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SCHOOL OF ADVANCED STUDIES

Doctorate course in Chemical Sciences

PhD thesis
Cesium and rubidium salts of Keggin-type
heteropolyacids as stable meso-microporous matrix
for anode catalyst for H2/O2 Proton Exchange
Membrane Fuel Cell, Direct Methanol Fuel Cell and
Direct Ethanol Fuel Cell

Cycle XXI
Scientific-sector CHIM/01

PhD Candidate

Tutor

Artur urowski

Professor Roberto Marassi


Professor Pawe J. Kulesza

2005/2006 2007/2008

Table of contents
Overview of the dissertation 4
Introduction
1. Fuel cell..7
1.1 History...7
1.2 Basic principles, types and efficiency...8
2. Anode electrocatalysis in PEMFC.....14
2.1 Hydrogen oxidation.14
2.2 Methanol oxidation..16
2.3 Ethanol oxidation.....20
3. Heteropoly compounds..........................24
3.1 Structure of heteropoly compounds (heteropolyacids)24
3.2 Properties of heteropolyacids..27
3.3 Salts of the heteropoly compounds..30
4.

Experimental techniques......34
4.1 Cyclic voltammetry..34
4.1.1

Rotating disk voltammetry37

4.2 Chronoamperometry39
4.3 Staircase voltammetry.40
4.4 Electrochemical impedance spectroscopy...41
4.5 Transmission electron microscopy .....43
4.6 Scanning electron microscopy ....45
4.7 Infrared spectroscopy.46
Experimental part
5. Chemical reagents and measuring equipment.......48
6. Preparation and characterization of Keggin-type matrix...51
6.1 Preparation of Keggin-type heteropolyacid salts.....51
6.2 IR characterization of Keggin-type matrix..51
6.3 SEM characterization of Keggin-type matrix..54
6.4 Cyclic voltammetry characterization of Keggin-type matrix..57
6.5 Conclusions.61
7.

Hydrogen oxidation reaction (HOR) on the catalytic layers


containing Cs2.5PW12 matrix....62
1

7.1

Preparation of the catalytic layers...62

7.1.1

Mixing method..62

7.1.2

Electrochemical method63

7.2 Electrochemical measurements on the Pt/C modified with


Cs2.5PW12 system prepared by mixing method.65
7.2.1

Cyclic voltammetry (CV) and rotating disc voltammetry


(RDE) measurements.65

7.2.2

Test of the Cs2.5H0.5PW12O40-containing anodes


catalyst in working single PEM fuel cell...74

7.3 Electrochemical measurements on the Pt/C modified with


Cs2.5H0.5PW12O40 system prepared by electrochemical method...78
7.3.1

Cyclic voltammetry (CV) study....78

7.3.2

CO electrooxidation on the catalytic layer containing


Cs2.5H0.5PW12O40 as a matrix.80

7.3.3

HRTEM characterization..81

7.3.4

Rotating disc voltammetry (RDE) measurements83

7.4

Comparison of catalytic layers containing Cs2.5PW12


matrix prepared by mixing and electrochemical methods88

8. Methanol oxidation reaction (MOR) on the catalytic layers


containing Keggin-type heteropolyacid salts as a matrix......90
8.1 Preparation of the catalytic layers...90
8.2 Electrochemical measurements at the Pt40%/C
modified with Cs2.5-HPAs matrix...91
8.2.1 Cyclic voltammetry (CV) study...91
8.2.2 Staircase voltammetry (SV) measurements..95
8.2.3 Chronoamperometry (CA) measurements97
8.2.4 Electrochemical impedance spectroscopy
for methanol electrooxidation ..99
8.2.5 CO stripping voltammetry study at Pt/C-Cs2.5HPAs..105
8.2.6 Electrochemical stability of investigated materials
containing Cs2.5-HPAs matrix107

8.3 Electrochemical measurements at system


containing Rb2.5-HPAs matrix....108
8.3.1 Cyclic voltammetry (CV) measurements...108
8.3.2 Staircase voltammetry (SV) measurements112
8.3.3 Chronoamperometry (CA) measurements..114
8.3.4 Electrochemical impedance spectroscopy measurements..116
8.3.5 CO stripping voltammetry study at Pt/C
modified with Rb2.5-HPAs......118
8.3.6 Electrochemical stability of investigated materials
containing Rb2.5-HPAs...120
8.4 Summary and conclusion..122
9. Ethanol oxidation reaction (EOR) on the Pt40%/Vulcan XC-72 carbon
modified with Cs2.5-HPAs...127
9.1 Cyclic voltammetry (CV) measurements..127
9.2 Staircase voltammetry (SV) measurements..130
9.3 Chronoamperometry (CA) measurements132
9.4 Electrochemical impedance spectroscopy
for ethanol electrooxidation...134
9.5 Electrochemical stability of investigated materials
containing Cs2.5-HPAs...136
Conclusions...138
Bibliography..141

Overview of the dissertation


In various applications, fuel cells are widely recognized as very attractive
devices to obtain directly electric energy from the electrochemical combustion of
chemical products. Low temperature fuel cells, which generally utilize proton
electrolyte membranes, seem to be also of utility for a large of power applications.
However, the final choice of the fuel is still difficult and depends greatly on the field of
application. Utilization of pure hydrogen or hydrogen-rich gases, rather than alcohols,
as fuels in Polymer Electrolyte Membrane Fuel Cell (PEMFC) leads to higher electric
efficiencies. Due to the problems related to the hydrogen storage, the hydrogen-oxygen
PEMFC is the best choice for stationary applications. Direct alcohols (methanol and
ethanol) fuel cells based on solid polymer electrolytes are widely proposed for portable
and mobile applications due to relatively low prices of the methanol and ethanol fuels
and easiness of storage. The major impediment in the development of fuel cells
operating on hydrogen, methanol, and ethanol is deactivation of the anode
electrocatalyst by trace level of CO. Thus, the most active Pt electrocatalyst for the
oxidation of hydrogen and alcohols (e.g. methanol, and ethanol) is deactivated by strong
adsorption of carbon monoxide, and leads to decreased performance of fuel cell.
Therefore, a new inexpensive, stable electrocatalyst must be developed, which is
tolerant to high levels of CO (particularly, for direct alcohol fuel cell) or that could
preferably utilize CO.
There are currently two state-of-the-art methods which increase CO tolerance of
the fuel cell anode. One method is to use a Pt-alloy catalyst (e. g. PtRu, PtSn, PtMo,
PtW).[1-6] The other method is to use the zeolite as matrix, and limit the preferential
formation of CO clusters on platinum by the steric constraints imposed by the zeolites
framework, followed by facile oxidation to CO2 by interaction with the surface or
bridged hydroxyls of the zeolites. Furthermore, the porous nature of the zeolite support
material provides relatively improved gas permeability and minimizes the disadvantage
associated with restricted gas diffusion in the electrode. The ideal support would also an
enhanced electrochemically active surface area by dispersion of the metal catalyst.[7, 8]
Keggin-type heteropolyacids show appreciable acid catalytic properties[9-14] that
are of practical importance[15] as illustrated in numerous recent reviews.[13, 15-18] The fact
that heteropolyanions undergo spontaneous adsorption (from aqueous solution) on

various substrates[32,33] provides a simple tool for modification of electrode surfaces[1922]

Among other important issues related to electrocatalysis are their ability to undergo

fast reversible multi-electron transfers and super-acid properties resulting in the


increased availability and mobility of protons at the electrocatalytic interfaces.
Consequently, polyacids were considered for fuel cell research.[23-29] With respect to the
oxygen reduction, the adsorbed heteropolyacid (particularly H3PW12O40) nanostructures
do not seem to block access of reactant molecules[21] to catalytic Pt. Further, their
presence at the interface shifts formation of the inhibiting Pt-oxo (PtOH or PtO) species
towards more positive potentials thus increasing the potential range where catalytic
metallic (Pt0) sites exist. It is reasonable to expect that, by analogy to the activating role
of WO3 and partially reduced hydrogen tungsten oxide bronzes during elect oxidation of
methanol, the related heteropolyblue tungstates should also enhance reactivity of Pt
during oxidation of organic fuels.[26,

30]

Stanis and co-workers[27] reported that the

addition of adsorbed HPAs can improve the performance of Pt anodes in a fuel cell
under CO-poisoned conditions. Also Farell et al. postulated that HPAs can act as cocatalysts with platinum for methanol electrooxidation.[28]
Among limitations in practical applications of heteropolyacids is their very good
solubility in aqueous solutions including acids as well as their ability to undergo
desorption during long-term operation. Thus it is necessary to stabilize heteropolyacid
layers at electrocatalytic interfaces without loosing their activating properties. An
interesting alternative arises from the possibility of formation of acidic salts of
heteropolytungstates or molybdates by partial exchange of protons with large cations
(such as Cs+, Rb+, NH4+ or K+) in the parent heteropolyacid. Consequently, a watersoluble polyacid of low surface area (<5 m2g-1) is transferred into a water-insoluble acid
salt precipitate characterized by the surface area exceeding 100 m2g-1.[31, 32] Contrary to
zeolites exchanged with alkali metals[14, 33], heteropolyacid salts remain strong acidity.
The resulting materials have occurred to be efficient solid shape-selective acid catalysts
for a variety of organic liquid-phase reactions[18] that include hydrogenations and
oxidations. The pore size and acidity of heteropolyacid salt can be controlled by the
cation content. For example, when the Cs content, x, is initially increased in CsxH3xPW12O40

from 0 to 2, the number of surface protons decreases but, later, it significantly

increases when x changes from 2 to 3 to show the highest surface acidity at x = 2.5.[14]
In the present work, we consider the salts of Keggin-type heteropolyacids
containing 2.5 moles of Cs+ and Rb+ cations in 1 mole of the heteropoly salt. The
5

system with such Cs or Rb-content is micro-mesoporous, and it is characterized by very


good stability and, while being insoluble in water, it exhibits high acidity (proton
availability and mobility).
The aim of this work is to study the applicability of the Cs and Rb salts of
Keggin type heteropolyacids as a stable meso-microporous matrix for anode catalyst for
H2/O2 Proton Exchange Membrane Fuel Cell, Direct Methanol Fuel Cell and Direct
Ethanol Fuel Cell.
The experimental part is divided into four chapters (from 6 to 9). In the Chapter
6, we present characterization of cesium, rubidium and ammonium salts of Keggin
types heteropolyacids by infrared spectroscopy (IR), scanning electron microscopy
(SEM), and cyclic voltammetry (CV) measurements.
In Chapter 7, we illustrate incorporation and activation of Pt centers in the
conductive high surface-area zeolite-type robust, Cs2.5H0.5PW12O40 matrices through
application of mixing and electrochemical methods. To evaluate electrocatalytic activity
towards the hydrogen oxidation of the investigated electrode material, we have
performed the diagnostic rotating disc electrode voltammetric measurements. In a case
of the catalytic layer prepared by corrosion of Pt counter electrode (electrochemical
method), CO-stripping and HRTEM measurements have been performed to comment
the electrochemically active area of catalyst, dimensions of Pt particles and platinum
loading.
In Chapter 8, we report on the performance of electrocatalysts (prepared by
mixing method) towards methanol oxidation in acidic media. The Cs and Rb salts of
H3PW12O40, H3PMo12O40, H4SiW12O40, H4SiMo12O40 were used as zeolite matrix for
Pt40%/Vulcan XC-72 carbon nanoparticles (Pt/C). The techniques of cyclic
voltammetry, staircase voltammetry, chronoamperometry, electrochemical impedance
spectroscopy, CO stripping voltammetry were applied to compare the Pt-base
electrocatalyst activity and stability to methanol oxidation.
In Chapter 9, the system composed of Pt40%/Vulcan XC-72 carbon modified
with Cs2.5-HPAs matrix (prepared by mixing method) has been examined with respect
to ethanol electrooxidation by several different electrochemical techniques. Comparison
has been made to commercial Pt/C.

1. Fuel cell

1.1 History
The principle of the fuel cell was discovered by the German scientist, who in
1839 published paper about current production in reaction between hydrogen and
oxygen. Based on this work, in 1839, British physicist and lawyer, Sir William R.
Grove develops the first working fuel cell. By connecting a hydrogen anode and an
oxygen cathode, he produced an electric current with the experimental set-up shown in
Fig. 1.

Fig.1. Four-cell version of Groves gas battery.[34]

He also, in 1844/1845, presented the first fuel cell power generator which consisted 10
cells connected in series and was supplied with hydrogen from corrosion of zinc in acid.

