Journal of

Electroanalytical
Chemistry
Journal of Electroanalytical Chemistry 561 (2004) 203–217
www.elsevier.com/locate/jelechem

Review

Reticulated vitreous carbon as an electrode material

J.M. Friedrich a, C. Ponce-de-Le

on a,*
, G.W. Reade b, F.C. Walsh a

a
Electrochemical Engineering Group, Department of Chemical Engineering, University of Bath, Claverton Down, Bath BA2 7AY, UK
b
Regenesys Technologies Limited, OTEF, Aberthaw Power Station, The Leys, Barry, Vale of Glamorgan CF62 4QT, UK
Received 10 April 2003; received in revised form 10 July 2003; accepted 18 July 2003

Abstract

An illustrated review of reticulated vitreous carbon (RVC) as an electrode material is presented. Early uses of RVC were largely
restricted to small-scale (< 1 cm3 ) electroanalytical studies in research laboratories. RVC properties of a high ratio of surface area to
volume and minimal reactivity over a wide range of process conditions, combined with low cost and easy handling, have resulted in
a steady diversification of its applications both in research laboratories and in industry. The physical structure of RVC (in terms of
pores per linear inch, strut length, strut thickness and area of the trigonal strut) is examined for 10, 30, 60 and 100 ppi (pores per
linear inch) grades using scanning electron microscopy. The accurate measurement of these geometrical values presents both the-
oretical (in terms of definition of trigonal strut area, beginning and end of single strand) and practical problems (large differences in
strut length and thickness in individual samples). Data are presented to show the relationships between geometrical properties.
Applications include electroanalytical studies and sensors, metal ion removal, synthesis of organics and FentonÕs reagent, H2 O2
production and batteries/fuel cells.
Ó 2003 Elsevier B.V. All rights reserved.

Keywords: Reticulated vitreous carbon; Porous electrodes; Three-dimensional electrodes

1. Introduction fluid flow, and very high resistance to temperatures in

non-oxidizing environments.
Three-dimensional electrodes are used to counteract RVC is a useful electrode material, particularly where
the limitations of the low space–time yield and low high current densities, low electrical/fluid flow resis-
normalised space velocity obtained in electrochemical tance, minimal cell volume loss to electrodes and the
processes with two-dimensional electrodes [1]. A three- ability to hold infused materials within controlled pore
dimensional electrode can be obtained in a number of sizes are required [1]. The skeletal structure of the ma-
ways, including a fluidised bed, a packed bed, or the use terial is brittle and needs support and the low volumetric
of a porous material, such as copper-plated, reticulated carbon content means that care has to be taken to en-
polyurethane, nickel mesh, etc. In this paper, the ap- sure a uniform potential- and current distribution
plications and properties of reticulated vitreous carbon through the material. The principles of RVC as a three-
(RVC) – a microporous, glassy carbon electrode mate- dimensional electrode, together with other carbon ma-
rial – are examined. terials, have been reviewed [2]. Other RVC applications
Vitreous carbon has a low density, a low thermal include: high temperature insulation, filters, storage
expansion, a high corrosion resistance and high thermal batteries, scaffolds for biological growth, the manufac-
and electrical conductivities. RVC is an open-pore foam ture of semiconductors and acoustic control [3–7].
material of honeycomb structure composed solely of
vitreous carbon. It has an exceptionally high void vol-
ume, high surface area, rigid structure, low resistance to 2. Manufacture and physical properties

The structure of RVC is achieved by polymerisation

*
Corresponding author. of a resin combined with foaming agents, followed by

0022-0728/$ - see front matter Ó 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.jelechem.2003.07.019
204 J.M. Friedrich et al. / Journal of Electroanalytical Chemistry 561 (2004) 203–217

Nomenclature

Ae Surface area per unit volume (m1 ) F Faraday constant (C mol1 )

a Geometrical factor IL Limiting current (A)
b Velocity exponent km Mass transport coefficient (cm s1 )
c Concentration (mol l1 ) Ve Volume of the electrode (cm3 )
E Potential v Electrolyte velocity (m s1 )
E1=2 Half-wave potential z Number of electrons transferred

carbonisation. The result is a low volume disordered solvent, the solution viscosity, the concentration of
glassy porous carbon with some crystallographic order, curing agents, the precursor foam pore size and the
low electrical resistance and a continuous skeletal firing temperature. Glassy porous carbon can also be
structure. Classically, polyurethane and phenolic resins obtained from high molar mass thermoplastic carbons
are used although furfuryl and epoxy resins can also be (pitch) [8]. During the production of RVC, a linear
used; these have 3% and 50% Ôcarbon yieldÕ, respectively. shrinkage of approximately 30% occurs.
The foam resin is, typically, dried and cured at 120 °C Reticulated vitreous carbon has a free void volume
then carbonised at 700–1100 °C. Important process between 90% and 97%, depending on the ppi grade,
variables include the concentration of resin, the type of and a surface area of ffi65 cm2 cm3 , for the 100 ppi

Fig. 1. SEM micrographs of: (a) 10, (b) 30, (c) 60 and (d) 100 ppi (nominal pores per linear inch) RVC samples. Closeups of struts for: (e) 10, (f) 30
and (g) 100 ppi RVC samples.
 J.M. Friedrich et al. / Journal of Electroanalytical Chemistry 561 (2004) 203–217 205

