Electrochemical sensor with record performance characteristics

Article abstract of DOI:10.1002/anie.200700341

Nanoelectrode sensor arrays were formed by depositing nanostructures of the electrocatalyst Prussian Blue onto an inert carbon support. The sensor thus obtained showed a high sensitivity toward hydrogen peroxide, with a detection limit of 1 × 10^-9 mol L^-1 (i.e., 0.03 ppb), and a broad linear calibration range, which extended over seven orders of magnitude (from 10^-9 to 10^-2 M L^-1 H₂O ₂, see graphic). (Graph Presented).

Full text of DOI:10.1002/anie.200700341

Communications
DOI: 10.1002/anie.200700341
Electrochemical Sensors
Electrochemical Sensor with Record Performance Characteristics
Arkady A. Karyakin,* Elena A. Puganova, Ivan A. Bolshakov, and Elena E. Karyakina
Accessing the limiting performance characteristics of sensors
is possible by means of their miniaturization. Microelectrodes
demonstrate a significantly improved sensitivity and signal-
to-noise ratio, the latter being inversely proportional to the
electrode radius.[1–3] However, a decrease in the electrode
dimensions limits the sensor response to very low current
values. To avoid this problem, it is possible to use micro-
electrode arrays, which are commonly produced by creating
an insulating layer on a macroelectrode surface and then
making holes in this layer.[4–7]
To develop a sensor with improved performance charac-
teristics, we propose nanostructuring of a highly active
electrocatalyst onto an inert electrode support. Since the
reduction—or the oxidation—of the analyte on the support is
negligible, the species diffuses to the place where it is being
consumed, namely, to the electrocatalyst islands, which are
thus expected to behave as nanoelectrodes. Herein we report
a hydrogen peroxide sensor composed of nanostructured
Prussian Blue on an inert carbon surface. This electrochem-
ical sensor displayed record performance in the flow-injection
mode, thereby exhibiting a linear calibration range that
extended over seven orders of magnitude of H2O2 concen-
tration, with its lower limit being 1 ” 10À9 molLÀ1 H2O2 (i.e.,
Figure 1. AFM images of Prussian-Blue-modified monocrystalline
graphite: a) conventional Prussian Blue, deposited without templates,
b) Prussian Blue electrochemically deposited through a vinyltriethoxysi-
lane sol template.
0.03 ppb). These results represent a record in electroanalysis.
We reported that Prussian Blue is the most advantageous
electrocatalyst for hydrogen peroxide reduction.[8–10] Prus-
sian-Blue-modified electrodes are characterized by an elec-
trochemical rate constant that is up to three orders of
magnitude higher than that observed with the most widely
used platinum electrodes. The deposition of Prussian Blue
through liquid-crystalline templates was carried out according
to the most common approaches for nanostructuring,[11–13]
thus obtaining a nanostructured inorganic polycrystal.[14]
The AFM image in Figure 1a shows that the Prussian-
Blue layer grown without templates covers the surface
completely. The inorganic film itself exhibits a polycrystalline
structure, with crystalline dimensions of less than 100 nm. To
estimate the thickness of the Prussian-Blue layer, a part of the
film was removed from the electrode surface by using a
droplet of an alkaline solution, which is known to solubilize
ferric ferrocyanide (Prussian Blue). The layer thickness,
determined by AFM, was found to be about 60–80 nm. An
increase in the deposition time results in thicker—but less
regular—polycrystalline structures.[10]
The best results in terms of nanostructuring were obtained
with vinyltriethoxysilane-based sol prepared from acetoni-
trile. An AFM image of Prussian Blue grown through this
template is shown in Figure 1b. Deposition through the
alkoxysilane sol results in an archipelago of structures. The
surrounding smooth area can be attributed to the blank
surface, taking into account the thickness of the Prussian-Blue
film grown without templates.
The optimal geometry of the micro- and nanoelectrode
arrays can be found considering the diffusion profiles of the
analyte at the electrode surface. An array of hemispherical
ultramicroelectrodes (Figure 2) is the best model for nano-
[*] Prof. A. A. Karyakin, Dr. E. A. Puganova, I. A. Bolshakov,
Dr. E. E. Karyakina
Chemistry Faculty, M. V. Lomonosov
Moscow State University, 119991, Moscow (Russia)
Fax : (+7)495-939-4675
E-mail: aak@analyt.chem.msu.ru
Supporting information for this article is available on the WWW
under http://www.angewandte.org or from the author.
Figure 2. Array of hemispherical microelectrodes (schematic).
7678
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2007, 46, 7678 –7680