Fig. 2. Groves fuel cell power generator.[34]

In 1905 Wilhelm Ostwald and Walter H. Nerst presented a general theory of the
fuel cells. Due to easily accessible and large amounts of oil and the invention of the

combustion engine by Carl Friedrich Benz and Gottlieb Daimler fuel cells were
forgotten until the middle of the 20th. Because of US Apollo space programme in the
1960s fuel cells exhibited their first renaissance. Gemini 5 was the first space shuttle
using a polymer membrane fuel cell instead of battery. In 1969 alkaline fuel cells were
used in the Apollo missions and supplied the electric power when the USA landed on
the moon.
The first oil crisis in 1973 led to the second renaissance of the fuel cells. At this
time interest for large power plants based on high-temperature fuel cells considerably
increased. In 1970 professor Karl Kordesch (early fuel cell pioneer) form University of
Graz, Austria, and his co-workers developed an alkaline fuel cell motorbike and a car.
The focus on increasing pollution level over the last two to three decades has
forced world society to search for cleaner energy technology, and thus fuel cells have
experienced an exponential increase in attention.

1.2 Basic principles, types and efficiency


A fuel cell is electrochemical device that continuously converts chemical energy
into electric energy (and some heat) for as long as fuel oxidant is supplied.
In the exchange membrane fuel cell (PEMFC), hydrogen (fuel) is oxidised to
protons and electrons at the anode. Protons migrate through the membrane electrolyte to
the cathode. As the membrane is an electric insulator, electrons are forced to flow in an
external electric circuit. At the cathode, oxygen (oxidant) reacts with protons to produce
water, which is the only waste product from a hydrogen-operated PEMFC. A schematic
representation of a fuel cell with the reactant/product gases and the ion conduction flow
directions through the cell is shown in Figure 3.
Anode reaction: H2 2H+ + 2e-

(1)

Cathode reaction: O2 + 2H+ + 2e- H2O

(2)

Total cell reaction: H2 + O2 H2O

(3)

Fig.3. Schematic of an individual fuel cell.[35]

From hydrogen and oxygen we obtain water, heat and power. There are other fuels,
electrolytes and charge-transferring ions for the other fuel cell types - but the principle
is the same.
When an external resistance, commonly referred to as a load, is applied to the cell,
non-equilibrium exists and a net current flows through the load. The net rate of an
electrochemical reaction is proportional to the current density which is defined as the
current of the electrochemical system divided by the active area devices. The cell
voltage becomes smaller as the net reaction rate increase because of irreversible
losses.[36] A representative polarization curve for hydrogen-oxygen PEMFC is illustrates
in Fig. 4. The voltage-current density relationship for a given fuel cell (geometry,
catalyst/electrode characteristic, and electrolyte/membrane properties) and operating
conditions (concentration, flow rate, pressure, temperature) is a function of the kinetic,
ohmic, and mass transfer resistance. Fuel crossover and internal current losses result
from the flow of fuel and electric current in the electrolyte. The electrolyte should only
transport ions, however a certain fuel and electron flow will always occur. Although the
fuel loss and internal currents are small, they are the main reason for the real open
circuit voltage (OCV) being lower than the theoretical one (Erev).

Fig. 4. A typical performance curve for a solid polymer fuel cell showing the relative effects of
electrode activation (kinetic losses), ohmic resistance and mass transport losses.[37]

Activation losses are caused by the slowness of the reactions taking place on the
electrode surface. The voltage decreases somewhat due to the electrochemical reaction
kinetics. The ohmic losses result from resistance to the flow of ions in the electrolyte
and electrons through the cell hardware and various interconnections. The
corresponding voltage drop is essentially proportional to current density, hence the term
"ohmic losses". Mass transport losses result from the decrease in reactant concentration
at the surface of the electrodes as fuel is used. At maximum (limiting) current, the
concentration at the catalyst surface is practically zero, as the reactants are consumed as
soon as they are supplied to the surface. In the thesis the investigation was principally
concerned with the activation losses of low temperature fuel cells.

Fuel cells can be classified according to their operating temperature, electrolyte


and the corresponding conductive ions (Tab. 1).

10

Alkaline Fuel
Cell (AFC)

Proton
Phosphoric
Exchange
Acid Fuel Cell
Membrane Fuel
(PAFC)
Cell (PEMFC)

Molten
Carbonate
Fuel Fell
(MCFC)

Solid Oxide
Fuel Cell
(SOFC)

Operating
temperature

70-220C

Up to 120C

130-220C

600-800C

700-1000C

Electrolyte

Potassium
hydroxide
(KOH)

Polymer
membrane

Concentrated
phosphoric
acid

Melted Li/K
carbonate

Solid oxide
ceramic

Fuels

Pure
hydrogen

Hydrogen,
natural gas

Hydrogen,
natural gas

Hydrogen,
natural gas

Power
range
realised
Application

Up to 12 kW

Hydrogen
(+reformate),
methanol,
ethanol
Up to 250 kW

Up to 1 MW

Up to 2 MW

Up to 10
MW

Portable,
Small power
mobile, APU,
plants, APU,
CHP
CHP
APU - Auxiliary Power Unit, CHP - Combined Heat and Power

Power plants

Power
plants,
APU, CHP

Space, submarine

Table. 1. Typical properties of the different fuel cell types.[37]

To the low-temperature group of fuel cells we can include Polymer Electrolyte


Membrane Fuel Cells (PEMFC), Direct Methanol Fuel Cells (DMFC), Direct Ethanol
Fuel Cells, Phosphoric Acid Fuel Cells (PAFC) and Alkaline Fuel Cells (AFC). Solid
Oxide Fuel Cells (SOFC) and Molten Carbonate Fuel Cells (MCFC) are hightemperature fuel cells.

The most important disadvantage of fuel cell at the present time is the same for all
types the cost. However, the are varied advantages[38]:

 Efficiency. Fuel cell is generally more efficient than combustion engines


whether piston or turbine based. They are small system which can be just as
efficient as large ones. This is very important in the case of the small local
power generating system needed foe combined heat and power system.
Fuel cells are not limited due to the Carnot theorem therefore, they are more
efficient in extracting energy from a fuel than conventional power plant. Waste
heat from some cells can also be harnessed, boosting system efficiency still
further. Typical efficiency of different fuel cells is placed below, in Table 2.

11

Type

Efficiency

Solid Oxide

45 65%

Molten Carbonate

50%

Phosphoric Acid

40%

Alkaline

50 60%

Direct Methanol

40%

Proton Exchange

40%

Membrane (PEM)
Table. 2. Typical efficiency of fuel cells.[37]

 Simplicity. The essential of a fuel cell are very simple, with few if any moving
parts. This can lead to highly reliable and long-lasting system.

 Low emissions. The by-product of the main fuel cell reaction, when hydrogen is
the fuel, is pure water, which means a fuel cell can be essentially zero
emission. This is their main advantage when use in vehicles, as there is a
requirement to reduce vehicle emissions, and even eliminated them within cities.

Water
Vapor
g / mile

CO2
g /mile

CO
g /mile

NOx
g /mile

Hydro
Carbons
g /mile

176.90

415.49

20.9

1.39

2.80

Gasoline ICE
Light Truck 1

N/a

521.63

27.7

1.81

3.51

Methanol FC 2

113.40

68.04

0.016

0.0025

0.0034

Hydrogen FC 2

113.40

0.00

0.00

0.00

0.00

Engine Type

Gasoline ICE
Passenger Car 1

1 2000 U.S. EPA Average Annual Emission for Passenger Cars and Light Trucks
2 Calculations from Desert Research Institute
1mile = 1.6 km

Table. 3. Systems emissions.[39]

12

 Silence. Fuel cell are very quiet, even those with extensive extra fuel processing
equipment. This is very important in both portable power applications and for
local power generation in combined heat and power schemes.
The advantages of fuel cell impact particularly strongly on combined heat and
power system (for both large and small scald applications), and on mobile power
systems, especially for vehicles and electronic equipments such as portable computers,
mobile telephones, and military communications equipment. These areas are the major
fields in which fuel cells are being used. A key point is the wide range of applications of
a fuel cell power, from systems of a few watts up to megawatts.

Table. 4. Chart to summarized the application of fuel cells of different types and different
applications.[38]

Among the applicable low-temperature acid-type systems, polymer electrolyte


membrane fuel cells (PEMFCs), direct methanol fuel cells (DMFCs) and direct ethanol
fuel cells (DEFCs) are probably the most promising devices, and they are subjects of
interest in many laboratories worldwide. While in the case of PEMFCs, hydrogen is
utilized; the methanol or ethanol fuel is oxidized in the anodic compartment of DMFCs
or DEFCs, respectively. To improve power densities of PEMFCs, DMFCs, and DEFs
there is a need to develop new electrocatalyst to inhibit the poisoning and significantly
increase the rate of electrooxidation. This study has been concerned with the catalysts of
the three low temperature fuel cells, the PEMFC, the DMFC and the DEFC.

13

2. Anode electrocatalysis in PEMFC

2.1 Hydrogen oxidation


The hydrogen oxidation reaction (HOR) is very important reaction which, serve
as a model for electrocatalytic reaction, and has significant practical utility in some
kinds of electrochemical sensors and fuel cells.[40-57] In acid media the catalysis of the
reaction is usually promoted by the platinum catalyst dispersed as fine particles on high
surface area carbon supports.[44,58,59] One important class of such devices are those
assembled using polymer electrolyte (PE) and polymer impregnated gas diffusion
electrodes, most commonly employing Nafion (E.I. DuPoint, U.S.A.) membranes and
ionomers. The electrochemical oxidation of dihydrogen:
H2 2H+ + 2e-

(E0 = 0.00 V vs. RHE)

(4)

on noble metal surfaces such as Pt and Pd is very facile.[44] Other metals also show high
activity for H2 electrooxidation, but in acidic electrolytes, noble metals show the
greatest stability towards corrosion or passivation.
The accepted mechanism of hydrogen electro-oxidation on Pt in acidic
electrolytes is formed by a primary chemical:
H2 + 2Pt 2Pt-Hads

(Tafel reaction)

(5)

and / or electrochemical:
H2 + Pt Pt-Hads + H+ + e- (Heyrovsky reaction)

(6)

adsorption steps, followed by a discharge path of the adsorbed hydrogen atom given by
MH M + H+ + e-

(Volmer reaction)

(7)

For a given electrode material and the electrolyte, the rates of reactions (5) and (6) may
be quite different, and the mechanism may be formed preponderantly by the
Tafel/Volmer steps or alternatively by the Heyrovsky-Volmer steps. On Pt electrode, a
Tafel-Volmer mechanism, with dissociative adsorption of dihydrogen (Tafel reaction)
being the rate determining step (rds), has been proposed for this reaction[34,44,45,51] in
acidic electrolytes.
14

While pure H2 is the ideal choice of fuel for the PEMFC, economical sources of
pure H2 are not readily available. Therefore, currently the most practical source of H2 is
the catalytic processing of hydrocarbons. Hydrogen produced by the stream reforming
or partial oxidation of hydrocarbon fuels (gasoline, diesel, methane, alcohols) contains
impurities such as CO (1 - 3%) and CO2 (19 25%). It is well known that CO binds
strongly Pt sites and reduces the number its catalytic centers available for H2 adsorption
and oxidation. Although the electrochemical oxidation of CO:
CO + H2O CO2 + 2H+ + 2e-

(E0 = -0.1 V vs. RHE)

(8)

is thermodynamically favorable, in practice a large overpotential is required on pure Pt


surfaces before oxidation occurs. For example, on dispersed Pt catalysts, the onset of
CO oxidation is no observed until 0.5 V at 80 0C. Therefore, in the potential region
where anodes need to operate (i.e. 0 - 0.1 V), CO is an inert adsorbate. The degree of
CO poisoning of Pt catalysts is very dependent on both temperature and CO
concentration.[34]
CO2 poisoning on pure Pt catalysts is modest when compared to the effect of
CO, especially when the large differences in relative concentrations in reformate are
considered. The poisoning effect comes from two possible mechanisms:
1) H2 + CO2 H2O + CO

(9)

2) CO2 + 2Pt-Hads Pt-CO + H2O + Pt

(10)

Both are forms of the reverse water-gas shift reaction with (9) being the
familiar gas-phase reaction, and (10) the electrochemical equivalent. In both cases, the
product is CO, which has the same effect as fuel stream CO.
The most elegant way to overcome anode poisoning is through the development
of CO- and CO2- tolerant electrocatalysts. Much effort has been spent modifying Pt
with others metals to improve CO tolerance. Niedrach et al.[60], in early 1960s, found
that the addition of Ru, Rh and Ir to Pt in the form of unsupported mixed metal powders
(blacks) get substantial tolerance, compared to Pt black alone, to the presence of CO in
a fuel stream at 85 0C in 2.5 M H2SO4 electrolyte. Moreover, they found that mixing Pt
blacks with metal oxides, such as CoMoO4, MoO2 and WO3, also improved CO
tolerance over Pt alone.[60] In particular, the oxide-containing electrodes showed

