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www.npl.co.uk
Advances in Combined
High-Resolution Electrochemical and
Topographical Imaging Techniques
The ability to characterize the electrocatalytic behavior of
heterogeneous surfaces on a localized scale is critical to our
understanding of interfacial processes and impacts a multitude
of applications, notably the development of energy conversion technologies such as fuel cells
and electrolyzers.
Scanning electrochemical microscopy (SECM) is a powerful approach to undertaking localized
electrochemical characterization and signifcant advances have been made recently in spatial
resolution, accurate concurrent topographical imaging and breadth of application.
This poster highlights the latest developments at NPL in the nanoscale electrochemical imaging
of surfaces decorated with electroactive materials.
Michael A. OConnell,* and Andrew J. Wain
National Physical Laboratory, Hampton Road, Teddington, TW11 0LW, UK
*mike.o-connell@npl.co.uk
Acknowledgements
This work was fnancially supported by the UK National Measurement System and the European
Metrology Research Programme (EMRP, Ind 15 - SurfChem). The EMRP is jointly funded by the EMRP
participating countries within EURAMET and the European Union. The authors also wish to thank
Christoph Richter at NanoWorld Services GmbH for supplying the cantilever probes.
Both SECM-AFM and SECM-SICM give high quality combined
electrochemical and topographical imaging. For highest resolution
imaging, especially for correlating nm height changes to activity,
SECM-AFM is extremely powerful, whereas SECM-SICM allows much greater fexibility and higher
quality electrochemistry at slightly reduced resolution.
Graphene Flakes
Exfoliated graphene on
SiO
2
substrate
AFM imaging is highly accurate to
sub-nm resolution
Positive feedback over carbon
(rapid electron transfer)
Graphene/graphite regions show
similar behaviour
Some electrochemical
non-uniformities do not correlate
with topography
Combined SECM with Atomic Force
Microscopy (SECM-AFM)
Batch fabricated probes with conical
Pt nanoelectrode (radius ~ 100nm)
Imaging undertaken in Lift-Mode using
FcMeOH
Conical probes give CVs with reasonable
capacitance
Approach curves give reasonable fts to
theory for conical probes
Gold Microbands
Au bands (50 nm high)
on SiO
2
substrate
Good quality topographical
imaging
Faradaic current enhancement
over Au (positive feedback)
AFM Topography SECM-Feedback
AFM Topography SECM-Feedback
Combined SECM
with Scanning Ion
Conductance Microscopy
(SECM-SICM)
Quartz q-capillary
pulled using laser puller
(aperture
~50 to 500 nm)
One barrel flled with
solid carbon by pyrolysis
of a hydrocarbon feed
Carbon electrode
platinized using
electrodeposition for
oxygen detection
CVs are sigmoidal with
low capacitance
SICM current decays with proximity to surface
(positional feedback)
SECM current sensitive to the nature of the surface
(i.e. active or inert) and compares well to theory for
disk-shaped probes
Platinum bands 50 nm
high. 2 m wide on glass
Probes of a few hundred
nm are typically used
Topography is closely
followed by SICM
Faradaic current is
measured in feedback
and substrate generation-
tip collection mode using
FcMeOH
Au disks (150 nm
diameter 50 nm high)
on SiO
2
Probes of <50 nm
typically used
SICM current tracks
topography faithfully
and compares well
to AFM
Positive feedback
(FcMeOH) observed
over Au disks
CV
Approach Curves
Negative Feedback Positive Feedback
SICM Topography SECM Feedback SECM SG-TC
Platinum Microbands
SICM Topography SECM Feedback AFM Comparison
Gold Nanodisks
Platinum Nanospheres
Pt nanoparticles (PtNPs,
diameter ~ 100 nm)
electrodeposited on
glassy carbon
(see SEM image)
Platinum-functionalized
carbon probes are
used to detect oxygen
Individual particles topographically resolved
Electrochemical imaging in O
2
redox
competition mode indicates local O
2

consumption at individual PtNPs
SICM Topography O
2
Reduction Current
Conclusions
SECM-SICM Introduction
SECM-AFM
CV
Approach Curves