Fig. 1. (continued)

grade [3]. RVC does not combust after heating to linear inch (ppi), the strut length, the strut thickness
bright incandescence in air followed by removal of the and the surface area of the trigonal strut, the area
heat source. However, heating above 315 °C in air re- where the struts meet. Using the images obtained by
sults in significant oxidation, producing a material with scanning electron microscopy (SEM), the lengths and
enhanced adsorption properties. It is highly resistant to widths of the carbon struts as well as the areas of the
intercalation by materials that disintegrate graphite and trigonal struts were determined for 10, 30, 60 and 100
it is inert to a wide range of very reactive acids, bases, ppi RVC samples. The strut length was measured from
and organic solvents. RVC material can be obtained the end of the trigonal struts on either side, where the
from suppliers offering a wide range of instruments and strand thickness was uniform and no longer influenced
supplies for electrochemical applications [9]. by the trigonal struts, as it is shown in Fig. 2(a). Sim-
The pressure drop of a flowing stream across an ilarly, for the strut thickness, the measurements were
RVC structure is small. The honeycomb structure, taken at the middle of a carbon strut between two
shown in Fig. 1(a)–(c) for 10, 30, 60 and 100 ppi trigonal struts. Fig. 2(b) shows the circle that approx-
samples, is formed by strands of carbon, also called imated the strut area. The area of this circle was de-
struts (see Fig. 1(e) and (f)) that form a so-called tri- termined and set equal to the area of the trigonal strut.
gonal strut, which appears like a triangle from above While this may not be entirely exact, it gives a rea-
but is in fact more like a tetrahedron, with one of the sonably accurate and reproducible measurement of the
strands hidden out of view under the others. Replica- trigonal strut area.
tion of this arrangement gives rigid structure to the The struts in a sample of RVC can vary considerably
RVC. In order to characterise the structure of a par- in length and width, as can be seen from the figures. The
ticular sample of RVC foam four variables need to be accuracy of the measurements is hampered by the need
taken into account, these are the number of pores per to define clearly where the transition from trigonal to
206 J.M. Friedrich et al. / Journal of Electroanalytical Chemistry 561 (2004) 203–217

sample. Fig. 4 shows the calculated specific surface area

Ae vs. porosity, the linear equation of this plot for a 100
ppi material corresponds to a volumetric surface area of
approximately 65 cm2 cm3 . This value agrees well with
those reported in the literature using pressure drop
measurements [10], and with the manufactured specifi-
cations available from Materials and Aerospace, Oak-
land, CA [11].

3. Electrochemical cell design for RVC electrodes

The large surface area and the high porosity of the

RVC material has attracted great interest, as potentially,
high rates of conversion per unit volume can be
achieved. The design of the electrochemical cell for an
RVC electrode should allow for uniform current and
potential distribution, low ohmic internal resistance and
high rates of mass transport of the electroactive species
to the electrode surface. This can be achieved if the
electrode is sufficiently thin for the voltage to be taken as
constant and the distribution of the reaction current
uniform over the electrode surface. The limitations of
conversion rate and maximum allowable potential drop
in a porous electrode, to prevent side reactions are well
documented in the literature [1–3,5,10,12,13]. Under
mass transport limitations, the overall performance of a
Fig. 2. SEM micrograph of: (a) 10 ppi RVC, the white lines mark the
end-points of length and thickness measurements made to obtain the cell can be written in terms of the average mass trans-
data in Table 1. (b) SEM micrograph of a 10 ppi RVC sample. The white port coefficient, km :
circle marks the region used to calculate the area of the trigonal strut.
IL ¼ zFkm Ae c; ð1Þ
where IL , z, F , Ae and c, are the limiting current, number
single strut takes place. To compensate for this, the data of electrons transferred, Faraday constant (96,485 C
were averaged from several measurements of length, mol1 ), electrode area per unit electrode volume and
strut thickness and circle radius for each porosity. bulk concentration of electroactive species in the elec-
The measured values obtained from Fig. 2 are shown trolyte, respectively. The mass transport properties are
in Table 1 and plotted in Fig. 3. At higher ppi grades, the usually discussed in terms of the dimensionless numbers,
strands become both shorter and thinner. At the same Reynolds, Sherwood and Schmidt [12,13]. For a par-
time, the trigonal strut radius and the strut thickness ticular electrolyte and electrode material at constant
have, as was to be expected, very similar values. The temperature the mass transport coefficient can be ex-
slight kink in the data for the strut length of the 10 ppi pressed as
foam, is most probably due to the difficulties presented
by the material structure and the measurement itself, as k m A e ¼ a v b ; ð2Þ
outlined above. 
where v is the electrolyte velocity; a and b depend on
The specific surface area, Ae , for 10, 20, 50, 60, 80 and electrode shape and type of flow, respectively: 0:3 <
100 ppi was calculated from SEM images by measuring b < 0:5 for laminar flow and 0:45 < b < 0:8 for turbu-
the struts and circle areas in a defined area of the RVC lent flow.

Table 1
Dimensions of the physical characteristics of four grades of RVC foams (taken from scanning electron optical micrographs)
Property Nominal pores per linear inch (ppi)
10 30 60 100
Strut length (mm) 0.810 0.686 0.250 0.130
Strut thickness (mm) 0.316 0.160 0.073 0.050
Trigonal strut circle radius (mm) 0.225 0.157 0.071 0.041
Trigonal strut area (mm2 ) 0.159 0.077 0.016 0.005
 J.M. Friedrich et al. / Journal of Electroanalytical Chemistry 561 (2004) 203–217 207

Fig. 3. (a) Strut dimension vs. pores per linear inch. (b) Strut area vs. pores per linear inch.

trodes in flow-through and flow-by configurations.