15

remarkable performances with pure CO as a fuel, with reported activities approaching


those with pure H2 even at low potentials.[34]
In the recent years, a number of workers have reported the superior CO and CO2
tolerance of carbon-supported PtRu catalysts when compared to Pt-only catalysts.[1,61-67]

2.2 Methanol oxidation

Introduction
The electro- oxidation of methanol is very important from practical point of
view and has been studied for more than three decades.[1,28,61-67,68-97] Methanol is used as
a liquid fuel in Direct Methanol Fuel Cell (DMFC). Among the different possible
alcohols, methanol is the most promising organic fuel because its use as a fuel has
several advantages in comparison to hydrogen: high solubility in aqueous electrolytes,
liquid fuel available at low cost, easily handled, transported and stored, high theoretical
density of energy (6 kWh/kg) comparable to that of gasoline (10-11 kWh/kg).[68,69,97]

Fig. 5. Sketch of a DMFC illustrating proton, water and methanol permeation


across the PEM and related characterization methods.[98]

The sketch of the DMFC is shown in Fig. 5.[98] The DMFC consist of an anode
at which methanol is electro-oxidized to CO2 and a cathode where oxygen, generally
from air, is reduced to form water. Both electrodes, usually formulated with platinum or
Pt-based catalysts, are separated by a proton-conducting electrolyte. The direct

16

methanol oxidation involves the transfer of six electrons to the electrode for complete
oxidation to carbon dioxide. In an acidic medium, this reaction can be written as
follows:
 Anode reaction:

CH3OH + H2O CO2 + 6H+ + 6e-

(11)

 Cathode reaction:
3

/2 O2 + 6H+ + 6e- 3 H2O

(12)

 Overall reaction:

CH3OH + 3/2 O2 CO2 + 2 H2O

(13)

The free energy associated with the overall reaction at 25 oC and 1 atm and the
electromotive force are[77,99]: G = -686 kJ mol-1CH3OH; E = 1.18 V vs. SHE
Methanol oxidation reaction
Iwastia[84] reported that the thermodynamic potential for methanol oxidation to
CO2, is very close to the equilibrium potential for hydrogen (E0=0.02 V), Eq. 11.
However, compared with hydrogen oxidation, this reaction is by several orders of
magnitude slower and requires high loading Pt-based electrocatalyst ( 2 mg cm-2).[77]
In fact, the ideal anodic reaction is not completely reached as methanol is mainly
decomposed into CO, which can further be oxidized into CO2. The formations of CO
and CO2 are assumed occurring according to the dual path mechanism in the oxidation,
one leading to CO (12) and another to CO2 (11)[100]:
CH3OH CO+ 4H+ + 4e-

(14)

Other CO-like species are also formed during the adsorption phase, COHads, HCOads,
HCOOads, and the principle by-products are formaldehyde and formic acid.[77,93, ,101,102]
The generally accepted mechanism of methanol electro-oxidation pathway is considered
as follows[83,85,103]:
Pt + CH3OH Pt(CH3OH)ads

(15)

Pt(CH3OH)ads Pt(CH4-nO) + n H+ + n e-

(16)

M + H2O M-OH + H+ + e-

(17)

Pt-CO + M-OH CO2 + H+ + e+

(18)
-

Pt-CO + H2O CO2 + 2 H + 2 e

(19)

17

where, M is a metal, e.g. Pt, Ru, W. The complexity of the methanol oxidation reaction
on involving different path of reaction is shown in Fig. 6.

Fig. 6. Detailed reaction mechanism of the oxidation of methanol on a platinum electrode.[97]

Since the complete oxidation of methanol to CO2 involves the transfer of 6 electrons to
the electrode, the overall reaction mechanism (Eqs. 15 19) involves several steps
including dehydrogenation, chemisorption of methanolic residues, rearrangement of
adsorbed residues, chemisorption of oxygenated species (preferentially on the alloying
element) and surface reaction between CO and OH to give CO2. There is a reasonable
consensus regarding the general mechanisms at different potentials on Pt surfaces. It is
known that at low potentials, less than 0.4 V vs. RHE, the rate determining step for Pt
and PtRu electrode is the methanol dissociative adsorption expressed by Eqs. (15) and
(16).[82,84] The most important potential regime for a fuel cell is ca. 0.4 - 0.45 V vs. RHE
and the consensus agreement is that at this potential the rate-determining process is the
oxidation of CO.[34,82]
Clean Pt is a good catalyst for methanol oxidation and initially show very high
activity for methanol oxidation, but these very rapidly decay in current on the formation
of strongly bound intermediates.[62,77,104-106] These intermediates (mainly COads) are only
removed on going to high overpotentials where they are oxidized. At potentials below
0.45 V, the surface of Pt becomes poisoned with a near-monolayer coverage of CO, and

18

further adsorption of water or methanol cannot occur. Hence, the methanol oxidation
rate drops to an insignificant level.[34]
The development of advanced Pt based catalysts has focused on the addition of a
secondary component (e.g., Ru, Sn, W) that is able to provide an adsorption site capable
of forming OHads species at low potentials adjacent to poisoned Pt sites. The adsorption
site is also less effective at adsorbing methanol itself. The OHads is then able to react
with the bound CO to produce CO2 and free sites for further methanol adsorption.
Superior catalytic activities have been reported for Pt based alloys, such as Pt-Ru, PtMo, Pt-Sn, Pt-Os, Pt-Ru-Os.[61-66,106-108] This enhancement effect has been explained by
models such as the bifunctional mechanism[64,109,110] and/or the electronic
effect[65,111,112], which indicates a promotional effect of the alloyed metal on Pt. For
promoters such as Ru, stable methanol oxidation currents occur at significantly lower
potentials (<0.25 V) to Pt[34], indicating the Ru is capable of the formation of OHads
without itself being poisoned by CO.[62,84]
Ru + H2O (OH)ads + H+ + e-

(20)

(CO)ads + (OH)ads CO2 + H+ + e-

(21)

Until now the most successful results have been achieved through the alloying of Sn
and Ru with Pt. It has been shown that these alloys give rise electrocatalysis which
strongly promote the oxidation of both methanol and CO. The promotion of CO
oxidation reaction on Pt-Sn catalysts appears to be mainly due to a modification of the
electronic environment around Pt-sites.[113-115] It becomes clear that Pt-Ru catalysts are
more effective for methanol oxidation since the reaction desires the electrocatalyst to be
operated in a potential regime where labile-bonded oxygen should be present on the
surface. In this situation, the supply of active oxygen to the surface is of paramount
importance since this apparently would facilitate the oxidation of adsorbed methanolic
residues to CO2. The presence of strongly-bonded oxygen species on Sn-sites in the PtSn system limits the oxidation of methanol to CO2.[113-115]
Out of all tested catalysts, for the practical applications in DMFC the most active
and stable catalysts are these based on platinum ruthenium alloys.[1,61,63,64,66,67,112]

19

2.3 Ethanol oxidation

Introduction
Direct ethanol fuel cells (DEFCs) have spurred more and more in the recent years
due to intrinsic advantages such as its low toxicity, renewability, and its easy production
in great quantity by the fermentation from sugar-containing raw materials.[97,116]
Furthermore, the high theoretical mass energy density (about 8.00 kWh/kg)[4,97]
provides it with a potential candidate fuel for polymer electrolyte membrane fuel cells.
Therefore, ethanol electro-oxidation reaction is extensively studied by numerous of
researchers.[2-6,79,91,92,97,116-139]

Fig. 7. Schematic principle of a direct ethanol/oxygen fuel cell (DEFC).[117]

The parts of which a direct ethanol fuel cell (DEFC) constitutes and its working
principle are shown in Fig. 7. At the anode (negative pole of the cell) the electrooxidation of ethanol aqueous solutions takes place as follows[97,117,118]:
CH3CH2OH + 3 H2O 2 CO2 + 12 H+ + 12 e-

(22)

E10 = 0.085 V vs. SHE


whereas the cathode (positive pole) undergoes the electro-reduction of oxygen, i.e.:

O2 + 4 H+ + 4 e- 2 H2O

(23)

E20 = 1.229 V vs. SHE

20

where Ei0 are the standard electrode potentials versus the standard hydrogen electrode
(SHE). This corresponds to the overall combustion reaction of ethanol in oxygen:
CH3CH2OH + O2 2 CO2 + 3 H2O

(24)

This gives a standard electromotive force (Eemf) equal to 1.145 V.


The complete oxidation of ethanol involves 12 electrons per methanol molecule
(Eq. 22). and the cleavage of the C-C bond. In view of the direct electro-oxidation of
ethanol in the fuel cells, the materials that could facilitate ethanol complete oxidation
and shift the onset oxidation potentials to lower values are the most interest.[119]

Ethanol oxidation reaction


The complete oxidation of ethanol to CO2 is the central challenge in the
electrocatalysis of this alcohol. In the recent years, several spectroscopic and
electrochemical studies have been taken to evaluate the mechanism of ethanol electrooxidation on Pt-based catalysts.[2,79,92,97,120-122] A generally accepted reaction sequence
comprises of the following steps (where M is an active site)[2]:
M + CH3CH2OH MCHOHCH3 + H+ + e-

(25)

MCHOHCH3 MCHOCH3 + H+ + e-

(26)

MCHOCH3 MCOCH3 H + e

(27)

MCOCH3 + M MCO + MCH3

(28)

M + H2O MOH + H+ + e-

(29)

MCO + MOH 2M + CO2 + H+ + e-

(30)

Ethanol can also react with adsorbed hydroxyl species directly to produce acetate via a
four-electron oxidation pathway[2,122]:
C2H5OH + MOH MCH3COO + 4H+ + 4e-

(31)

An efficient electrocatalyst should facilitate each of the processes of dehydrogenation


(Eqs. (25)(27)), CC bond cleavage (Eq. (28)) and COads oxidation (Eq. (30)) for the
complete conversion of ethanol to CO2 to take place. In addition, water activation (Eq.
(29)) at low electrode potential is important for the subsequent COads oxidation step.

21

Platinum is recognized to be the most active material for ethanol oxidation, however, it
should be noted that the self-inhibition happens in the case of Pt alone, especially in the
steady state operation mode. Furthermore, in order to increase the fuel utilization and
the fuel cell efficiency, it is crucial to break C-C bond and provoke its complete
oxidation into carbon dioxide. Therefore, in order to improve the electrocatalytic
activity of platinum to ethanol electro-oxidation, platinum was often modified by a
second or a third additive like PtRu[2,3], PtRh[123], PtMo[124], PtSn[4,5], PtW[6], PtRuMeOx (Me = W, Mo, V ect.).[91,125-130] Fig. 8 presents the effect of different additives to
Pts activity to ethanol electrooxidation in a single DEFC. As one can distinguish that
all the additives can promote more or less the platinums electrocatalytic activity
towards ethanol oxidation.[119]

Fig. 8. The effect of the different additives on the Pts activity toward ethanol electrooxidation
in single direct ethanol PEMFCs under the same operation conditions. Tcell = 90 0C. Anode:
PtM/C, 1.3 mg Pt/cm2, Cethanol = 1.0 mol/L, flow rate: 1.0 mL/min. Cathode: Pt/C (20%,
Johnson Matthey Corp.), 1.0 mg/ cm2, PO2 = 2.0 atm. Electrolyte: Nafion1-115 membrane.[119]

From the attempts of Lamy et al.[131] to identify the suitable electrocatalysts for ethanol
oxidation, it was concluded that Sn can lead to encouraging results especially at lower
potential values, three times increase in maximum power density. They also found that
when the Sn atomic ratio in PtSn electrocatalyst is in the range of 1020%, it shows
desirable results. Moreover, they found that the addition of tin to Pt promotes the
oxidation of ethanol to acetic acid at lower potentials and proposed the mechanism of
ethanol electrooxidation over Pt and PtSn catalysts.[119] Both the bifunctional
mechanism and ligand effect have been proposed to be involved in the ethanol
electrooxidation over PtSn catalyst.[79]
22

At the end of this chapter we have to note that even if PtSn/C catalysts exhibit
higher electrocatalytic activity to ethanol oxidation, the majority of the oxidation
products are still the species containing CC bond, which will have an obviously
negative effect on the fuel cell performance.[4] It is crucial and necessary to develop a
novel catalyst or add a third element to modify the PtSn/C and PtRu/C to present higher
specific activity of dehydrogenation, CO and CC bond cleavage during the ethanol
oxidation process.

