Atomically precise nanoclusters predominantly seed gold nanoparticle syntheses

Liang Qiao; Nia Pollard; Ravithree D Senanayake; Zhi Yang; Minjung Kim; Arzeena S Ali; Minh Tam Hoang; Nan Yao; Yimo Han; Rigoberto Hernandez; Andre Z Clayborne; Matthew R Jones

doi:10.1038/s41467-023-40016-3

Atomically precise nanoclusters predominantly seed gold nanoparticle syntheses

Nat Commun. 2023 Jul 21;14(1):4408. doi: 10.1038/s41467-023-40016-3.

Authors

Liang Qiao^{1

2}, Nia Pollard³, Ravithree D Senanayake⁴, Zhi Yang¹, Minjung Kim¹, Arzeena S Ali¹, Minh Tam Hoang⁴, Nan Yao⁵, Yimo Han⁶, Rigoberto Hernandez^{4

7

8}, Andre Z Clayborne³, Matthew R Jones^{9

10}

Affiliations

¹ Department of Chemistry, Rice University, Houston, TX, 77005, USA.
² Division of Fundamental Research, Petrochemical Research Institute, PetroChina, Beijing, 102206, China.
³ Department of Chemistry & Biochemistry, George Mason University, Fairfax, VA, 22030, USA.
⁴ Department of Chemistry, Johns Hopkins University, Baltimore, MD, 21218, USA.
⁵ Princeton Materials Institute, Princeton University, Princeton, NJ, 08544, USA.
⁶ Department of Materials Science & Nanoengineering, Rice University, Houston, TX, 77005, USA.
⁷ Department of Chemical and Biomolecular Engineering, Johns Hopkins University, Baltimore, MD, 21218, USA.
⁸ Department of Materials Science and Engineering, Johns Hopkins University, Baltimore, MD, 21218, USA.
⁹ Department of Chemistry, Rice University, Houston, TX, 77005, USA. mrj@rice.edu.
¹⁰ Department of Materials Science & Nanoengineering, Rice University, Houston, TX, 77005, USA. mrj@rice.edu.

Abstract

Seed-mediated synthesis strategies, in which small gold nanoparticle precursors are added to a growth solution to initiate heterogeneous nucleation, are among the most prevalent, simple, and productive methodologies for generating well-defined colloidal anisotropic nanostructures. However, the size, structure, and chemical properties of the seeds remain poorly understood, which partially explains the lack of mechanistic understanding of many particle growth reactions. Here, we identify the majority component in the seed solution as an atomically precise gold nanocluster, consisting of a 32-atom Au core with 8 halide ligands and 12 neutral ligands constituting a bound ion pair between a halide and the cationic surfactant: Au₃₂X₈[AQA⁺•X^-]₁₂ (X = Cl, Br; AQA = alkyl quaternary ammonium). Ligand exchange is dynamic and versatile, occurring on the order of minutes and allowing for the formation of 48 distinct Au₃₂ clusters with AQAX (alkyl quaternary ammonium halide) ligands. Anisotropic nanoparticle syntheses seeded with solutions enriched in Au₃₂X₈[AQA⁺•X^-]₁₂ show narrower size distributions and fewer impurity particle shapes, indicating the importance of this cluster as a precursor to the growth of well-defined nanostructures.

Abstract

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