Fig. 5(a) shows an electrochemical cell using an RVC
electrode in the flow-through configuration; the elec-
trolyte and current flow are parallel. This mode of op-
eration has been used in many electrochemical
applications [15–21]. Fig. 5(b) shows another electro-
chemical cell in the flow-by configuration; in this case
the electrolyte flow is perpendicular to the current flow.
The cell, originally designed by Walsh and constructed
by Marshall, consisted of four blocks of polypropylene
(A, B, C and D) each 280 mm  100 mm  12 mm thick
[12]. The steel plate current collector, sunk into one of
the inner blocks, held the RVC cathode (50 mm  50
mm  12 mm thick) in the centre of the catholyte
channel. This configuration has been popular for some
large-scale electrochemical applications, e.g., metal ion
removal [18,22–26].
Rotating electrodes allow a very efficient design of
flow-through electrochemical cells, coupling the large
surface area of RVC with the efficient mass-transport of
Fig. 4. Electrode area per unit electrode volume vs. porosity grade of the rotating electrode produces large analytical currents.
RVC (data obtained from scanning electron microscopy). Using pulsed-rotation techniques to compensate for the
background current, well-defined current–potential
curves and low detection limits can be achieved [27].
Most electrochemical reactors operate in a mode that
Fig. 5(c) shows a schematic drawing of a rotating cyl-
can be approximated to three modes of operation: (1)
inder RVC cell which has been used for metal ion re-
the simple batch reactor, SBR, (2) the plug flow reactor,
moval [28].
PFR, and (3) the continuously stirred tank reactor,
CSTR [12,13]. Electrochemical cells performance at a
particular point in time, space or area is assessed by
their figures of Merit: yield, fractional conversion, cur- 4. Electrochemical applications
rent efficiency, overall selectivity, cell voltage, active
electrode area per electrode volume, space–time and The first use of RVC as an electrode in an optically
space–time yield [12–14]. Electrochemical cells with transparent electrode cell, RVC-OTE, was to study
RVC electrodes include stationary and moving elec- the spectroscopic and electrochemical properties of
208 J.M. Friedrich et al. / Journal of Electroanalytical Chemistry 561 (2004) 203–217

Fig. 5. Electrochemical cells: (a) RVC electrode in the flow-through configuration for potential distribution studies under limiting current conditions
[21]. (b) RVC electrode in the flow-by configuration used for the removal of metal ions [22]. (c) Two compartment cell with a rotating RVC cylinder
electrode [28]. (d) Optically transparent, thin layer, RVC electrode [29].

o-tolidine and MnO 4 [29]. The small volume of the cell

400–550 ll, Fig. 5(d), allows complete electrolysis in a
short period of time. The values of both cathodic and
anodic peak currents during the cyclic voltammogram of
4.05 mM K3 Fe(CN)6 solution at 1 mV s1 were identical
indicating negligible diffusion of the electroactive ma-
terial into the bulk solution. More recently, a similar cell
was used for both flow and batch spectro-electrochem-
ical measurements [30]. Over time, other applications
have been developed for RVC, these include: sensors,
metal ion removal, synthesis of organics, FentonÕs re-
agent for the destruction of organics and energy con-
version, among others. The following sections give an
overview of these applications.

5. Electroanalytical studies and sensors

An early review on RVC, by Wang, appeared in 1981

[3] and predicted increasing applications in analytical Fig. 6. Pulsed rotation response for 1, 2, 3 lM ascorbic acid at a
chemistry, particularly in sensor development. In an constant flow rate of 2.25 ml min1 in a 0.1 M phosphate buffer. RVC
earlier paper, Blaedel and Wang demonstrated the use thickness was 1.8 mm. Applied potential +0.75 V vs. Ag j AgCl [27].
 J.M. Friedrich et al. / Journal of Electroanalytical Chemistry 561 (2004) 203–217 209

of RVC as a sensor [27]. Fig. 6 illustrates their results mesh electrode, RVC showed higher sensitivity and
obtained from a pulse rotation voltammetry technique stability, better reproducibility and less dependence on
used in a flow through RVC electrode for the determi- the relative humidity; while having inferior dynamic
nation of micro molar concentrations of ascorbic acid in properties; RVC could be used to replace the more ex-
0.1 M phosphate buffer. Through this technique, they pensive noble metal electrodes. Flowers et al. [30] used
were able to detect concentrations of ascorbic acid down the reduction of ferricyanide as a model reaction in a
to 0.1 lM. In glucose determination, for example, a spectro-electrochemical cell with a 60 ppi RVC electrode
number of studies use immobilized enzymes attached to in batch and flow injection analysis arrangements.
a RVC substrate. Lange and Chambers [31] fabricated
and evaluated an electrode to determine glucose in hu-
man blood plasma, down to 1.2 mg ml1 . The glucose 6. Metal ion removal
oxidase enzyme and ferrocene couple were trapped in
polyacrylamide gel, packed into a strip of RVC. Despite Various cell configurations and electrolyte conditions
the fact that the chemical stability of the electrode was have been studied for the removal of metal ions from
good, its physical stability in aqueous solutions was aqueous wastewater, using RVC electrodes. The tech-
limited. nology competes with traditional methods of wastewater
Wieck et al. [32] attached glucose oxidase to a 80 ppi treatment such as precipitation, cementation, solvent
RVC cylinder, both covalently and by adsorption in a extraction and ion exchange. Despite this, the recovery
flow-through configuration. Their findings suggested of heavy metals using RVC electrodes can offer a highly
that covalent attachment resulted in higher activity for efficient and low cost process. Due to the RVC prop-
glucose detection. In a further study [33], they measured erties, electrolysis yields near 100% can be achieved,
the concentration of H2 O2 , produced by the oxidation with the electrode still sufficiently porous to allow for
of glucose at a constant potential at flow rates from 1 to low flow resistance after the deposition of metals in
4.5 ml min1 . The oxidation currents were linearly comparison to a bed of loose particles [18].
correlated to the glucose concentration in the range of Whyte [10] demonstrated the use of an RVC electrode
2.5–10 mM only. for the recovery metals in a mixed metal ion solution
Glucose oxidase enzyme was immobilised with glu- with initial concentrations of  10 ppm in a solution of
taraldehyde in a platinized RVC cylinder electrode to 0.1 M NaCl at pH 7. Fig. 7 shows the normalized
measure glucose in human blood serum by flow injection concentration decay of copper, cadmium and zinc ions.
analysis (FIA) by Yacynych et al. [34]. The lifetime of Over the first 60 minutes, a potential of )0.5 V vs. SCE
the electrode was claimed to be 1.5–3 months with a
throughput of 130 samples per hour. Detection was
accurate up to a glucose concentration of 100 mM.
Similarly, Heider et al. [35] detected glucose on a plati-
nized 80 ppi RVC electrode amperometrically under
similar conditions, achieving a detection range of 0.025–
0.1 mM. Stopped-flow, linear sweep voltammetry with a
RVC cylindrical electrode in a flow-through configura-
tion was used to determine dopamine in the presence of
ascorbic acid down to 5  107 M levels by Tougasand
and Curran [36]. On the other hand, Jaraba et al. [37]
used 100 ppi RVC, coated with poly(3-methylthioph-
ene), as an enzyme reactor material in a flow injection
configuration for the amperometric determination of L -
lactate and NADH. The detection limit was 1  105 M,
despite the interference of ethanol, citric, malic and tar-
taric acids at five times the concentration of lactate and
acetic acids at twice the concentration of the analyte.
Saidman and Bessone used RVC and paraffin-coated
RVC, among other graphite pastes, for the voltametric
determination of NADþ . They observed only oxidation
peaks of NADþ in the paraffin-coated RVC [38].
Hrn
ıov
a, et al. [39] used RVC for the amperometric
Fig. 7. Concentration decay vs. time for the reduction of 10 ppm of (d)
determination of NO2 in air, using a planar sensor
constructed on a glass plate with a solid polymer elec-