23

3. Heteropoly compounds
Transition metal polyoxometalates (POMs) are well-defined clusters with an
enormous variation in size, metal-oxygen framework topology, composition, and
functions. The preparation of POMs is based on the programmed self-assembly of metal
oxide building blocks, which result in discrete, structurally uniform, nanoscopic
clusters.[140] Although the first polyoxometalates [PMo12O403-] was reported in the 1826
by Berzelius[16] they have wide drawn attention since 1933 when it was possible to
characterized a believing variety of POM structure and the first X-ray crystal structure
analysis of the Keggin anion, [PW12O403-], appeared in the literature.[141] Most of the
chemical and physical properties of POMs have been growing interest for variety
applications, particularly in medicine, homogeneous and heterogeneous catalysis.[18,142]
There are two generic families of polyoxometallates[19]:
(1) the isopoly compounds (isopolyanions or isopolyoxometalates) contain only d0
metal cations and oxide anions
(2) the heteropoly compounds (called heteropolyanions, heteropolyoxometalates, or
heteropolyacids, when contain in the structure H+, H3O+, H5O2+) contain one or
more p-, d- or f-block heteroatom in addition the other ions.
As heteropolyanions are more numerous and their structural and electronic properties
are easier to modify synthetically than those of the isopolyanions, the former is a field
of increasing importance (particularly, in acid catalysis).

3.1 Structure of heteropoly compounds (heteropolyacids)


Heteropolyacids

(HPAs)

are

complex

proton

acids

that

incorporate

polyoxometallates anions (heteropolyanions) having metal-oxygen octahedral as basic


structure units.[18] Their general formula may be presents as [XxMmOy]q- (x < m) for
heteropoly anions. M is usually Mo or W and to a lesser extent V, Nb, or Ta. The
heteroatom X, can be one of 64 elements that belong to a various groups of the periodic
table except the noble gases.[143]

24

Heteropolyacids can be classified into four different groups according to their


molecular architectures[144,145]:
(1) Keggin (e. g. H3[PW12O40]),
(2) Wells-Dawson (e. g. H7[P2Mo17VO62]),
(3) Finke-Droege (e. g. Na16[Cu4(H2O)2(P2W15O56)2]) and
(4) Pope-Jeannin-Preyssler (e. g. (NH4)14[NaP5W30O110]).
Among the various structural classes, the heteropolyacids comprised of the
Keggin structure (represented by the formula Xn+M12O4n-8), and in particular the
compounds containing molybdenum and tungsten, are the most often studied due to
their acids and redox properties, stability at elevated temperatures, availability and
relative ease of synthesise what is the most important in catalysis.[16] In 1864 Marignac
observed two isomeric forms of the H4SiMo12O40, now know as the - and isomers.[146] In 1933 Keggin reported an the structure the -isomer of [PW12O40]3-.[147]
The -Keggin anions are know with a wide range of heteroatoms (for example, X =
Al(III), Si(IV), P(V), Fe(III), Co(III), Cu (I) and Cu (II) for M=Mo and W. -isomers
are much less common and the structure of -[SiW12O40]4-, was first determinated by
crystallography in 1973 by Yamamura and Sasaki.[146]
Figure 9 illustrates two views of the -Keggin structure. The Keggin anions has
a diameter of ca. 1.2 nm and is composed of a central tetrahedron XO4 surrounded by
12 ege- and cornersharing metal-oxygen octahedra MO6. The octahedra are arranged in
four M3O13 groups, one of which is shown in Fig. 1A. Each group is formed by three
octahedra sharing edges and having a common oxygen atom which is also shared with
the central tetrahedron XO4 to give molecular symmetry. The metal atoms M occupy the
centres of distorted octahedra with one terminal M-Ot bond. There are four types of
atoms in the Keggin anion: 12 terminal M=Ot, twelve edge-bridging angular M-Oc-M
shared by the octahedra within a M3O13 group, 12 corner-bridging quasi-linear M-Oe-M
connecting two different M3O13 groups, and 4 internal X-Op-M.[148] The -isomer
structure may be considered as derived from the -structure by rotation of one M3O13
group by 60o about its threefold axis.

25

Op
X

Fig. 9. The -Keggin (primary) structure shown (A) as a combination of [M3O13] groups and
(B) as individual bonds showing the distorted octahedral geometry around each metal.[28,146]

The examples of the Keggin type heteropolyacids:

 H3PW12O40 (PW12) 12-phosphotungstic acid


 H3PMo12O40 (PMo12) 12-phosphomolybdic acid
 H4SiW12O40 (SiW12) 12-silicotungstic acid
 H4SiMo12O40 (SiMo12) 12-silicomolybdic acid
Generally, heteropolycompound (heteropoly acids and their salts) form ionic
crystals composed of heteropolyanions (primary structure), countercanions (H+, H3O+,
H5O2+), hydratation water, and other molecules (Fig. 10). This three dimensional
arrangement is the secondary structure (pseudoliquid).[149] A relatively stable form of
hydrated HPA contains six water molecules per Keggin unit (KU). The hexahydrate has
a body-canter cubic structure with Keggin units at the lattice points and H5O2+ bridges
along the face. Each of 12 terminal oxygen atoms of the Keggin unit is bond to
hydrogen atom of an H5O2+ bridge.
The secondary structure of HPAs depends on the amount of hydration water and
heteropolyanion and can change from flexible to solid. Fro example 12tungstophosphoric acid (H3PW12O40) exhibits different packing arrangements as the
hydration water is lost.[148] This water can be easily removed on heating, whereby the
acid strength is increased due to the dehydration of protons. This a reversible process
accompanied by chancing the volume of crystal cell. Unlike the rigid network structure
of zeolites, in HPA crystal the Keggin anions are quiet mobile. Not only water but also

26

a variety of polar organic molecules can enter and leave HPA crystal. Such structural
flexibility is important when using HPA as a heterogeneous catalyst.

Fig. 10. Schematic diagram illustrating the structure of the hexahydrate H3PW12O406H2O as
two interpenetrating simple cubic structures. The H+ of an H5O2+ species coordinated to the
body centered KU is located at the midpoint of an edge of the conventional cubic cell. The KUs
are shown in polyhedral representation.[150]

The tertiary structure is the structure of heteropolyacids as assembled. The size


of particles, pore structure, surface area, and distribution of protons in the particles are
the elements of the tertiary structure.[14]

3.2 Properties of heteropolyacids

Heteropolyacids (HPAs), also know as polyoxometalates (POMs), are early


transition metal oxygen anion clusters that exhibit a wide range of molecular size,
compositions and architectures.[16,151]
A most attractive attribute of heteropoly compounds is the size dependence of their
physicochemical properties. Most notable is the size-dependent tendency of the metaloxygen framework to accommodate excess electrons.[140,152] Heteropoly compounds are
commonly strong oxidizing agents, which are readily reversibly reduced by addition of
various specific numbers of electrons depending upon the pH and the potential
employed. The ability of heteropoly compounds to accept electrons under alteration of
the optical properties can be use for the construction of functional electrooptical
materials.[153,154] The reduction products, which typically retain the general structures of
their oxidized parents, are characteristically deep blue in colour and comprise a vary
large group of complexes known as the poly blue, or heteropoly blue if the

27

framework includes heteroatoms.[155] Heteropoly blues corresponds to class II systems


in the Robin and Day classification of mixed-valence compounds. The added (blue)
electrons are delocalized over certain atoms or regions of the structure. The electron
delocalization is viewed as operating through two mechanisms[156]:
 a thermally activated electron hopping processes from one addendum (e. g. Mo
or W) atom to the next,
 a ground-state delocalization presumably involving -bonding through bridging
oxygen atoms from reduced metal atom to its neighbours.
The heteropoly blue provide important potentialities as specialized reducing agent, with
a wide range of controllable reduction potentials. Heteropoly blue are use as
electroreduction catalyst. By fixing the potential, one fixes the heteropoly blue species
involved and thus controls the number of electrons per reduction event.[147]
At the lattice energies of heteropoly compounds are low, and so are the salvation
energies of heteropoly anions, the solubility of heteropoly compounds largely depends
on the salvation energy of the cation. Heteropolyacids (HPAs) are extremely soluble in
water and oxygen-containing organic solvents such as lower alcohols, ethers, ketones,
ect. On the other hand, they are insoluble in nanpolar solvents such as benzene.[148] The
Keggin anions may be consider a nanoscale, isolated particle within an aqueous matrix,
which allows classification of Keggin type heteropolyacids as a strongly acidic particle
hydrate.[149,157] In aqueous solution H3PW12O40 (PW12), H4SiW12O40 (SiW12) and
H3PMo12O40 (PMo12) are strong fully dissociated acids, and there are stronger then the
usual mineral acids such as H2SO4, HCl, HNO3, ect. (Table 5).[18]

Table 5. Dissociation Constants of Heteropolyacids in Acetone at 25oC.[18]

The acid strength of crystalline heteropolyacids decrease in the series PW12 > SiW12 >
PMo12 > SiMo12 which is the same to that in solution (Table 5). The tungsten acids are
markedly stronger than molybdenum ones. Although, the effect of the central atom is no

28

as great as that of the addenda atoms, phosphorus-based heteropolyacids are slightly


more acidic than silicon based heteropolyacids.
A strong polarization of the outer electrons of the surface oxygen towards the
Mo6+ ions gives a strong Brnsted acidity to all surface oxygen, particularly the terminal
oxygen (Ot). As a result, the equilibrium reaction is shifted strongly the right to create a
high concentration of protons in hydrogen-bonded aqueous matrix with which the
anions are located (Equation 32).[149]

(32)

However, when the HPA has been fully dehydrated, the location of the protons is not as
easily defined. The terminal (M=Ot) and bridging (M-O-M) atoms of oxygen are the
most probable positions for the protons. The calculation were proved that the most
energetically favourable site for the acid proton is a bridging oxygen atom.[158]
The heteropolyacids are widely use as acid, redox, and bifunctional catalysts in
homogenous and heterogeneous system because of their high solubility in polar solvents
and fairly high thermal stability in the solid sate.[14,15,18] The thermal stability of
hydrogen forms of heteropolyacids change as follows: H3PW12O40 > H3PMo12O40 >
H4SiMo12O40 > H4SiW12O40.
The ability of heteropolyanions to undergo spontaneous adsorption from
aqueous solution on various electrode substrates[159,160] provides a simple tool for the
modification of the surface.[19-23] Further, their ability to exhibit fast reversible multielectron transfers and super-acid properties resulting in the increased availability and
mobility of protons at the electrocatalytic interface. Heteropolyacids have been known
as good matrix for traces of platinum reactive towards reduction of oxygen[19-21].
Because of interaction between heteropolyanions and Pt surface by mainly corner
oxygen (from heteropolyanions) only a few percent of interfacial reactive platinum
atoms would be blocked to the access of oxygen molecules.[21] Another issue concerns
ability of the adsorbed heteropolyanions (particularly H3PW12O40) to shift of
voltammetric peaks referring to the formation of Pt-oxo (PtOH or PtO) species towards
more positive potential and increase of the potential range where platinum is not

29

covered with platinum oxide adsorption and activation of oxygen molecules during
electrocatalysis may be facilitate.[21] Heteropolyanions due to their exceptionally high
solid state protonic conductivity were considering for fuel cell research.[23-25,27,28,161]
Stanis and co workers have presented that the addition of adsorbed heteropolyacids
can improved the performance of Pt anodes in a fuel cell under CO poisoned
conditions.[27]
Though, heteropolyacids have been identified to be good candidates as materials
for catalytic applications, the insolubility in water and increasing the surface area of
heteropoly compound are necessary. For this purpose, the mine approach has been
followed in the literature: the direct preparation of acid porous and water-insoluble salts.