Angewandte
Chemie
structured electrocatalysts. Assuming that the analyte con-
centration at a distance d from the electrode surface tends to
its bulk value, the best performance characteristics of micro-
and nanoelectrode arrays can be accessed if the individual
electrodes are separated by a distance 2d (Figure 2). Indeed,
at smaller distances, the individual electrodes interfere with
each other, and the diffusion profiles are not hemispherical. A
larger separation, on the other hand, results in a decreased
current density, which reduces both the sensitivity and the
signal-to-noise ratio of the resulting sensor.
ysis, as it allows reproducible detection at low analyte
concentrations.
The calibration plot for H2O2 in the flow-injection mode
(with the use of nanostructured Prussian Blue as a detector) is
presented in Figure 3. The slope of the linear calibration
range is 0.7 ALmolÀ1 cmÀ2, which is similar to that of
conventional (unstructured) Prussian Blue (namely, (0.6 Æ
0.1) ALmolÀ1 cmÀ2). Hence, we succeeded in forming nano-
electrode arrays without any loss of sensor sensitivity.
The value of d for hemispherical ultramicroelectrodes can
be calculated from the relations for the steady-state current.[1]
We found that d is equal to the radius (r) of the ultra-
microelectrode; hence, the optimal configuration for an array
of hemispherical ultramicroelectrodes is that with an elec-
trode separation equal to their diameter. The nanostructured
Prussian Blue shown in Figure 1b is roughly reminiscent of
such an optimal configuration, which allows us to expect
limiting-performance characteristics for the corresponding
sensor.
Sensor performance characteristics were investigated in a
flow-injection system equipped with a flow-through wall-jet
cell. Flow-through electrodes are known to provide the most
reproducible and stable hydrodynamics, which are necessary
to investigate sensor response in a wide concentration range.
A wall-jet electrode consists of a jet of solution issued from a
circular nozzle and allowed to impinge normally on a working
disk electrode.
Figure 3. Calibration plot of the sensor: peak-current density versus
H2O2 concentration. Total amount of Prussian Blue:
GPB ꢀ10 nmolcmÀ2, operating potential: 50 mV, phosphate buffer
(pH 6.0) + KCl (0.1m), flow rate: 0.7 mLminÀ1. Inset: low-concentra-
tion limit of the calibration graph in linear coordinates.
Forced-hydrodynamic
techniques—including
flow-
through electrodes—create specific depolarizer concentra-
tion profiles, which include the Nernstꢀs (diffusion) layer at
the electrode surface. In this layer mass transport is known to
occur only by diffusion.[1]
The lower limit of the linear calibration range of the
nanostructured H2O2 sensor (that is, 1 ” 10À9 molLÀ1 H2O2
(0.03 ppb), see Figure 3) is two orders of magnitude lower,
and the upper limit (that is, 1 ” 10À2 molLÀ1 H2O2) is one
order of magnitude higher, than those observed for conven-
tional (unstructured) Prussian Blue.
An important analytical parameter is the sensor dynamic
range. As can be seen, nanostructured Prussian Blue in the
flow-injection mode displays a linear calibration range that
extends over seven orders of magnitude of H2O2 concen-
tration, and this range represents a record in electroanalysis.
The diffusion-layer thickness of a wall-jet electrode, which
was first estimated by Yamada and Matsuda,[15] reaches its
lowermost value in the center of the impinging jet; however,
this value is not equal to zero, as originally assumed by these
authors.[15] The correct value can be obtained from the
limiting case, in which the electrode is much thinner than the
nozzle.[16,17] The lower limit of the diffusion-layer thickness of
the wall-jet electrode used herein was estimated to be 4.5–
5 mm, which is one to two orders of magnitude larger than the
dimensions of Prussian-Blue clusters (Figure 1b). Hence,
mass transport at the electrode surface mainly takes place by
diffusion to the nanoelectrode arrays, which results in
improved analytical characteristics of the sensor. Moreover,
for nanostructured Prussian Blue, the signal-to-noise ratio
was independently found to be almost one order of magnitude
higher than that of the unstructured electrocatalyst.
Flow-injection analysis (FIA) is based on the injection of a
liquid sample into a moving, nonsegmented, continuous
carrier stream of a suitable liquid. The FIA response is a
current peak, whose height, multiplied by the dispersion
coefficient (which in our experiments has value of approx-
imately two), is equal to the steady-state-current response
obtained through a continuous flow of the analyte.[18] In
FIA—relative to batch or continuous-flow analysis—the
response (peak current) is better recognizable from the
baseline noise. This feature is advantageous for electroanal-
Experimental Section
Prussian Blue was electrodeposited from a solution of K3[Fe(CN)6]/
FeCl3 (4mm each) in the supporting electrolyte, HCl/KCl (0.1m each),
by means of cyclic voltammetry at a sweep rate of 20–40 mVsÀ1
(switching potentials: 0.4 V (cathodic) and 0.7–0.8 V (anodic), see
references [9,10]).
Nanostructuring was carried out by electrodepositing the electro-
catalyst through sol templates of alkoxysilane (0.5–4 wt%), water
(1.1–7.5 wt%), and an organic solvent (acetonitrile, 2-Propanol), and
then drying it at room temperature. After deposition of the Prussian
Blue, the sol template was removed using acetone.
Received: January 25, 2007
Revised: June 13, 2007
Published online: August 23, 2007
Angew. Chem. Int. Ed. 2007, 46, 7678 –7680
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org 7679

Communications
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Owen, J. H. Wang, Science 1997, 278, 838 – 840.
Keywords: electrochemistry · nanostructures · peroxides ·
Prussian Blue · sensors
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