Cuþ2 , ( ) Cdþ2 and (.) Znþ2 in a N2 purged 0.1 M NaCl, pH 7,
solution at a 100 ppi RVC electrode. Mean linear velocity 0.083 m s1 .
trolyte (SPE). They concluded that, compared to an Au Electrode potentials ¼ )0.5, )1.0 and )1.4 V vs. SCE, T ¼ 298 K [10].
210 J.M. Friedrich et al. / Journal of Electroanalytical Chemistry 561 (2004) 203–217

was applied to remove only the Cuþ2 ions. This was

achieved successfully although 15–20% removal of Znþ2
ions was noticed at this potential with no change in the
Cdþ2 level. During the following hour, the potential was
changed to )1.0 V to remove Cdþ2 ions. Cadmium re-
covery was successful but the removal of Znþ2 reached
50%. The depletion of Znþ2 was achieved by changing
the potential to )1.4 V. The final concentrations were
<0.1, <0.05 and <0.5 ppm for Cuþ2 , Cdþ2 and Znþ2 ,
respectively. Copper and cadmium depletion followed a
logarithmic decay indicating mass transport control,
however, zinc removal appeared to be more complex,
probably due to the formation of hydroxide species ev-
idenced by the increase of pH of the solution. Studies for
the removal of individual metals using RVC have been
published; the following is a profile of published works.

6.1. Copper deposition

The deposition of copper has been extensively studied

and has been used as a reference for more complex li-
quors [40]. Copper ions are part of industrial effluents in
a number of important processes such as electroplating,
circuit-board manufacture and some catalyses; there-
fore, strong environmental, legal and hence economical
pressures on finding efficient ways of effluent cleanup
exist. Fig. 8(a) and (b) show SEM micrographs of de-
posited copper on an RVC electrode, using 0.1 M NaCl
at pH 7 [28]. At this relative high magnification, the Fig. 8. Copper deposition onto bare RVC from a solution containing
crystal features protruding from the electrode surface initially 0.5 mM cupric ion in a deoxygenated 0.1 M NaCl, pH 7, so-
are over 10 lm high. In the higher magnification, lution, T ¼ 298 K, x ¼ 157 rad s1 (1500 rpm) [28]: (a) 40 and (b) 10 lm.
Fig. 8(b), the individual crystals appear angular and
dendritic. These types of crystal account for the increase
in the mass transport coefficient associated with the
specific electrode area, km Ae .
Wang and Dewald [18] examined the use of a cylin-
drical RVC electrode in a flow-through configuration
for metal removal in combination with on-line moni-
toring of the effluent. They studied the recovery of
Cu(II) in 0.1 M KNO3 among other metals, reporting an
efficiency of more than 90% at potentials negative to
)0.5 V vs. SCE. Complete Cu(II) removal was achieved
at potentials of )0.9 and )1.2 V vs. SCE with lower
efficiency. Copper deposits were discontinuous and did
not clog the RVC porous even after many successive
experiments.
Pletcher et al. [41] used several RVC porosities to
remove low levels of Cu(II) from acidic sulphate media.
Fig. 9 shows the logarithmic decay of the normalized
copper ion concentration using 10, 30, 60 and 100 ppi
RVC electrodes. As was expected, the concentration of
copper decays faster as the porosity of the electrode
Fig. 9. Logarithm of normalized copper(II) concentration versus time
increases. The current efficiency as a function of copper
for (d) 10, (s) 30, (.) 60 and (O) 100 ppi reticulated vitreous carbon.
ion concentration for the four grades of RVC was re- Controlled potential electrolysis at )0.5 vs. SCE. cð0Þ 0.16 M (10 ppm)
ported to be less than 80%. Low current efficiencies for Cuþ2 in a N2 purged 0.5 M Na2 SO4 , pH 2, solution. Mean linear flow
the higher ppi foams were attributed to difficulties in the velocity of 0.083 m s1 [40].
 J.M. Friedrich et al. / Journal of Electroanalytical Chemistry 561 (2004) 203–217 211