3.3 Salts of the heteropoly compounds


Keggin type heteropolyacid salts, described by formula M1xHy-xM2M312O40,
where M1 is Cs+, Rb+, M2 is P or Si, M3 is W or Mo, x is 2.5 and y is 3 or 4 if M2 is P
or Si, respectively, are produced by partially exchanging protons in the parent
heteropolyacids. They are efficient solid acid catalyst for a variety of organic reaction,
particularly for liquid-phase reaction.[14,18,162]
Salts of heteropoly compounds can be classified into two groups[163]:
(1) group A, the small cation group (like Na+, Cu2+), which posses:
 low surface area (1 15 m2 g-1),
 high solubility in water,
 absorption capability of polar or basic molecules in the solid bulk,
(2) group B, the large cations group (like Cs+, Rb+), which is:
 with high surface area (50 200 m2 g-1),
 insoluble in water,
 unable to adsorb molecules.
Partial exchange of heteropolyacids with large cations, such as Cs+, Rb+, NH4+, K+, ect.
change a water-soluble acid with low surface area (<5 m2g-1) into a water-insoluble acid
salt precipitates with surface area exceeding 100 m2g-1.[31,32] Further, strong acidity
remains on acids salts what is opposite to alkali-exchanged zeolites.[14,33]

30

Primay
structure

Secondary
structure

W3O13

The crystal structure of


Cs salts are the same as

the
H+ (H2O)n, Cs2+,
Cu2+, K+, Mg2+, ect.

cubic

of

H3PW12O406H202,

with

cations at the sites of H+


(H2O)2

sites,

called

second structure, which


corresponds
Tertiary
structure

to

the

of

the

micocrystallites.
Aggregates

microcrystallites
called

the

are
tertiary

structures corresponding.
[14, 164]

Fig. 11. Hierarchical structure of Keggin


type heteropolyacids salts.[164,165]

Okuhara has presented the change of the surface area with the extent of Cs
substitution for proton in H3PW12O40 (Fig. 12).[162] The pore size of heteropolyacids
salts can be precisely controlled by the cation content. The surface are decrease when
the Cs content, x in CsxH3-xPW12O40 increase from 0 to 2, and then the surface are
increase when x change from 2 (1m2 g-1) to 3 (156 m2 g-1). The author has estimated the
acid amount on the surface (called surface acidity) from the surface area and the formal
concentration of proton attached to the polyanion. Figure 12 illustrates that the surface
acidity decreases at first with the content of Cs, but sharply increases when x exceeds 2.
The maximum appeared at x = 2.5. The Cs2.5H0.5PW12O40 and H3PW12O40 have similar
acid strength.[162,166]

31

Fig. 12. Changes in the surface area and surface acidity of CsxH3xPW12O40 as a function of the
Cs content.[162]

Okuhara and co workers have estimated from surface area the particles size of
the heteropoly aids and its salts.[160] The particles size were 2000 for H3PW12O40 and
5000-10000 for Cs1 (x = 1) and Cs2 (x = 2), respectively. Conversely, particle sizes of
Cs2.5 and Cs3 were 60-70 . Morphologies of the CsxH3xPW12O40 were examined using
scanning electron microscopy (Fig. 13). It was apparent that the surface of Cs2 is
smooth (Fig. 13A). The same observations were made for Cs1. On the contrary, Cs2.5 is
composed of fine particles with the size about 100 and the surface are rough (Fig.
13B). As well as the primary spherical particles, pores between particles can be seen for
Cs2.5. The authors obtained the similar SEM image for Cs3 to that of Cs2.5.

Fig. 13. SEM images of (A) Cs2HPW12O40 and (B) Cs2.5H0.5PW12O40.[160]

It is well know that the pore-width of zeolites can be controlled by the kind of
cation and the pore-width increased as the cation size decreased (Cs > Rb > K).[167] The
salts of Rb and K gave change in the surface area (Fig. 14) similar to that of Cs salts
32

(Fig. 12).[162] A marked increase of the surface area when the Rb content increases was
observed at x = 1.8, while it was detected at 2.1 for the Cs salts. In the case of K salts,
the change of the surface are with the increase of the content of K was rather loose.

Fig. 14. Surface areas of RbxH3xPW12O40 (A) and KxH3xPW12O40 (B) as a function of cation
content.[162]

Heteropoly salts are frequently more stable than the parent acid. The relative
stabilities, however, depended on the counteraction.[148] The thermal stability change
generally in the order of Ba2+, Co2+ < Cu2+, Ni2+ < H+, Cd2+ < Ca2+, Mn2+ < Mg2+ <
La3+,Ce3+ < NH4+ < K+, Tl+, Cs+.[14] The acidic cesium salt Cs2.5H0.5PW12O40 is more
stable than H3PW12O40. No decomposition of the salt was observed at 500 0C.
Due to the presence of meso-micropore in the Keggin type heteropolyacids salts
(particularly,

where

2.5),

it

is

possible

to

introduce

the

platinum

nanoparticles.[162,164] The size and dispersion of nanoparticles of Pt can be control by


quantity of platinum in the structure of heteropolyacids salt. Okuhatra and Nakato
reported that the presence of Pt 0.5 wt% in the Cs2.5H0.5PW12O40 did not influence the
pore width of these Cs salts, and the size of Pt was probably less than 10 .
The Keggin type heteropolyacids salts (particularly, when cation content is equal
2.5, e.g. Cs2.5H0.5PW12O40) are evidently a vary promising materials as matrix for
catalytic centres (for example Pt nanoparticles) for fuel cell research.

33

4. Experimental techniques

4.1 Cyclic voltammetry

Cyclic voltammerty (CV) is often the first experimental performed in an


electroanalytical study. In particular, it offers a rapid location of redox potentials of the
electroactive species, and convenient evaluation of the effect of media upon the redox
process.[168]
Cycling voltammetry consists of scanning linearly the potential of a stationary
working electrode immersed in a quiescent solution (Fig. 15) and measuring the
resulting current.[168-170]

Fig. 15. Potential time excitation signal in cyclic voltammetric experiment.[168]

In CV a constant-surface electrode (platinum, gold, glassy carbon, hanging


mercury drop electrode) are used as working electrodes.
During the change of the potential (when the oxidized form, O) from E1 to E2 (in
negative direction), a cathodic current begins to increase, until a peak is reached (Fig.
16). After traversing the potential region in which the reduction process take place, of
the potential sweep is reversed. During the reverse scan, R molecules (generated in the
forward half cycle, and accumulate near the surface) are deoxidised back to O and the
anodic peak results.[168]

34

Fig. 16. Typical cyclic voltammogram for a reversible O + ne- R redox process.[168]

In cyclic voltammetry for the reversible systems the position of the peaks on the
potential axis (Ep) is related to the formal potential of the redox process. The formal
potential for a reversible couple is centered between the anodic peak potentials (Ep,a)
and the cathodic peak potentials (Ep,c)[168]:

Eo =

E p,a + E p,c

(33)

The separation between the peak potentials (for reversible couple) is given by

E p = E p,a E p,c =

0.059
V
n

(34)

Thus, the peak separation ca be used to determinate the numbers (n) of electrons
transferred, as a criterion for a Nernstian behaviour. Accordingly, a fast one-electron
process exhibits a Ep of about 59 mV. Both the cathodic and anodic peak potentials are
independent of the scan rate. For irreversible process, the individual peaks are reduced
in size, widely separated and depended of the scan rate.

35

The peak current (ip) for a reversible electrode process is presented by the
Randles-Sevcik equation[168,169]:
ip = 2.72 x 105n3/2D1/2AV1/2c0

(35)

It follows from Eq. 35 that the peak current depends on the concentration of the
depolarized in the bulk of the solution (c0), the diffusion coefficient of the substance
being reduced or oxidized (D), the area of the electrode surface (A), and the number of
electrons taking parts in the elementary electrode process (n). Furthermore, the current
increase with the increasing polarisation rate (V). The liner dependence of the peak
current on the concentration of the reacting substance makes this method useful in
quantitative analysis. The peak dependent on the square root of the scan rate, and the
liner dependents means that the value of current is control by diffusion of electroactive
substance to the electrode surface.
Different behaviour is observed when the reagent or product of an electrode
reaction is adsorbed strongly or weakly on the electrode. The separation between the
peak potentials is smaller than expected for solution phase process. The ideal Nernstian
behaviour of surface-confined nonreacting species is manifested by symmetrical cyclic
voltammetric peaks (Ep = 0), and a peak half-width of 90.6/n mV (Fig. 17).

Fig. 17. Ideal cyclic voltammetric behaviour for a surface layer on an electrode. The surface
coverage, , can be obtained from the area under the peak.[168]

36

The peak current is directly proportional the surface coverage () and potential scan
rate[168]:
ip =

n 2 F 2 A
4 RT

(36)

The surface coverage, , can be calculate from the peak area (i.e., the quantity of charge
consumed during the reduction or adsorption of the adsorbed layer):

Q = nFA

(37)

This can be used for calculation the area occupied by the adsorbed molecule and hence
to predict its orientation of the surface.
In practices, the ideal behaviour is approached for a relatively slow scan rate, and for
adsorb layer that show non intermolecular interaction and fast electron transfer.[168]
The cyclic voltammetry method was used in the thesis for initial electrochemical
studies of Keggin type heteropolyacids salts and examination of proposed catalysts
towards oxidation of hydrogen, methanol and ethanol.

4.1.1 Rotating disk voltammetry


The rotating disk electrode (RDE) is vertically mounted in the shaft of the
synchronous controllable-speed motor and rotated with the constant angular velocity ()
about an axis perpendicular to the plan disc surface (Fig. 18).[168]

Fig. 18. Rotating disc electrode.[168]

37

The primary advantages gained by the utilization of electrochemical techniques based


on rotated electrodes is the precise, quantitative control

of mass transport to the

electrode through forced convection included by electrode rotation.[171] This is possible


because the motion of a RDE drags a layer of fluid near the disc surface along with it as
rotates. At the same time the liquid layers is subjected to centrifugal forces that cause to
move rapidly away from the rational axis of the electrode describing an S-shape path as
it does so. As a consequence of fluid motion parallel to the disk surface, new liquid is
drawn to the disc along the path that is parallel to the rotational axis of the electrode.
According to the simple Nernst diffusion layer concept, a thin layer of stagnant solution
is present at the electrode surface, within which the concentration of the electroactive
species that is undergoing oxidation or reduction varies linearly from its value in the
bulk solution to a new value at the electrode surface. The current, i, is given
approximately by the expression[171]:

i=

nFAD( c o c )

(38)

where A is electrode area, is the thickness of diffusion layer, F is the Faraday


constant, D is the diffusion coefficient, n is the number of electrons taking parts in the
elementary electrode process, co and c are the concentration of the electroactive species
in the bulk solution and at the electrode surface, respectively. For RDE in a solution
with the kinematic viscosity, , Levich presented that the diffusion layer thickness is
dependent on the inverse square root of the angular velocity of the rotating electrode:
= 1.61D1/31/6-1/2

(39)

The limiting current il (for a reversible system) is thus proportional to the square root of
the angular velocity, as described by Levich equation[169]:
il = 0.62nFAD2/31/2-1/6co

(40)

An increase in from 400 to 2500rpm thus results in a twofold increase of the signal. A
deviation from linearity of a plot of il vs. -1/2 suggests some kinetic limitations.
38

Since 1960 the rotating disc technique has been employed in the study of the
kinetics of electrode process, as well as of that of chemical reactions taking place at the
electrode surface.[169]
In the thesis rotating disc voltammetry was applied to study the kinetics of
hydrogen oxidation reaction (Chapter 7.2.1 and 7.3.4).

4.2 Chronoamperometry
Chronoamperometry[168] involves stepping the potential of the working electrode
from a value at which no faradic reaction occurs to a potential at which the surface area
concentration of the electroactive species is effectively zero (Fig. 19a). A stationary
working electrode and unstirred solution are used. The resulting current time
dependence is monitored. As mass transport under these conditions is solely by
diffusion, the current time curve reflects the change in the concentration gradient in
the vicinity of the surface. This involves a gradual expansion of the diffusion layer
associated with the depletion of the reactants, and hence decreased slope of the
concentration profile as time progress (Fig. 19b).
The current corresponding to the transformation of Ox in to Red, for linear
diffusion of reactants to the electrode, change with the time according to the Cottrell
equation[169]:

1/ 2
0
nFDOx
AcOx
il =
1/ 2 t 1/ 2

(41)

where, iL is the limiting current, i.e. the maximum current that can be obtained under the
given conditions. Its value depends on the bulk depolarized concentration (C0ox), the
diffusion coefficient (Dox), the electrolysis time (t), and the electrode surface area (A). F
is the Faraday constant, and n is the number of electrons exchanged between one ion or
molecule of a reactant an electrode. According to equation 41 the current of
chronoamperometric electrocatalysis tends to zero when the time tends to infinity. This
is due to the progressive decrease of the reactant concentration in the region close to the
surface, and change the current with time corresponds to the curve illustrates in Fig.
19c.

39

Fig. 19. Chronoamperometric experiments: (a) potential time waveform, (b) change of
concentration profiles with time, (c) the resulting current time response.[168]

In the thesis the chronoamperometry method was used to evaluate the reactivity
of our electrocatalytic system for the methanol (Chapter 8.2.3, 8.3.3) and ethanol
(Chapter 9.3) oxidation.

4.3 Staircase voltammetry


Staircase voltammetry[168,172] has been proposed as a useful tool for rejecting
background charging current. The potential time waveform involves successive
potential step (E) of c.a. 10 mV height and about 50 ms duration (tp) (Fig. 20). The
current is sampled at the end of each step, where the charging current has decayed to a
negligible value. This method of polarization of the electrode enable the double layer to
be charged, making it possible to discriminate capacitive current component, if the
current is measured at a sufficiently long time after application of the pulse. Such a
method of polarisation and current sampling should give current vs. potential curves
that are similar to those recorded in linear scan voltammetry.[169]

40

Fig. 20. Potential time waveform used in staircase voltammetry.[168]

In the thesis staircase voltammetry method was applied to get insight into the
systems reactivity towards oxidation of methanol and ethanol (Chapter 8.2.2, 8.3.2,
9.2).

