A1 Journal article (refereed)
[Pt2Cu34(PET)22Cl4]2–: An Atomically Precise, 10-Electron PtCu Bimetal Nanocluster with a Direct Pt–Pt Bond (2021)

Lee, S., Bootharaju, M. S., Deng, G., Malola, S., Häkkinen, H., Zheng, N., & Hyeon, T. (2021). [Pt2Cu34(PET)22Cl4]2–: An Atomically Precise, 10-Electron PtCu Bimetal Nanocluster with a Direct Pt–Pt Bond. Journal of the American Chemical Society, 143(31), 12100-12107. https://doi.org/10.1021/jacs.1c04002

JYU authors or editors

Publication details

All authors or editors: Lee, Sanghwa; Bootharaju, Megalamane S.; Deng, Guocheng; Malola, Sami; Häkkinen, Hannu; Zheng, Nanfeng; Hyeon, Taeghwan

Journal or series: Journal of the American Chemical Society

ISSN: 0002-7863

eISSN: 1520-5126

Publication year: 2021

Publication date: 27/07/2021

Volume: 143

Issue number: 31

Pages range: 12100-12107

Publisher: American Chemical Society (ACS)

Publication country: United States

Publication language: English

DOI: https://doi.org/10.1021/jacs.1c04002

Publication open access: Not open

Publication channel open access:

Abstract

Heteroatom-doped metal nanoclusters (NCs) are highly desirable to gain fundamental insights into the effect of doping on the electronic structure and catalytic properties. Unfortunately, their controlled synthesis is highly challenging when the metal atomic sizes are largely different (e.g., Cu and Pt). Here, we design a metal-exchange strategy that enables simultaneous doping and resizing of NCs. Specifically, [Pt2Cu34(PET)22Cl4]2– NC, the first example of a Pt-doped Cu NC, is synthesized by utilizing the unique reactivity of [Cu32(PET)24Cl2H8]2– NC with Pt4+ ions. The single-crystal X-ray structure reveals that two directly bonded Pt atoms occupy the two centers of an unusually interpenetrating, incomplete biicosahedron core (Pt2Cu18), which is stabilized by a Cu16(PET)22Cl4 shell. The molecular structure and composition of the NC are validated by combined experimental and theoretical results. Electronic structure calculations, using the density functional theory, show that the Pt2Cu34 NC is a 10-electron superatom. The computed absorption spectrum matches well with the measured data and allows for assignment of the absorption peaks. The calculations also rationalize energetics for ligand exchange observed in the mass spectrometry data. The synergistic effects induced by Pt doping are found to enhance the catalytic activity of Cu NCs by ∼300-fold in silane to silanol conversion under mild conditions. Furthermore, our synthetic strategy has potential to produce Ni-, Pd-, and Au-doped Cu NCs, which will open new avenues to uncover their molecular structures and catalytic properties.

Keywords: nanoparticles; nanostructures; metals; molecules; chemical properties

Contributing organizations

Related projects

Ministry reporting: Yes

Reporting Year: 2021

JUFO rating: 3