Experimental and theoretical evidence for unprecedented strong interactions of gold atoms with boron on boron/sulfur-doped carbon surfaces

Samya Banerjee; Juliusz A Wolny; Mohsen Danaie; Nicolas P E Barry; Yisong Han; Houari Amari; Richard Beanland; Volker Schünemann; Peter J Sadler

doi:10.1039/d3na00956d

Experimental and theoretical evidence for unprecedented strong interactions of gold atoms with boron on boron/sulfur-doped carbon surfaces

Nanoscale Adv. 2023 Dec 11;6(7):1837-1846. doi: 10.1039/d3na00956d. eCollection 2024 Mar 26.

Authors

Samya Banerjee^{1

2}, Juliusz A Wolny³, Mohsen Danaie⁴, Nicolas P E Barry^{1

5}, Yisong Han⁶, Houari Amari⁶, Richard Beanland⁶, Volker Schünemann³, Peter J Sadler¹

Affiliations

¹ Department of Chemistry, University of Warwick CV4 7AL Coventry UK P.J.Sadler@warwick.ac.uk.
² Department of Chemistry, Indian Institute of Technology (BHU) Varanasi Uttar Pradesh 221005 India samya.chy@itbhu.ac.in.
³ Department of Physics, University of Kaiserslautern-Landau Erwin-Schrödinger-Straße 46 67663 Kaiserslautern Germany wolny@rhrk.uni-kl.de.
⁴ Diamond Light Source Ltd, electron Physical Science Imaging Centre (ePSIC), Harwell Science & Innovation Campus Didcot Oxfordshire OX11 0DE UK mohsen.danaie@diamond.ac.uk.
⁵ School of Chemistry and Biosciences, University of Bradford Bradford BD1 7DP UK.
⁶ Department of Physics, University of Warwick Gibbet Hill Road Coventry CV4 7Al UK.

Abstract

The 16e square-planar bis-thiolato-Au(iii) complexes [Au^III(1,2-dicarba-closo-dodecarborane-1,2-dithiolato)₂][NBu₄] (Au-1) and [Au^III(4-methyl-1,2-benzenedithiolato)₂][NBu₄] (Au-2) have been synthesized and fully characterized. Au-1 and Au-2 were encapsulated in the symmetrical triblock copolymer poloxamer (Pluronic®) P123 containing blocks of poly(ethylene oxide) and poly(propylene oxide), giving micelles AuMs-1 and AuMs-2. High electron flux in scanning transmission electron microscopy (STEM) was used to generate single gold atoms and gold nanocrystals on B/S-doped graphitic surfaces, or S-doped amorphous carbon surfaces from AuMs-1 and AuMs-2, respectively. Electron energy loss spectroscopy (EELS) data suggested strong interactions of gold atoms/nanocrystals with boron in the B/S-doped graphitic matrix. Density-functional theory (DFT) calculations, also supported the experimental findings, pointing towards strong Au-B bonds, depending on the charge on the Au-(B-graphene) fragment and the presence of further defects in the graphene lattice.