4.4 Electrochemical impedance spectroscopy

Electrochemical impedance spectroscopy is an experimental technique that


involves imposing a small sinusoidal (AC) voltage or current signal of knows amplitude
and frequency - the perturbation to an electrochemical cell and monitoring the AC
amplitude and phase response of the cell. The AC perturbation is typically applied over
a wide range of frequencies, from 10 kHz or greater to less than 1 Hz, hence the name
impedance spectroscopy. The ratio and phase-relation of the AC voltage and current
signal response is the complex impedance, Z (j). The results of an impedance
spectroscopy experiment is a rich data set from which many properties of the
electrochemical cell may be extracted via application of physically responsible
equivalent circuit models.[36,173] Properties of the electrochemical system commonly
evaluated using impedance spectroscopy include ohmic (bulk) resistance, electrode
properties such as charge transfer resistance and double layer capacitance, and transport
(diffusion) effects.
An electrochemical impedance experiments is based on monitoring the AC
response of an electrochemical cell that results from imposing a small AC signal (Fig.
21). The impedance is the ratio of the AC voltage and current output.
41

Fig. 21. Schematic of an electrochemical impedance spectroscopy.[36]

sinusoidal

current

signal

of

amplitude

IAC

(amps)

and

frequency

(radiations/seconds) can be defined:

I() = IACsin (t)

(42)

where t is time (s). The output AC voltage signal from the electrochemical cell can be
defined:

V () = VACsin[(t)-]

(43)

where VAC is the amplitude for the output voltage signal (volts) and is the phase
angle (radians). The phase angle is the difference in the phase of a sinusoidal voltage
and current signals. In the case of AC signal, the resistance of circuit of the
electrochemical device, which is not purely resistive, will be function of the frequency
of oscillation of the input signal. Ohms Law for the AC case is expressed:

Z(j) = V(j) / I(j)

(44)

where Z (j) is the complex impedance () and j is imaginary operator,


j -1

(45)

Equation (44) indicates that impedance is a complex value. That is, it can take on both
real and imaginary components. Note that the imaginary component of the impedance is
a real measurable quantity: j is for bookkeeping purposes and allows description of
the out-of-phase component of the impedance. The complex relationship of impedance
is implicit so Z(j) is normally written as Z(). Although one can think of impedance as
resistance to current, it is more general than that because it takes into account the
phase difference between voltage and current. Equation (44) also indicated that
42

impedance depends on the frequency at which it is measured. Z can change as the


frequency of the AC signal changes.
Frequency in cycles per second, f (Hz = 1/s), is obtained through the relation:
= 2f

(46)

Equation (44) can be written in complex notation:

Z = Z + Z

(47)

where,
Z = Re(Z) = |Z|cos

real (in-phase) component of impedance

(48)

Z = Im(Z) = |Z|sin

imaginary (out-of-phase) component of impedance

(49)

Z = ( Z ) 2 + ( Z ) 2

magnitude of impedance

(50)

and,
= tan-1 (Z/Z)

(51)

In the impedance spectroscopy experiment, the frequency of the AC perturbation


is swept over a range, from ~ 10 kHz to less than 1 Hz and the impedance is evaluated
as a function of frequency to evaluate the properties of the electrochemical system
under investigation. Usually the real (Z) and imaginary (Z) parts of the impedance are
plotted as a function of frequency.
In the thesis the AC-Impedance was used to analyzed reaction mechanism of
methanol and ethanol electrooxidation on Pt40%/Vulcan XC-72 carbon modified with
Keggin type heteropolyacids salts (Chapter 8.2.4, 8.3.4, and 9.4).

4.5 Transmission electron microscopy

The fathers of electron microscopy were Knoll and Ruska (1931), and the first
commercial TEM was built in 1939 by Siemens. Since then, the theory and the
instrumentation have developed and modern TEMs have become a fundamental tool
for material science.[174]

43

A TEM microscope is composed by an optical column, operated under high


vacuum that enclose[175]:

 Illumination system. It takes the electrons from


the gun and transfers them to the specimen
giving either a broad beam or a focused beam. In
the ray-diagram, the parts above the specimen
belong to illumination system.
 The objective lens and stage. This combination
is the heart of TEM.
 The TEM imaging system. Physically, it
includes the intermediate lens and projector lens.

Fig. 22. Schamatic of a Transmition Electron Microscope.[175]

The diffraction pattern and image are formed at the back focus plane and image plane of
the objective lens. If we take the back focus plane as the objective plane of the
intermediate lens and projector lens, we will obtain the diffraction pattern on the screen.
It is said that the TEM works in diffraction mode. If we take the image plane of the
objective lens as the objective plane of the intermediate lens and projector lens, we will
form image on the screen. It is the image mode.
TEM is applied to analysis of electrochemical power sources, since novel
electrode materials for electrochemical energy storage devices are currently synthesized
with constantly smaller dimensions, down to nanosize level. This is very important in
catalysts used for fuel cells, since smaller particles have higher specific surface and
catalytic activity. Control of morphology, granulometry and microstructure at
nanometric level is, thus, very important in predicting or explaining the performances
obtained by the different electrodes or preparation methodologies.
In the thesis TEM was used to investigate size of Pt nanoparticles obtained by
corrosion of platinum counter electrode (Chapter 7.3.3).

44

4.6 Scanning electron microscopy

In Scanning Electron Microscopy (SEM), a high energy (up to 50 keV), very


thin electron beam is finely focused over a sample and swept in a raster across the
surface. The electron beam/sample interactions cause the emission of different signals
that are collected by specific detectors and converted into an image of the sampled area
and viewed or recorded on a cathode ray tube (CRT). The generated signals include
secondary electrons, backscattered and Auger electrons, photons of various energies and
characteristic X-rays. The signals of greatest interest for surface topography are
secondary and backscattered electrons.[174] The basic components of the SEM
microscope are presented in Fig. 23.

Fig. 23. Schematic of operation a typical Scanning Electron Microscope.[174]

The SEM permits the observation of materials in macro and submicron ranges. When
SEM is used in conjunction with EDS (Energy Dispersive X-ray Spectrometer) the
analyst can perform an elemental analysis on microscopic sections of the material or
contaminants that may be present.

45

In the thesis the scanning electron microscopy was used to investigate


morphology of the Keggin types heteropolyacids salts (Chapter 6.3).

4.7 Infrared spectroscopy


Infrared spectroscopy (IR) involves examination of the twisting bending,
rotating and vibrational motions of atoms in a molecule.[170]
Molecules contain bonds of specific spatial orientation energy. These bonds are
seldom completely rigid, and when is supplied, they may band, distort or stretch. A vary
approximate model compares the vibration to that of a harmonic oscillator, such as an
ideal spring. If the spring has a force constant, k, and masses mA and mB at the end, than
the theoretical vibration frequency is given by[176]:
= (1/2)(k/)

(52)

where = mA mB / (mA + mB) is called the reduced mass.


Each type of molecular vibration is characterized by a vibrational quantum
number, . For a simple stretching vibration, there is a series of levels whose energy is
given by approximately by:

E = h0( + )

(53)

This means there is a set of levels spaced energy by h0 or in wavenumber by 0. The


selection rule for an ideal harmonic oscillator allows transition where = 1, giving a
single, fundamental vibrational absorption peak.
However, when the bonds are stretched they weaken, so better model takes this
into account, and the molecules are treated as anharmonic oscillators. Thus, where high
energies are involved, larger energy transition may occur, where = +2, +3, ect.
giving the first overtone at wavenumber approximately double that the fundamental,
and so on.
The electric field of incident radiation interacts with the molecular dipole. When
the frequency of the radiation (~1013 Hz) resonates with a molecular vibration,
absorption can occur, particularly if excitation of that vibration has an effect on the

46

molecular dipole moment. The energy changes involved in exciting vibrational modes
in this way correspond to the infrared spectral region. A full infrared spectrum consists
of bands (group frequencies), assignable to particular moieties (e.g. -CH2-, -CH3, C=O),
in characteristic frequency regions that are relatively independent of the other groups in
the molecule. Since infrared spectroscopy probes molecular vibrations that involve
changes in the dipole moment, the vibrations of polar molecular bonds generally
correspond to strong infrared bands.
Most IR spectra are recorded by measuring the absorption of the incident
radiation as a function of wavelength (wavenumber) in the range of 2.5 - 25 m (4000 400cm-1) by solid, liquid or gaseous samples. Both qualitative and quantitative
information can be obtained from vibrational spectra. The use of IR spectrometry for
qualitative measurements is extensive and wide ranging, and for this purpose
transmission spectra are conventionally recorded as function of wavenumber. In order
to make quantitative measurements, it is necessary to convert the transmittance readings
to absorbance, A, the relation between the two being[176]:

A = log (100 / T%)

(54)

In the thesis infrared spectroscopy was used as an established tool for the
structural characterization of heteropolyacids salts (Chapter 6.2).

47

5. Chemical reagents and measuring equipment

A) Chemical reagents using in the measurements:

Phosphotungstic acid hydrate, H3PW12O40nH2O (PW12), Sigma-Aldrich


Phosphomolybdic acid hydrate, H3PMo12O40 nH2O (PMo12), Sigma-Aldrich
Tungstosilicic acid hydrate, H4SiW12O40nH2O (SiW12), Sigma-Aldrich
Silicomolybdic acid hydrate, H4SiMo12O40nH2O (SiMo12), Sigma-Aldrich
Cesium nitrate, CsNO3, Aldrich
Rubidium nitrate, RbNO3, Aldrich
Ammonium Chloride, NH4Cl, Carlo Ebra
Potassium chloride, KCl, Aldrich
Sulphuric acid 99,999%, H2SO4, Aldrich
Methanol 99, 9%, CH3OH, J. T. Baker
Ethanol 99, 9%, C2H5OH, J. T. Baker
Nafion solution 5% wt, Ion Power, Inc
Pt10% on Vulcan XC-72 (Pt/C), E-tek
Pt40% on Vulcan XC-72 (Pt/C), E-tek
Vulcan XC-72, E-tek
High purity argon, carbon monoxide, hydrogen, oxygen gas
Ultra-pure water (Millipore Milli-Q)

B) Equipments used during performed experiments:


 IR spectra in the range 1800 to 500 cm-1 were recorded with a Perkin
Elmer System 2000 FT-IR instrument.
 The morphology of platinum particles was monitored using a JEM2100F electron microscope (TEM) operating at 200 kV.
 The morphology of heteropolyacid salts was monitored using a JOEL
Model JSM-5400 scanning electron microscope (SEM).
 Electrochemical measurements were carried out by CHI 660B
electrochemical working station (CH Instruments Inc.).

48

 RDE voltammetric measurements were done using a variable speed


rotator, Pine Instruments, USA.
 For the electrochemical impedance studies, the data were collected by
CHI 660B with a frequency sweep of 0.05 Hz to 100 KHz and ac sine
wave amplitude of 5 mV.
 The PEMFC test stand consists of fuel cell hardware, backpressure
regulators, water traps, a humidifier and mass flow controller. The fuel
cell hardware (Fuel Cell Technologies Inc.) is a single cell with area 4.84
cm2 and single-serpentine flow fields.

C) Electrodes applied during the measurements:


 Glassy carbon electrode (as working electrode), GC (area 0.071cm2), CH
Instruments, Inc.
 Rotating disc (glassy carbon) electrode (as working electrode), RDE
(area 0.1256cm2), Pine Researcher Instrumentation.
 A saturated calomel electrode (as references electrode), SCE, Amel
Electrochemistry
 Platinum flag (as counter electrode, area ca. 1cm2)
 Nafion Membrane 115 (as solid electrolyte in PEM cell), Ion Power, Inc.
 Low-temperature ELAT GDL microporous layer on woven web, tin
configuration (as diffusion layer in electrode for fuel cell), E-tek

D) Experimental conditions:

 The measurements were carried out in a three-electrode cell with a


platinum flag as a counterelectrode and a saturated calomel electrode
serving as the reference electrode, placed in a separated compartment
and connected to the main cell by a Luggin capillary.
 CO stripping voltammetry study: prior to electrochemical measurements
0.5 mol dm-3 sulphuric acid solution was purged with argon for 30
minutes. Subsequently, five consecutive CV (scan rate 20 mV s-1) were
performed in the potential range 0.025 1.125 V vs. RHE. For CO

49

stripping measurements, pure CO was bubbled into the electrolyte for 10


minutes and then its adsorption on the electrode was driven under
potential control at 0.1 V vs. RHE for 4 minutes. The electrolyte was
purged for 35 minutes with argon, keeping electrode potential at open
circuit potential (OCP) to eliminate CO reversibly adsorbed on the
surface. Five cyclic voltammetry (scan rate 20 mV s-1) were recorded
from 0.025 to 1.125 V versus RHE. The first anodic sweep from 0.025 to
1.125 V vs. RHE was performed to electro-oxidize the irreversibly
adsorbed CO and the subsequently voltammetries in order to verify the
completeness of the CO oxidation.
 At the beginning of experiments, each catalytic layer was cycled
continuously (san rate, 50 mV s-1) through the potential region from 0 to
1.05 V vs. RHE until a steady state voltammogram was obtained
 Before experiment working electrode was polished (on a cloth) with
Al2O3 water suspension, particle size 5 - 0.05 m.
 All the electrochemical experiments were carried out at 22 2 0C (except
PEMFC measurements).
 All potentials in these studies were reported here versus RHE.

