to tune the electronic properties of clusters, and then improve their photothermodynamic and electrochemical stability simultaneously for potential photocatalytic applications.

Dataset Information

Single Au Atom Doping of Silver Nanoclusters.

Publications

Single Au Atom Doping of Silver Nanoclusters.

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