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Issue 2, 2015
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Nucleation, aggregative growth and detachment of metal nanoparticles during electrodeposition at electrode surfaces

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Abstract

The nucleation and growth of metal nanoparticles (NPs) on surfaces is of considerable interest with regard to creating functional interfaces with myriad applications. Yet, key features of these processes remain elusive and are undergoing revision. Here, the mechanism of the electrodeposition of silver on basal plane highly oriented pyrolytic graphite (HOPG) is investigated as a model system at a wide range of length scales, spanning electrochemical measurements from the macroscale to the nanoscale using scanning electrochemical cell microscopy (SECCM), a pipette-based approach. The macroscale measurements show that the nucleation process cannot be modelled as either truly instantaneous or progressive, and that step edge sites of HOPG do not play a dominant role in nucleation events compared to the HOPG basal plane, as has been widely proposed. Moreover, nucleation numbers extracted from electrochemical analysis do not match those determined by atomic force microscopy (AFM). The high time and spatial resolution of the nanoscale pipette set-up reveals individual nucleation and growth events at the graphite basal surface that are resolved and analysed in detail. Based on these results, corroborated with complementary microscopy measurements, we propose that a nucleation-aggregative growth-detachment mechanism is an important feature of the electrodeposition of silver NPs on HOPG. These findings have major implications for NP electrodeposition and for understanding electrochemical processes at graphitic materials generally.

Graphical abstract: Nucleation, aggregative growth and detachment of metal nanoparticles during electrodeposition at electrode surfaces

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Publication details

The article was received on 10 Sep 2014, accepted on 07 Nov 2014 and first published on 07 Nov 2014


Article type: Edge Article
DOI: 10.1039/C4SC02792B
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Citation: Chem. Sci., 2015,6, 1126-1138
  • Open access: Creative Commons BY license
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    Nucleation, aggregative growth and detachment of metal nanoparticles during electrodeposition at electrode surfaces

    S. C. S. Lai, R. A. Lazenby, P. M. Kirkman and P. R. Unwin, Chem. Sci., 2015, 6, 1126
    DOI: 10.1039/C4SC02792B

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