50

6. Preparation and characterization of Keggin-type matrix


This thesis is focused on applying salts of Keggin-type heteropolyacids as a
material for the new stable, water-insoluble matrix for the films containing Pt
nanoparticles. From several possible salts of Keggin-type heteropolyacids those
containing 2.5 moles of Cs+, Rb+ and NH4+ cations in 1 mole of the heteropolyacids salt
have been chosen. Advantages of these salts are the highest surface acidity, high ionic
conductivity, water insolubility and high surface area characterized by the presence of
meso and micro pores.

6.1 Preparation of Keggin-type heteropolyacid salts

Keggin-type heteropolyacids salts were prepared by adding stoichiometric


amounts of 0.25 mol dm-3 aqueous solution of CsNO3, RbNO3 or NH4Cl, to the desired
volume of 0.1 mol dm-3 aqueous solution of desired heteropolyacid[177-180], using a
molar ratio M/Y = 2.5, (where M = Cs+, Rb+ or NH4+ and Y = P or Si). The suspension
was then stirred for 24 h. The precipitates was washed four times with ultra pure water,
separated from the liquid phase by centrifugation and freeze dried (40 - 75 0C).

6.2 IR characterization of Keggin-type matrix


IR

spectra

of

H3PW12O40

(HPW),

Cs2.5H0.5PW12O40

(Cs2.5PW)

and

Rb2.5H0.5PW12O40 (Rb2.5PW) are shown in Fig. 24A. Four bands at 700-1100 cm-1
region corresponding to Keggin unit structural vibrations[181,182] are observed for all
samples what suggesting that the framework of the primary Keggin structure remained
unaltered. The origin of the Keggin anion vibration bands is as follows: at 1077 cm-1 is
from the as (P-Oa) vibration; 971 cm-1 is due to the terminal as (W=Od) vibration; at
883 and 756 cm-1 should be assigned to as (W-Ob-W) and as (W-Oc-W), respectively.
Weaker absorptions appearing at 592 and 523 cm-1 are due to bending vibrations of the
type (Oa-P-Oa) and s (W-O-W), respectively.[183] The absorption at c.a. 1697 cm-1 is
indicative of the presence of the protonated water clusters, probably proton-type H5O2+,
and it is assigned to (H2O) vibration.[178,184] The proton substitution with Cs+ or Rb+
ion to form M2.5H0.5PW12O40 (M = Cs+, Rb+) causes a decrease of the intensity of the

51

(H2O) peak at 1697 cm-1. Absorption band detected at 1620 cm-1 for cesium and
rubidium salt of 12-phosphotungstic acid can be attributed to the presence of neutral
water.[178]
Fig. 24B shows the IR spectra of 12-phosphomolybdic acid, H3PMo12O40
(HPMo) as well as its cesium and rubidium salts. There is no apparent difference
between the three spectra. All showed bands at 1060, 961, 875, 760 cm-1 that are in
agreement with those reported in the literature.[22,185-187] A shift in the frequency in the
oxygen Mo-Ob-Mo stretching mode from 875 cm-1 (for HPMo) to 865 cm-1 (for
Cs2.5H0.5PMo12O40 or Rb2.5H0.5PMo12O40) is probably related to the organization and in
particular to the presence of positively charged cation in the material. The absorption at
1610 cm-1 is related to the presence of neutral water.[178]
The IR spectra recorded for Fig. 24C shows the 12-silicotungstic acid,
H3SiW12O40 (HSiW) and its cesium and rubidium salts, while Fig. 24D shows the IR
spectra of 12-silicomolybdic acid, H3SiMo12O40 (HSiMo) and their cesium and
rubidium salts. The band around 1700 cm-1 (Fig. 24C) for HSiW is due to oxonium ions
(H3O+) or more likely to dioxonium ions (H5O2+).[188,189] As in the case of HPW, proton
substitution with Cs+ or Rb+ causes a decrease of the intensity of the peak at 1700 cm-1.
The absorption band at c.a. 1624 cm-1 is indicative of the presence of neutral water.
From the spectrum of HSiW and their cesium and rubidium salts in the 700-1100 cm-1
region, we can obtain information on the bonds between Keggin units.[190] The bands at
ca. 730 and 871 cm-1 were assigned to the stretching of tungsten-oxygen-tungsten
chains, the former to W-Oc-W, and the latter to W-Ob-W. The Oc oxygen atom is
common for two [WO6] octahedra in [W3O10] subunits, joined by Ob atoms. The band at
ca. 905 cm-1 was assigned to Si-Oa stretching (there are four Oa atoms connected to the
central Si atom). The absorption at 970 cm-1 is related to the W=Od bond. The
assignments of the bond at ca. 1020 cm-1 is not known.
In the spectra of HSiMo (Fig. 24D) and its cesium and rubidium salts, we can
see four bands at 700-1100 cm-1 region corresponding to Keggin unit structural
vibrations. This means that, also in this case, the structure of the salts still retains the
basic framework of the Keggin structure.

52

A
Rb 2.5 H 0.5PMo 12 O 40

R b 2 .5 H 0 .5 P W 1 2 O 4 0
883

1620
1077
883
592
975
760

865
591

523

760

C s 2 .5 H 0 .5 P W 1 2 O 4 0

1060

592

975

523

961

Transmittance

1077

Transmittance

1610

1620

760

1610

Cs 2.5 H 0.5PMo 12 O 40
1060

865
591

961

760

1697
1610
1060

1077
883
971

H 3P W 12O 40

1800

1600

1400

1200

1000

W avenum ber / cm

875

H 3 PMo 12 O 40

756

592
523

800

600

590

961
1800

1600

-1

1400

1200

760

1000

W avenum ber / cm

800

1020

162 4

1614

R b 2 .5 H 1.5 S iW 12 O 40

R b 2.5 H 1.5 S iM o 12 O 40

97 0
8 71
91 0

959
851

735

900

1020

162 4

Transmittance

Transmittance

600

-1

C s 2.5 H 1.5 S iW 12 O 40
97 0

87 1

740

1612

C s 2.5 H 1.5 S iM o 1 2 O 40
959

910

900

735

851
740

102 1
1700
964

1610

9 70
9 05 8 71

H 4 S iW 12 O 40

H 4 S iM o 12 O 40
727

851
901

180 0

1600

1400

1 200

1000

W avenum ber / cm

800

600

1800

1600

-1

1400

1200

1000

W avenum ber / cm

740
800

600

-1

Fig. 24. IR spectra of the: A) H3PW12O40 and their cesium and rubidium salts (Cs2.5H0.5PW12O40,
Rb2.5H0.5PW12O40), B) H3PMo12O40 and their cesium and rubidium salts (Cs2.5H0.5PMo12O40,
Rb2.5H0.5PMo12O40), C) H4SiW12O40 and their cesium and rubidium salts (Cs2.5H1.5SiW12O40,
Rb2.5H1.5SiW12O40)

and

D)

H4SiMo12O40

and

their

cesium

and

rubidium

salts

(Cs2.5H1.5SiMo12O40, Rb2.5H1.5SiMo12O40) recorded at ambient temperature.

53

We can conclude from the results that the primary Keggin structure remains
unaltered even when the protons form parental heteropolyacid are substituted by the
cesium or rubidium cations. The peak at ca. 1700 cm-1 in the HPW and HSiW IR
spectra is due to the presence of dioxonium ions (H5O2+) and their relative intensity
decay is observed upon proton substitution by Cs+ or Rb+ cation. Such pattern is
observed here because the hexahydrate structures isomorphous with H3PW12O406H2O
also exist in other dodecaheteropolyacids, like tungstosilicic acids in which only three
of four protons are forming dioxonium ions. Thus their proper formula is
(H5O2+)3(HSiW12O403-) as described in the literature.[190]

6.3 SEM characterization of Keggin-type matrix


Scanning electron micrographs (SEM) of pure 12-phosphotungstic acid, 12phosphomolybdic acid, 12-silicotungstic acid, 12-silicomolybdic acid and their cesium
and rubidium salts are shown in Fig. 25, Fig. 26, Fig. 27 and Fig. 28, respectively. The
SEM image of pure phosphotungstic acid (HPW) reveals the presence of a (Fig. 25A)
mixture of small (micro size) crystals together with few larger crystals.[191,192] The SEM
micrograph of Cs2.5H0.5PW12O40 (Fig. 25B) shows that the bulk salt consists of
agglomerates of smaller nanocrystals. The nanosize spherical aggregates of bulk
Rb2.5H0.5PW12O40 (Fig. 25C) appear to be bigger than those of Cs2.5H0.5PW12O40.
Fig. 26A shows the SEM micrograph of the pure phosphomolybdic acid (HPMo)
in which arrays of uniformly small crystals are observed. The SEM micrograph of pure
HPMo suggests a more uniform crystal texture as compared to that of pure HPW. The
presence of Keggin structure is not so prominent in HPMo as compared to HPW
because molybdenum (Mo) atom is of smaller size, Cs2.5H0.5PMo12O40, when compared
to tungsten (W). Both salts consist of aggregates composed of small spherical
nanocrystals grains that appear to be smaller for Cs2.5PMo12 than for the analogous
rubidium salt.

54

Fig. 25. SEM micrographs of

Fig. 26. SEM micrographs of

A) H3PW12O40 (3000x magnification),

A) H3PMo12O40 (3000x magnification),

B) Cs2.5H0.5PW12O40 (8000x magnification),

B) Cs2.5H0.5PMo12O40 (8000x magnification),

C) Rb2.5H0.5PW12O40 (8000x magnification).

C) Rb2.5H0.5PMo12O40 (8000x magnification).

55

Fig. 27. SEM micrographs of

Fig. 28. SEM micrographs of

A) H4SiW12O40 (3000x magnification),

A) H4SiMo12O40 (3000x magnification),

B) Cs2.5H1.5SiW12O40 (8000x magnification),

B) Cs2.5H1.5SiMo12O40 (8000x magnification),

C) Rb2.5H1.5SiW12O40 (8000x magnification).

C) Rb2.5H1.5SiMo12O40 (8000x magnification).

The SEM image of pure silicotungstic acid (Fig. 27A) and silicomolybdic acid
(Fig. 28A) shows sizeable agglomerates containing mixture of micro size crystals. In
contrast, the cesium and rubidium salts of HSiW and HSiMo are composed of fine

56

particles. Smaller particles are obtained for Rb+ than for Cs+ salts of HSiMo and HSiW
(Fig. 27, 28), what is opposite to cesium and rubidium salts of HPW and HPMo (Fig.
25, 26).
In conclusion, we have to note that the surface state and microstructure of Cs+
and Rb+ salts are in strict contrast with heteropolyacids. The relatively smallest particles
were obtained for cesium salt of tungsten heteropolyacid (Fig. 25B).

6.4 Cyclic voltammetry characterization of Keggin-type matrix

In order to prepare inks for cyclic voltammetric characterization, 0.02 g of


cesium, rubidium and ammonium salts of 12-phosphotungstic acid, (HPW), 12phosphomolybdic acid, (HPMo), 12-silicotungstic acid, (HSiW) or 12-silicomolybdic
3
acid, (HSiMo) (described by the general formula M1x H yx M 2 M 12
O 40 , where M1 is Cs+,

Rb+ or NH4+ and M2 is P or Si, M3 is W or Mo and x is 2.5 and y is 3 or 4 if M3 is P or


Si, respectively) was mixed with Nafion (5% alcoholic solution) and ethanol (>99.9%)
as a solvent and left for 12 hours on the magnetic stirrer. Next 3 l of the suspension
was dropped on the glassy carbon electrode surface (GC) and left for 30 minutes to dry.
Cyclic voltammetric response of investigated heteropolyacid salts deposits on
glassy carbon electrode recorded in argon saturated 0.5 mol dm-3 H2SO4 (scan rate: 50
mV s-1) are presented in Fig. 29.
Fig.

