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Reversible Redox Cycling of Well-Defined, Ultrasmall Cu/Cu2O Nanoparticles

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Title: Reversible Redox Cycling of Well-Defined, Ultrasmall Cu/Cu2O Nanoparticles
Authors: Pike, SD
White, ER
Regoutz, A
Sammy, N
Payne, DJ
Williams, CK
Shaffer, MSP
Item Type: Journal Article
Abstract: Exceptionally small and well-defined copper (Cu) and cuprite (Cu2O) nanoparticles (NPs) are synthesized by the reaction of mesitylcopper(I) with either H2 or air, respectively. In the presence of substoichiometric quantities of ligands, namely, stearic or di(octyl)phosphinic acid (0.1–0.2 equiv vs Cu), ultrasmall nanoparticles are prepared with diameters as low as ∼2 nm, soluble in a range of solvents. The solutions of Cu NPs undergo quantitative oxidation, on exposure to air, to form Cu2O NPs. The Cu2O NPs can be reduced back to Cu(0) NPs using accessible temperatures and low pressures of hydrogen (135 °C, 3 bar H2). This striking reversible redox cycling of the discrete, solubilized Cu/Cu(I) colloids was successfully repeated over 10 cycles, representing 19 separate reactions. The ligands influence the evolution of both composition and size of the nanoparticles, during synthesis and redox cycling, as explored in detail using vacuum-transfer aberration-corrected transmission electron microscopy, X-ray photoelectron spectroscopy, and visible spectroscopy.
Issue Date: 13-Mar-2017
Date of Acceptance: 7-Mar-2017
URI: http://hdl.handle.net/10044/1/48951
DOI: https://dx.doi.org/10.1021/acsnano.6b07694
ISSN: 1936-0851
Publisher: American Chemical Society
Start Page: 2714
End Page: 2723
Journal / Book Title: ACS Nano
Volume: 11
Issue: 3
Copyright Statement: © 2017 American Chemical Society. This is an open access article published under a Creative Commons Attribution (CC-BY) License (https://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.
Sponsor/Funder: Engineering & Physical Science Research Council (EPSRC)
Engineering & Physical Science Research Council (EPSRC)
Funder's Grant Number: EP/H046380/1
EP/K035274/1
Keywords: Science & Technology
Physical Sciences
Technology
Chemistry, Multidisciplinary
Chemistry, Physical
Nanoscience & Nanotechnology
Materials Science, Multidisciplinary
Chemistry
Science & Technology - Other Topics
Materials Science
organo-copper(I)
copper nanoparticles
copper(I) oxide nanoparticles
redox switching
ultrasmall nanoparticles
transmission electron microscopy
SUPPORTED COPPER PARTICLES
CU NANOPARTICLES
ELECTRON-MICROSCOPY
COUPLING REACTIONS
IONIC LIQUIDS
ARYL HALIDES
OXIDE
OXIDATION
REDUCTION
CATALYST
MD Multidisciplinary
Publication Status: Published
Appears in Collections:Materials
Chemistry
Faculty of Natural Sciences



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