Simple phosphinate ligands access zinc clusters identified in the synthesis of zinc oxide nanoparticles

Journal article

The bottom-up synthesis of ligand-stabilized functional nanoparticles from molecular precursors is widely applied but is difficult to study mechanistically. Here we use 31 P NMR spectroscopy to follow the trajectory of phosphinate ligands during the synthesis of a range of ligated zinc oxo clusters, containing 4, 6 and 11 zinc atoms. Using an organometallic route, the clusters interconvert rapidly and self-assemble in solution based on thermodynamic equilibria rather than nucleation kinetics. These clusters are also identified in situ during the synthesis of phosphinate-capped zinc oxide nanoparticles. Unexpectedly, the ligand is sequestered to a stable Zn 11 cluster during the majority of the synthesis and only becomes coordinated to the nanoparticle surface, in the final step. In addition to a versatile and accessible route to (optionally doped) zinc clusters, the findings provide an understanding of the role of well-defined molecular precursors during the synthesis of small (2-4 nm) nanoparticles.

Authors: Pike, S; White, E; Shaffer, M; Williams, C

• Publication status: Published
• Peer review status: Peer reviewed
• Publisher: Nature Publishing Group
• Journal: Nature Communications
• Volume: 7
• Publication date: 2016-10-13
• Acceptance date: 2016-08-25
• DOI: 10.1038/ncomms13008
• EISSN: 2041-1723
• ISSN: 2041-1723
• Language: English
• Keywords: SOLAR-CELLS; METHANOL SYNTHESIS; Science & Technology - Other Topics; PRECURSORS; ZNO NANOCRYSTALS; Multidisciplinary Sciences; STABILIZED ZNO; QUANTUM DOTS; Journal Article; COLLOIDAL SOLUTIONS; METAL-ORGANIC FRAMEWORKS; Science & Technology; GROWTH; IN-SITU