Size-tunable platinum
nanoparticles (PtNPs) prepared by a facile
method in an aqueous environment without the use of catalyst-poisoning
reagents are used here in the electrocatalytic detection of hydrogen
peroxide. Spherical nanoparticles with sizes as small as 4 and 20
nm are obtained as shown by transmission electron microscopy (TEM)
analysis only using small easy-to-remove molecules such as sodium
citrate. PtNPs are freed from the citrate capping agent at the surface
by changing the pH to basic values and then deposited on a glassy
carbon electrode by a very simple and rapid drop-casting method, achieving
high cleanliness of the nanoparticle surface without the need for
further treatments. The superior quality of nanoparticles on the glassy
carbon is further investigated by scanning electron microscopy (SEM)
analysis, which shows a highly homogeneous distribution of well-dispersed
nanoparticles on the electrode surface, as well as by X-ray photoelectron
spectroscopy (XPS) analysis, which confirms a drastic decrease of
the citrate content, providing useful information about the citrate–platinum
interaction, and evidences a related remarkable increase of conductivity
of capping-free washed nanoparticles. Due to such key features, PtNPs
possess excellent electrocatalytic properties, which have been tested
in hydrogen peroxide electroreduction, a well-known catalytic reaction
of nanostructured platinum materials. The size effect on PtNPs electrocatalytic
properties is demonstrated, achieving higher performances with smaller
NPs in the amperometric detection of hydrogen peroxide at −0.1
V in the concentration range of 25–750 μM, with a detection
limit of 10 μM. Good sensing results toward hydrogen peroxide
have also been obtained in terms of sensitivity, selectivity, repeatability,
stability, and in tests performed in tap water samples. In addition,
the strong adhesion of nanoparticles to the electrode surface has
been verified and ascribed to their coating-free surface.