nucleation of copper or to the reduction of surface ox- application and possible arrangements for a practical
ide. A general trend was that current efficiency was high effluent treatment system. Both batch and single pass
and constant at large concentrations but fell rapidly at flow systems were examined with current efficiencies for
lower cupric ion levels. They also found that air satu- copper deposition up to 39% for 99.9% fractional ex-
ration of the solutions had only minor adverse effects on traction.
performance while chloride ions and decreasing ionic
strength had no adverse effects at all. The normalised 6.2. Lead deposition
space velocity, the power requirement and the energy
consumption were more advantageous than those Lead is a major pollutant; environmental legislation
achieved with other three-dimensional electrodes. has increased pressure on industries such as manu-
Walsh et al. [40] continued their work into Cu(II) facturers of paints, batteries and some alloys, to re-
removal from dilute sulphate solutions. They found duce their lead effluent levels. Therefore, lead removal
values of the product of the averaged mass transport has received a great deal of attention in the literature
coefficient (km ) and cathode area per unit electrode area [47]. As well as Cu(II) and Ag(II), Wang and Dewald
(Ae ) for different RVC grades. They presented detailed [18] investigated the deposition of Pb(II) ions onto
numerical data to demonstrate the satisfactory perfor- RVC, coupled with on-line Pb(II) monitoring. Clean-
mance of RVC in the chosen system. up efficiency was dependent on the RVC potential.
Following their previous paper [41], Pletcher et al. Similar to the results reported for copper, Pb(II) was
[42] examined the performance of a single pass reactor completely removed at potentials of )0.9 and )1.2 V.
for the removal of Cu(II) ions using a cell of 400 mm The deposits were very similar to those observed for
long RVC constructed from eight segments controlled copper and silver, i.e., bare areas and a discontinuous
independently. This arrangement demonstrated the deposit.
feasibility of systems with practicable flow rates and Berrettoni et al. [48,49] plated a disk and cylinder
efficiencies without the use of recycling or the drawbacks RVC electrodes with a thin mercury film in order to
of pressure drop usually associated with flow-by con- determine traces of lead by staircase anodic voltammet-
figurations with low porosity electrodes. The results ric stripping technique. This technique allowed higher
showed that Cu(II) could be reduced from 10 ppm to scan-rates than differential pulse anodic stripping vol-
<0.1 ppm in a single pass along the segmental 400 mm tammetry, while still retaining the capacity to discrimi-
RVC cathode with current efficiencies as high as 69%. nate against charging currents. RVC was particularly
The normalised electrolytic energy consumption, [43], useful in this application; the large electrode area re-
was below 30 W h m3 . Scale-up was found to be pos- sulted in high sensitivities as large amounts of metal were
sible with cell behaviour being well described by PFR reduced during the deposition step.
expressions. Podlaha and Fenton [44] carried out a se- The influence of the anions Cl , NO  
3 , ClO4 , BF4
ries of mass-transport studies on a single pass, flow-by and SO 4 on the removal of Pb(II) at different temper-
RVC reactor. The electrode was effective for the removal atures on 10, 60 and 100 ppi RVC electrodes was ex-
of copper ions from dilute solutions, however, plugging amined by Ponce-de-Le
on and Pletcher [22]. Pb(II) ions,
of the 45 ppi electrode during longer runs was reported. analysed by an AA technique, could be removed from
Polcaro et al. [45] reported on the effect of dissolved all the electrolytes down to levels that allowed discharge
oxygen in the removal of copper from dilute acid solu- into rivers and sea. However, the anion in solution had
tions. They presented a mathematical model to interpret an unexpected influence over the necessary conditions
the influence of O2 during copper deposition and con- for satisfactory removal of the Pb(II) ion. Fig. 10 shows
cluded that an increase in flow rate enhanced the current the decay in the concentration of Pb(II) ions in each of
for copper deposition, (a logical consequence of mass the five electrolytes used for an electrolysis carried out
transport control). Only a small effect of faradic effi- with a 60 ppi RVC electrode at potentials in the range of
ciency was observed. This was attributed to the fact that )0.8 to )0.9 V at 298 K. For ClO 
4 , BF4 and NO3


the reduction of O2 was under mixed control due to media, the Pb(II) concentration drops smoothly with
mass transport being an important stage in the process time to a less than 1 ppm, however, the decay is not as
for copper deposition. Purging the solution did not ap- fast as in Cl medium, indicating that lead deposition
pear to yield appreciable benefits, in terms of faradic was not mass transported controlled in these media ex-
efficiency. Instead, they suggested that an improved cept for chloride. The removal of Pb(II) ions from a
performance could be obtained by minimising the con- SO 4 medium was much slower at this temperature and
tact surface area between electrolyte and air to limit re- only 20% was removed after 3000 s of electrolysis. With
absorption of oxygen during electrolysis. increase of the temperature to 333 K, the removal of
Fisk and Boyle [46] examined the removal of metals Pb(II) reached 90% in 2000–2500 s (80 s for a fully mass
using 10–100 ppi RVC over a wide range of flow rates transported controlled electrolysis in chloride medium).
(0.1–3.2 l min1 ). They reported on the economics of the The conclusions were that addition of trace chloride ions
212 J.M. Friedrich et al. / Journal of Electroanalytical Chemistry 561 (2004) 203–217

Carre~no et al. [52] examined the influence of anions

such as Cl , NO 
3 and SO4 ions during the deposition of
Pb(II) on an RVC electrode from aqueous solution. As
in previous works [22], they reported higher removal
efficiencies in chloride electrolytes than in sulphate
electrolyte. They proposed fractured vitreous carbon
(FVC) as a model surface to study the morphology of
the deposits on the RVC electrodes by atomic force
microscopy.

