Electrodeposition of ligand-free copper nanoparticles from aqueous nanodroplets

Tarolla, Nicole E.; Voci, Silvia; Reyes-Morales, Joshua; Pendergast, Andrew D.; Dick, Jeffrey E.

doi:10.1039/d1ta02369a

Title: Electrodeposition of ligand-free copper nanoparticles from aqueous nanodroplets

Journal Article · 17 August 2021 · Journal of Materials Chemistry. A

DOI: https://doi.org/10.1039/d1ta02369a · OSTI ID:1853737

^[1]; Voci, Silvia ^[2];

^[2];

^[2]

Univ. of North Carolina, Chapel Hill, NC (United States); OSTI
Univ. of North Carolina, Chapel Hill, NC (United States)

Copper nanoparticles have emerged as promising electrocatalysts for energy storage and conversion. Generally, homogenous nanoparticle synthesis requires a stabilizing ligand, which may influence the electrocatalysis. Ligands can be avoided by direct nanoparticle electrodeposition. Here, we extend nanodroplet-mediated electrodeposition to the electrodeposition of copper nanoparticles from aqueous nanodroplets suspended in 0.1 M tetrabutylammonium hexafluorophosphate ([TBA][PF₆]) and 1,2-dichloroethane. Stochastic electrochemistry on microelectrodes was used to elucidate nanoparticle growth kinetics for various solution conditions and substrate materials. A study on the effect of surfactants on nanoparticle morphology and growth kinetics demonstrated the surfactant's role as an avenue for morphological control. Nanoparticle morphology was studied by Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM). Energy-dispersive X-ray Spectroscopy (EDX) confirmed the presence of copper nanoparticles. TEM and Selected Area Electron Diffraction (SAED) confirmed nanoparticle size, morphology, and polycrystallinity. We demonstrate tunable nanoparticle size using cyclic voltammetry on single aqueous nanodroplets by altering the voltammetric sweeping potentials of copper electroreduction. Finite element simulations validate the voltammetric response and ability to control the nanoparticle size with nanometer resolution during a voltammetric sweep. These results inform the electrodeposition of copper nanoparticles from aqueous nanodroplets for important applications, such as the conversion of CO₂ to hydrocarbon fuels.

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Research Organization:: Univ. of North Carolina, Chapel Hill, NC (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES); the National Science Foundation (NSF)

Grant/Contract Number:: SC0021173

OSTI ID:: 1853737

Journal Information:: Journal of Materials Chemistry. A, Journal Name: Journal of Materials Chemistry. A Journal Issue: 35 Vol. 9; ISSN JMCAET; ISSN 2050-7488

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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