Imaging Size Effects on the Electrocatalytic Activity of Gold Nanoparticles Using Electrochemical Microscopy

Andrew J. Wain
National Physical Laboratory, Hampton Road, Teddington, TW11 0LW, UK Email: andy.wain@npl.co.uk

Introduction
Understanding the effects of particle size and surface structure on the electrochemical behaviour of nanomaterials is of critical importance to the optimization of electrocatalysts. In particular, oxygen reduction and hydrogen peroxide oxidation are reactions of continued interest due to their application in energy conversion technologies such as fuel cells and electrolysers. In order to achieve a confident grasp of structure-activity relationships new approaches to comparative performance screening are sought. In this work the innovative application of scanning electrochemical microscopy (SECM) to imaging the electrocatalytic activity of ensembles of gold nanoparticles (AuNPs), immobilized in an array platform, is demonstrated. By varying the average AuNP diameter across the array, the effect of particle size on relative electrocatalytic performance can be monitored on a single surface. Remarkably, an increase in normalized activity with decreasing particle size was observed, which can be correlated to the ratio of Au(110) to Au(111) sites.

Characterisation of Gold Nanoparticles

TEM Imaging
Experiments were conducted using a commercial source of colloidal AuNPs (BBI, Cardiff, UK) with nominal particle diameters between 5 and 50 nm. Particles were generally spherical, although faceting is discernible in the TEM imaging (pictured for 5 nm AuNPs).

Electrochemical Behaviour
Oxygen Reduction
(O2 saturated 0.1 M NaOH)

Hydrogen Peroxide Oxidation

(1 mM H2O2 in 0.1 M NaOH)

Glassy Carbon Electrode Glassy Carbon + 50 nm AuNP Glassy Carbon + 5 nm AuNP

Surface Structure
The ratio of exposed Au(110)/Au(111) facets was estimated by electrochemical fingerprinting:  AuNP colloid drop cast onto glassy carbon substrate  Lead underpotential deposition voltammetry undertaken in 1 mM Pb2+/0.1 M NaOH  Stripping peaks assigned to different miller planes  Au(110)/Au(111) ratio systematically decreased with increasing particle diameter

5 nm AuNPs exhibited a higher electrocatalytic activity than 50 nm AuNPs g

Scanning Electrochemical Microscopy (SECM)

In SECM a microelectrode probe is scanned laterally across the substrate, and is used to monitor processes locally in solution and map corresponding surface reactivity.

Nanoparticle Arrays
AuNP ensembles were immobilized in an array pattern on a 1 cm 1 cm glassy carbon substrate using a picolitre solution dispenser (CH Instruments, Texas, USA).

Probe Reference Auxillary

10 mm
Substrate

AuNP Diameter /nm 5 10 20 50

Au(110)/ Au(111) Ratio 3.0 2.6 1.2 0.4

SECM Screening
Oxygen Reduction
Competition Mode SECM: A  rray immersed in 0.1 M H2SO4 or 0.1 M NaOH solution
Decreasing coverage

Coverage Variation:

Particle Size Variation:

Substrate Potential Variation:

 Platinum SECM tip positioned ~10 m from substrate  Diffusion controlled O2 reduction electrochemically driven at tip Substrate biased to drive O2 reduction at AuNPs Tip current monitored as probe is scanned laterally  Depletion of O2 close to AuNPs causes local drop in tip current

n Current drop increases with AuNP coverage within array spots

n In both acid and alkali media, O2 reduction activity increased with decreasing particle size
NOTE: AuNP coverages within array were normalized so that each spot consisted of the same total Au surface

Substrate Substrate Bias Bias

Current drop increases with g

AuNP coverage within array spots

In both acid and alkali media, O reduction g

2

activity increased with decreasing particle size

Systematically decreasing the substrate potential g highlights the activity contrast

NOTE: AuNP coverages within array were normalized so that each spot consisted of the same total Au surface area

Hydrogen Peroxide Oxidation

Substrate Generation Tip Collection SECM:  Array immersed in 0.1 M NaOH solution + 1 mM H2O2 O2 reduction electrochemically driven at tip  Substrate biased to drive H2O2 oxidation at AuNPs  Generation of O2 close to AuNPs causes local increase in tip current

Particle Size Variation:

Conclusions
 By depositing AuNP ensembles in an array platform, the electrocatalytic performance of AuNPs with different diameters could be compared within a single experiment on a single surface  A clear size effect is evidenced for O2 reduction, in which electrocatalytic activity increases with decreasing AuNP diameter  This can be rationalized by the systematic exposure of more active Au(110) facets with decreasing particle size, in accordance with the established view that O2 reduction is a structure sensitive reaction

Substrate Bias

 No clear size effect for H2O2 oxidation is apparent for the larger particles, in keeping with single crystal studies for low index planes
2

Trend less clear than for O g

reduction, but 5 nm AuNPs exhibit highest electroactivity

 High H2O2 activity of the smallest AuNPs may therefore be influenced by exposure of higher index planes (A. J. Wain, Electrochimica Acta 92 (2013) 383 391)

Acknowledgements
This work was funded by the Innovation R&D Program of the National Measurement System, part of the Department for Business, Innovation and Skills

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