6.3. Zinc deposition

Zinc is used both in the electroplating industries and

in the production of high power density batteries. These
applications offer challenges both in electrode produc-
tion and in effluent treatment. Lanza and Bertazzoli [53]
for example, proposed a flow-through cell for the re-
moval of zinc both from synthetic and industrial efflu-
ents. In the mass-transport control region with an 80 ppi
RVC electrode at 120 l h1 flow rate, the Zn(II) con-
Fig. 10. Normalized concentration of Pb(II) vs. time for a 60 ppi RVC
electrode in (d) Cl , (s) ClO    centration was depleted from 50 to 0.1 mg l within 20–40
4 , (N) BF4 , (O) NO3 , (j) SO4 at 298 K
and (
) SO 4 at 333 K, pH 2. Potentials )0.8 to )0.9 V for all except
min, depending on RVC porosity, flow rate and pH.
for )1.4 V vs. SCE for sulphate solution at 333 K. Initial solution; 10 With an industrial effluent, zinc removal was under mass
ppm Pb(II) for all except 14 ppm for sulphate solution at 333 K. Mean transport control only within the 1.5 mm below the
linear flow velocity 0.088 m s1 [22].
electrode surface; deeper in the electrode, the reaction
was under mixed control; this was attributed to the poor
was an option to improve process performance and conductivity of the electrolyte. In another paper, a seg-
higher temperatures to improve the electrolysis in sul- mented porous flow-through electrode was used for the
phate medium. The use of electrochemical techniques separation of mixtures of Cu(II), Ni(II), Zn(II), Ag(I)
would allow results as good as those reported for and Cd(II) with an RVC reactor [54]. Electrodeposition
precipitation technology for the removal of Pb(II) to be rates were not dependent on flow rate or RVC porosity,
achieved. but were dependent on pH. The multi-stage RVC reac-
Czerwiski and Z_ elazowska [23,24] examined the de- tor successfully separated ternary mixtures of Ag/Cu/Zn
position of Pb(II) on RVC from acidic and basic solu- and Cu/Cd/Zn.
tions. The electrochemical behaviour of lead deposited
onto platinised RVC was reported to resemble that of 6.4. Cadmium deposition
metallic lead. They concluded that RVC was a very
good matrix for lead deposition and that in acidic con- A very poisonous heavy metal with strong cumula-
ditions, some influence on the electrochemistry of de- tive effect in living systems, its discharge limits have
posited lead from the matrix material (platinum) had been continuously lowered over recent years. Its re-
been observed. Brennsteiner et al. [50] used 100 ppi RVC moval from effluent streams has been considered in
electrodes in a flow-through configuration to compare conjunction with other metals by several authors [54].
RVC with other novel forms of carbon, the results As well as determining Pb(II), Berrettoni et al. [48,49]
showed improved performance of RVC against the used a mercury-plated RVC disk and cylinder elec-
other materials. Widner et al. [51] used 20, 45, 60 and 80 trodes to determine traces of Cd(II) through staircase
ppi RVC electrodes in a flow-through configuration for voltammetric stripping analysis. Similarly, Brennsteiner
the electrolytic removal of Pb(II) at flow rates between et al. used a flow-through small-scale electrolytic cell
60 and 240 l h1 . The potentials at which the reduction for the removal of Cd(II), among other metals, on a
was mass transport controlled were determined in bo- series of conductive carbons, including RVC [50]. The
rate + nitrate solution on a vitreous carbon rotating disc RVC electrode was satisfactory for Cd(II) removal.
electrode. The concentration of Pb(II) was depleted Cadmium was removed up to 16% and 50% when the
from 43 ppm to <0.5 ppm in 800 s using a 80 ppi RVC electrode was held at 0 and )1 V vs. Ag j AgCl, re-
electrode at 240 l h1 with a current efficiency of 14%. spectively.
The concentration was <0.1 ppm after 20 min to 2 h A laboratory scale electrolytic flow-by cell with an
electrolysis, depending on the RVC porosity and flow RVC cathode permitted the purification of aqueous
rate. solutions containing cadmium ions from 200 to 0.1 ppm,
 J.M. Friedrich et al. / Journal of Electroanalytical Chemistry 561 (2004) 203–217 213

with current efficiencies up to 40%, in 85 min of oper- variety of organic compounds with better selectivity
ation in a mass transport regime [55]. than other production routes. Mattiello and Rampazzo
[59] described the electrochemical synthesis of 9.90 -spi-
6.5. Deposition of other metals robifluorene derivatives using an RVC electrode. They
described their redox properties in terms of voltam-
There are a large number of other metal ions that metric responses. The electrolysis of the derivates
appear in industrial effluents, however, not all of them modifies the RVC electrode by an olygomeric-poly-
have received attention regarding their recovery by RVC meric structure. On the other hand, Sz
anto et al. [60]
electrodes. Some of them are silver, vanadium and used the FM01-LC electrolyser (INEOS Chlor-Chemi-
molybdenum. Silver is particularly important in efflu- cals), to evaluate the electrosynthesis of coumestan and
ents from photographic processes and as is the case with catecholamine derivatives on several electrodes. The
many other metals, its recovery offers environmental performance of 30, 60 and 100 ppi RVC was compared
and economic benefits. Besides copper and lead, Wang with that of porous three-dimensional nickel electrodes.
and Dewald [18] also examined the deposition of Ag(I) Both 30 and 60 ppi RVC were found to perform in-
with a flow-through RVC electrode. Like copper, the differently, while the 100 ppi RVC had a performance
depositions were discontinuous, with regions of RVC comparable to the nickel stacked net. Conversion effi-
left bare. Henry and Van Lierde used an electrochemical ciencies for the oxidation of catechol were around 80%.
ion exchange process employing an RVC cathode, However, the formation of a polymeric film reduced
having pores filled with an ion exchange resin loaded the efficiency and proved difficult to remove. Vaudano
with V and Mo from a hydrodesulphurisation process. and Tissot [61] investigated the anodic production of p-
They used a three-compartment electrode cell, in order isopropylbenzaldehyde (p-cuminal) in both flow-
to elute the co-adsorbed vanadium and molybdenum through RVC and cylindrical graphite cells. High ro-
selectively [56]. This technique was first used for de- tation speeds and high flow rates increased selectivity
contamination of nuclear wastes. Their results showed up to 35% for RVC and 60% for graphite; conversion
93% and 7% vanadium and molybdenum recovery, re- was >95% at both electrodes. Krische and co-workers
spectively, at 323 K using 30 g l1 H2 SO4 eluant. The investigated the reduction mechanism of phenyl
use of lower temperatures, constant current density, and substituted bis(enone) in 0.1 M LiClO4 in CH3 CN, on
more acidic eluants were all shown to decrease elution a vitreous carbon electrode. The starting material was
selectivity of vanadium towards molybdenum. consumed and the current felt to nearly zero when only
Gonz
alez and co-workers [57] studied the problems 30% of the theoretically required electrical charge had
associated with the recovery of low concentrations of been passed. However, the overall yield was 76% with
silver when high concentrations of copper and cyanide other polymeric products accounting for the mass
exist in solution. This is a typical problem found in the balance. The authors proposed a mechanism involving
mining industry where cyanide baths are the most the cycloaddition of an anion radical as an intermedi-
common leaching agents. Chemical speciation, cyclic ate [62].
voltammetry and the electrolysis of a cyanide solution
containing Ag, Cu and CN showed that high Cu(II)
and CN concentration do not interfere in the selective 8. Fenton’s reagent and peroxide production
deposition of silver. The electrochemical reduction of
chromate ions has received increased attention; Njau There has been a great interest in the electrogenera-
and Janssen compared the performance of several three- tion of hydrogen peroxide by the reduction of oxygen in
dimensional cathode electrode materials such as a solution, as it can be produced in situ at high selectivity
packed bed of graphite particles, activated carbon, and efficiency. Today, FentonÕs Reagent is used to treat
RVC, expanded titanium mesh and graphite felt. RVC a variety of industrial wastes containing a range of toxic
and expanded titanium were found to passivate when in organic compounds [63]. The chemistry of the reagent
contact with chromate ions solution and, therefore, can be represented as follows:
were not suitable for the reduction of chromate ions.
However, the concentration of chromate could be de- Fe2þ þ H2 O2 ! Fe3þ þ OH þ  OH ð3Þ
creased below 0.5 ppm using the other cathode materi-
Fe3þ þ H2 O2 ! Fe2þ þ  OOH þ Hþ ð4Þ
als [58].
Ponce de Le
on and Pletcher [64] investigated the removal
of formaldehyde from aqueous solutions via oxygen re-
7. Synthesis of organics duction in an RVC cathode cell, in an alkaline medium.
The current–potential curves for an air saturated
The stability and inertness of RVC in a wide range 1 M NaOH solution showed two waves (at E1=2 ¼ 460
of acids and bases can be exploited to produce a mV and E1=2 ¼ 970 mV vs. SCE), attributed to the
214 J.M. Friedrich et al. / Journal of Electroanalytical Chemistry 561 (2004) 203–217

formation of H2 O2 and H2 O, respectively. This was

confirmed by controlled potential electrolysis. The con-
centration of H2 O2 in the catholyte increased linearly
with time during the electrolysis and the current effi-
ciency decayed from >90% to 57% at )0.6 and )1.4 V vs.
SCE, respectively. The reaction of H2 O2 with formalde-
hyde produced either formic acid or carbon dioxide using
an iron salt as catalyst to generate the FentonÕs reactant
during the electrolysis of O2 at )0.6 V vs. SCE. The ex-
periment was carried out with three different formalde-
hyde concentrations, 5, 13 and 116 ppm. In all cases, the
formaldehyde concentration decreased below 1 ppm;
however, the removal of formaldehyde was not mass
transport controlled as it was limited by the rate of for-
mation of hydrogen peroxide, hence by the supply of
oxygen to the electrode surface and the kinetics of the
reduction of oxygen at the RVC electrode surface. The
results indicated that adding a trace of iron salt could
treat effluents and, if needed, a small amount of an
electrolyte, e.g., NaCl (+FeCl2 ) in an acidic media, to
achieve the oxidation of formaldehyde to CO2 . During Fig. 11. Chemical oxygen demand (COD) as a function of charge
the oxidation of 13 ppm of formaldehyde in an acidic passed for electrolyses of different organic compounds at 0.33 mM
media with added FeCl2 , the total organic carbon (TOC) concentration in 0.05 M Na2 SO4 + 1 mM Fe(II) solution at pH 2 in a
dropped from 6.8 to 1.3 mg dm3 , indicating substantial membrane cell with a RVC electrode. Cathode potential )0.70 V vs.
oxidation of formaldehyde to carbon dioxide. SCE, mean linear velocity of the catholyte of 0.13 m s1 at room
temperature [66].
In a following paper, Alvarez-Gallegos and Pletcher
[65] reported current efficiencies between 40% and 70%
for the electro-synthesis of H2 O2 in aqueous acidic so-
lutions in a similar cell. The presence of Fe(II) in the density, H2 O2 was reduced rapidly, as its concentra-
catholyte reduced the half-life of H2 O2 down to min- tion was high. The generation of H2 O2 was more ef-
utes. At pH 2, the RVC electrode was found to be ficient in the presence of EAQ. In the second paper
suitable to oxidise organic compounds. Further inves- Huissoud and Tissot [68] examined the production of
tigations by the same authors focused on the removal of alkaline H2 O2 by intermediate electro-reduction of
phenols and related compounds in the presence of EAQ in a flow-by RVC electrode in two-phase liquid–
Fe(II) + H2 O2 in aqueous solutions at pH 2 [66]. Aro- liquid flow. The two-phase electrolyte used was a
matic molecules such as dyes between 0.1 and 1 mM mixture of tributylphosphate (TBP) and diethylbenzene
concentrations were completely oxidised and their (DEB) as the organic phase and NaOH as the aqueous
chemical oxygen demand (COD) was reduced to insig- phase. They investigated the influence of current, flow
nificant levels at a current efficiency above 50%. Fig. 11 rate, EAQ concentration in the organic phase, organic/
shows the decay in COD for different organic molecules aqueous phase volume ratio and RVC grade on the
reported by the authors at an initial concentration of process. A new method of producing alkaline hydro-
0.33 mM. The authors estimated, that in a suitable cell gen peroxide was developed in the intermediate elec-
design the treatment of 0.33 mM phenol solution would tro-reduction of EAQ in a two-phase medium on an
require 1.25 kW h m3 to reduce the COD to below 10 RVC cathode in the presence of oxygen. Current effi-
ppm. They suggested that higher rates of destruction ciencies were 85% and H2 O2 concentration reached 0.8
would be possible with a gas diffusion electrode, or in- M. The results showed that current efficiency was fa-
deed by increasing the size of the RVC or applying a voured at low organic/aqueous phase volume ratios
more negative potential than )700 mV vs. SCE value and one-step electrolysis was more efficient than two-
used in the experiments. step electrolysis.
Huissoud and Tissot [67,68] published two papers Gyenge and Oloman [69] studied the influence of
investigating the production of H2 O2 by the interme- cationic, non-ionic and anionic surfactants, on the re-
diate reduction of 2-ethyl-9,10-anthraquinone (EAQ) duction of O2 to H2 O2 in Na2 CO3 and H2 SO4 elec-
on 45, 60 and 80 ppi RVC electrodes at current den- trolytes on a 30-ppi RVC electrode. They found that
sities between 05 and 0.8 mA cm2 . Current efficiencies the surfactant Aliquant 336 tricaprylmethylammonium
around 50% as well as hydrogen evolution were re- chloride increased the rate of O2 reduction to H2 O2 in
ported for all runs, but over 0.9 mA cm2 current both electrolytes due to the well-organized surfactant
 J.M. Friedrich et al. / Journal of Electroanalytical Chemistry 561 (2004) 203–217 215

structures formed on the surface of the electrode. efficiency of about 60% under high current density cy-
However, the non-ionic and anionic surfactants Triton cling conditions (3.8 A g1 per gram electrode) was re-
X and sodium dodecyl sulphate, respectively, retarded ported for the Li/LiClO4 cell using the PANI–PSS
the reduction of O2 to H2 O2 as they formed less or- modified RVC electrode. Further application of the
ganized surface aggregates that blocked the access of PANI–PSS composites in this system was made depen-
O2 to the electrode. They achieved 0.31 and 0.26 M dent on optimisation of the current density and the
peroxide concentration in Na2 CO3 and H2 SO4 , re- amount of modified PANI–PSS composite on the RVC
spectively, at current efficiencies of 61% and 55%, re- electrode.
spectively. Without surfactant, the concentration of More recently, Gyenge et al. [74] reported the use of
H2 O2 was 0.07 and 0.014 M with 14% and 7% current electroplated RVC substrates with a Pb–Sn (1 wt%) al-
efficiency in the acid and alkaline electrolytes, respec- loy as current collectors for lead-acid batteries. Several
tively. electrochemical techniques were used to evaluate the
current collectors. A battery with a 137 cm2 current
collector completed 500 cycles and over 1500 h of con-
9. Batteries and fuel cells tinuous operation. The results indicated that electro-
plated RVC is a promising material for the development
Since the early 1980s, researchers have reported the of lower weight lead-acid batteries with RVC current
use of RVC as an electrode material for different bat- collectors. RVC has also been used to study the kinetics
teries [70]. The inertness, high current densities and the of redox couples with the aim of use in storage redox
high temperature resistance of RVC make it worthwhile flow cell batteries: together with other carbon base
to consider it for fuel cell design [71]. Iacovangelo and electrodes, Chong and Skyllas-Kazacos [75] determined
Will [72] studied current density, flow rate, electrolyte the kinetic parameters of the V(V)/V(IV) couple. Ma-
composition, substrate thickness and pore size of zinc stragostino and Gramellini [76] studied the electro-
deposits on RVC electrodes, with the aim of using them chemical processes of the aqueous Br2 /Br system using
as substrates in Zn batteries. They found that high a rotating disc electrode both at reticulated and solid
electrolyte flow rates and thicker foams produced uni- vitreous carbon. On both electrodes, the cathodic and
form Zn deposits. The best results were obtained with 2 the anodic processes involve two consecutive electro-
mm thick 100 ppi RVC at flow rates with Reynolds chemical steps. The Br3 reduction occurs via formation
numbers close to 500. An organic dendrite inhibitor– of Br2 , with which Br3 is in rapid equilibrium, where-
solubiliser helped to produce dendrite free Zn deposits upon Br2 is reduced.
inside the RVC structure, allowing current densities of
100 mA cm2 .
Mastragostino and Valcher [5] used 60 and 100 ppi
RVC electrodes as supports for a polymeric salt as 10. Other applications
bromine complexing agent in a Zn–Br2 battery. The
large surface area of RVC helped to overcome diffi- Wauters and Winnick [77] used an electrolytic mem-
culties related to low current density while its porosity brane to recover bromine from waste hydrogen bromide
also helped to retain the solid complex of bromide that streams, the system being based on a molten salt satu-
was generated during the charging stage. Increasing the rated membrane with RVC gas-diffusion electrodes.
amount of PBr at constant RVC thickness or de- Experiments at 573 K and process stream concentra-
creasing the RVC thickness while keeping the amount tions from 25% to 75% hydrogen bromide at flow rates
of PBr constant impaired battery performance. The of 50–300 ml min1 showed a fractional conversion of
best performance was reported for 100 ppi RVC. The reactant as high as 95%.
charge/discharge experiments carried out to evaluate RVC has been used in a number of other applica-
the performance of the zinc–bromine battery with a tions, including: (a) a cathode in cathodoluminescent
RVC/PBr electrode showed near constant charging light source applications [78], (b) in reactor shutdown,
potential over the entire charge period, while the dis- decontamination, and decommissioning activities of
charging potential decreased slightly while discharging nuclear reactors for the removal of Cs-137 inside a
at constant current. Tests to determine the self-dis- pressure vessel [79], (c) as an electrode contact in an
charge rate, a key parameter in battery construction, innovative food powered mobile robot that uses a mi-
found it to be only 0.01 A dm2 at 298 K. Overall, the crobial fuel cell (MFC) system to convert carbohydrate
authors saw the results as a promising starting point fuel to an electrical power source [80], (d) as a plasma
for future investigations. generator in a 10 torr pressure microwave [81] and (e) as
Tsutsumi et al. [73] used a polyaniline (PANI)– an electrode in gas-phase pulsed streamer corona reac-
poly(p-styrenesulfonic acid) (PSS) modified RVC elec- tors for the removal of NO/NOx from the exhaust of a 5
trode in a rechargeable lithium battery. A coulombic kW diesel engine [82].
216 J.M. Friedrich et al. / Journal of Electroanalytical Chemistry 561 (2004) 203–217

11. Summary [8] Y. Aoki, PhD Thesis, University of Bath, 1993.

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