29a

shows

typical

cyclic

voltammogram

for

Keggin-type

12-

phosphotungstic acid. The two couples of peaks at potentials -27 mV and 240 mV
correspond to two redox reactions and can be described in terms of two consecutive
reversible one-electron processes[20,21,193]:
VI

3-

VI

PW12 O40 + ne + nH HnPWn W12-n O40

3-

(55)

where n is equal to 1 or 2. Voltammograms recorded for cesium (Fig. 29b), rubidium


(Fig. 29c) and ammonium (Fig. 29d) salt of tungsten heteropolyacid are slightly
different from those obtained for H3PW12O40. In the cyclic voltammogram of
Cs2.5H0.5PW12O40 and Rb2.5H0.5PW12O40 instead of two couples of peaks only one peak
at circa 68 mV can be seen in the potential range from 0.2 to 0.85 V. Thus the peaks
characteristic of salts are shifted towards lower potentials in comparison to the original
tungsten heteropolyacid and that only the first reduction can be observed in the potential
57

window examined. A different behavior is observed for ammonium salt of HPW,


((NH4)2.5H0.5PW12O40). In the Fig.29d we see two couples of peaks at 23 mV and 235
mV. This voltammogram is similar to that of pure HPW and may indicate that the salt is
partially soluble in aqueous solution of H2SO4 thus releasing the acidic anion.
Cyclic voltammogram of 12-phosphomolybdic acid (HPMo) is presented in
the Fig. 29e. In this case we can see three couples of peaks at 280, 445 and 640 mV.
These peaks correspond to the three consecutive two-electron processes that can be
described by the following reaction[21,22,187]:
VI

3-

VI

PMo12 O40 + ne + nH HnPMon W12-n O40

(56)

where n is equal to 2, 4 or 6. Fig. 29f-h illustrates the cesium (Cs2.5PMo12), rubidium


(Rb2.5PMo12) and ammonium ((NH4)2.5PMo12) salt of HPMo. In all these
voltammograms we observe three couples of peaks like in parental 12phosphomolybdic acid, but only for Cs2.5PMo12 the peaks are shifted towards less
positive potentials values (from 640 to 570 mV, from 445 to 400 mV and from 280 to
210 mV). The cyclic voltammogram of (NH4)2.5H0.5PMo12O40 is very similar to that
obtained for unmodified H3PMo12O40.
A typical cyclic voltammogram for Keggin-type silica heteropolyacid,
H4SiW12O40 (HSiW) is shown in Fig. 29i. The two couples of peaks that are present in
the cyclic voltammogram at potentials -170 mV and 42 mV correspond to two redox
reaction and can be described in terms of two consecutive reversible one-electron
processes[20,193]:
VI

4-

VI

SiW12 O40 + ne + nH HnSiWn W12-n O40

4-

(57)

where n is equal to 1 or 2. In Fig. 29j we can see that for Cs2.5SiW peaks are shifted
towards less positive potential values (from 42 to 25 mV and from 170 to 220 mV).

58

0.6

0.04

0.05

0.3

0.00

-0.05

-0.3

-0.04

-0.6
0.03

0.2

-2

-0.2

0.2
0.0

-0.03

-0.2

-0.06

0.1

-0.10

0.00

0.0

j / mA cm

0.00

0.0

0.1

-0.4
0.2

0.0

0.0

-0.1

-0.2

0.0

-0.1

-0.2

0.2

0.6
0.3

0.0

-0.4
0.05
0.00

0.0

-0.05

-0.3

-0.2

-0.6

-0.2

0.0

0.2

0.4

0.6

0.2

0.8

E / V vs. RHE

0.4

0.6

0.8

-0.10
-0.2 0.0 0.2 0.4 0.6 0.8

E / V vs. RHE

E / V vs. RHE

0.3

Fig.29. Cyclic voltammetric response of


0.0

(a) H3PW12O40, (b) Cs2.5H0.5PW12O40,

-0.3

j / mA cm

-2

(c) Rb2.5H0.5PW12O40, (d) (NH4)2.5H0.5PW12O40,

em

-0.6
0.2

(g) Rb2.5H0.5PMo12O40, (h) (NH4)2.5H0.5PMo12O40,

0.0

(i) H4SiW12O40, (j) Cs2.5H1.5SiW12O40,


(k) Rb2.5H1.5SiW12O40, (l) (NH4)4SiW12O40,

-0.2

fn

-0.4
0.2

0.4

0.6

0.8

-2

(m) H4SiMo12O40, (n) Rb2.5H1.5SiMo12O40,


(o) Cs2.5H0.5SiMo12O40
deposits on glassy carbon electrode.

E / V vs. RHE
j / mA cm

(e) H3PMo12O40, (f) Cs2.5H0.5PMo12O40,

Electrolyte: argon saturated 0.5 mol dm-3 H2SO4.

0.02

Scan rate: 50 mV s-1.


0.00
-0.02

go

-0.04
0.3

0.4

0.5

0.6

0.7

0.8

E / V vs. RHE

59

This behavior is not observed for rubidium (Rb2.5SiW12) and ammonium


((NH4)4SiW12) salts of 12-silicotungstic acid. Fig. 29l shows, instead of cyclic
voltammogram of (NH4)2.5H1.5SiW12O40 ((NH4)2.5SiW12), voltammetric response of
(NH4)4SiW12O40. Having in mind the fact that ammonium salt of 12-silicotungstic acid
containing 2.5 moles of NH4+ is completely soluble in water, it cannot be used as a
matrix material.
Fig. 29m shows a typical cyclic voltammogram of Keggin-type 12silicomolybdic acid. The three couples of peaks at potentials 270 mV, 450 mV and 550
mV correspond to three consecutive redox processes each involving two-electron[20,194]:
VI

4-

VI

SiMo12 O40 + ne + nH HnSiMon W12-n O40

4-

(58)

where n is equal to 2, 4 or 6. The cyclic voltammetric responses of Rb2.5H1.5SiMo12O40


(Rb2.5SiMo12) and Cs2.5H1.5SiMo12O40 (Cs2.5SiMo12) are presented in Fig.29n and
Fig.29, respectively. Three peaks located at potential similar to those of HSiMo are seen
for Rb2.5SiMo. In the potential range studied, only two couples of peaks can be
observed for Cs2.5SiMo12. The cyclic voltammetric response of ammonium salt of
HSiMo is not presented because (NH4)2.5H1.5SiMo12O40 is completely soluble in water.
Full substitution of all the protons in the 12-silicomolybdic acid to produce
(NH4)4SiW12O40 also results into a completely soluble product.
Some of the voltammograms recorded for investigated materials deposited on the glassy
carbon electrodes shows similar behavior to those voltammograms obtained for their
analogues in the solution. It is due to partial solubility in solution.
It can be concluded, judging from CV measurements, that the most promising
materials for the anode matrix in fuel cells are cesium salts of Keggin-type
heteropolyacids (HPA). It seems that rubidium salt of HPA could also be of practical
importance. Ammonium salts of Keggin-type heteropolyacids are certainly less
attractive because they are more soluble in comparison to cesium and rubidium salts.

60

6.5 CONCLUSIONS
1) The results obtained using Infrared Spectroscopy technique (IR) demonstrate
that the primary Keggin structure remains unaltered when the protons existing in
parental heteropolyacid (HPW, HPMo, HSiW, HSiMo) are substituted with cesium or
rubidium cations (Cs2.5PW12, Rb2.5PW12, Cs2.5PMo12, Rb2.5PMo12, Cs2.5SiW12,
Rb2.5SiW12, Cs2.5SiMo12, Rb2.5SiMo12). The peak at c.a. 1700 cm-1 in the HPW and
HSiW IR spectra due to dioxonium ions (H5O2+) decreases in intensity with increasing
the number of protons substituted by Cs+ and Rb+ cation.
2) Images obtained using Scanning Electron Microscope (SEM) clearly show
that cesium and rubidium substituted Keggin-type heteropolyacids posses higher surface
area than theirs parental heteropolyacids. Consequently formation of small spherical
crystallites where proton in HPA is substituted by cesium or rubidium cations is
feasible.
The smallest nanoparticles were obtained when protons in Keggin-type 12phosphotungstic acid were substituted by cesium cations (to produce Cs2.5H0.5PW12O40).
3) The voltammograms indicate that the most promising material for the anode
matrix in fuel cells are salt of Keggin-type heteropolyacids containing cesium and
rubidium cations.
4) Results obtained here show that, relatively high solubility in the water,
ammonium salts of HPAs are less attractive than their cesium or rubidium salt
analogues. This observation is of practical importance when it comes to preparation of
catalytic layers for fuel cells.
5) On the basis of our results described in this chapter, the salts of Keggin-type
heteropolyacids containing 2.5 moles of cesium and rubidium cations in 1 mole of the
heteropolyacids salts (Cs2.5PW12, Rb2.5PW12, Cs2.5PMo12, Rb2.5PMo12, Cs2.5SiW12,
Rb2.5SiW12, Cs2.5SiMo12, Rb2.5SiMo12) have been chosen for future research.

61

7. Hydrogen oxidation reaction (HOR)


on the catalytic layers containing Cs2.5PW12 matrix
This chapter is devoted to the development of a catalyst consisting of Pt
nanoparticles supported on insoluble salts of Keggin-type heteropolyacids to be used for
hydrogen oxidation reaction (HOR). Two methods of preparation of catalytic layers are
described through mixing and the electrochemical method. The best systems in each
preparation method contained a new type of matrix as demonstrated and compared to
unmodified commercial carbon supported platinum catalyst using rotating disc electrode
(RDE) voltammetry. High resolution transmission electron microscopy (HRTEM) has
been used to study the dispersion platinum nanoparticles deposited on the matrix by
using electrochemical method. CO stripping voltammetry has also been applied to
estimate the active surface of Pt existing in the catalytic layer (prepared by
electrochemical method).

7.1. Preparation of the catalytic layers

7.1.1. Mixing method


The steps followed for the preparation of composite catalytic layers by mixing is
shown schematically in Fig. 30. A suspension in ethanol of Pt10%/Vulcan XC-72
carbon and heteropolyacid salt (Cs2.5H0.5PW12O40) was mixed with know amount of
Nafion (5% alcoholic solution) and stirred in a close vial for 12 h. The mass ratio
between Pt10%/Vulcan XC-72 : heteropolyacids salts : Nafion was 1:2:1.1,
respectively. A portion of the resulting ink was then dropped using micropipette on to
the surface of glassy carbon electrode (RDE electrode) in such way to obtain Pt loading
equal 30 g cm-2. The resulting catalytic layer was left to dry for 30 min. at room
temperature. For comparison, the heteropolyacid salt-free ink of Pt10%/Vulcan XC-72
carbon and Nafion was also prepared.

62

Ethanol
Nafion

Pt 10%/C Cs2.5PW12
Mixing for 24h

Cs2.5H0.5PW12O
Pt on Vulcan
Nafion

Glassy carbon

Pt 10%/C
Cs2.5PW12 with
Nafion

Fig. 30. Schematic of the preparation of a composite catalytic layer by mixing.

7.1.2. Electrochemical method


To prepare the matrix for electrochemical plating the Cs2.5H0.5PW12O40 was
mixed with Vulcan XC-72 carbon, Nafion solution (5% of aliphatic alcohols) and
ethanol. After 12 hours of mixing (under magnetic stirring) desired amount of the
suspension was dropped on the glassy carbon rotating disc electrode (RDE) surface and
left for 30 minutes to dry. The best results were obtained when the catalytic ink was
prepared by mixing Cs2.5H0.5PW12O40 with Vulcan XC-72 carbon and Nafion in the
following proportion 2:1:1.1.
A standard three-electrode cell (described previously in the chapter 5) was used
to prepare films and to perform other electrochemical measurements. A platinum flag
served as a counter electrode; a saturated calomel electrode (SCE), placed in a separated
compartment and connected to the main cell through a Luggin capillary, was used as
reference electrode.
Preparation of catalytic layer Pt-Cs2.5H0.5PW12O40 with Vulcan XC-72 carbon
and Nafion was accomplished by cycling (2500 cycles) the electrode between -0.05 V

63

to 1.05 V vs. RHE at scan rate 50 mV s-1 in a solution of 0.5 M of H2SO4 containing 5
10-3 M KCl. During cycling the counter electrode can reach very anodic potentials
causing partial oxidation of the Pt flag. The Pt ions may eventually deposit on the
-

working electrode. The presence of ions Cl in the solution helps the process, and
decrease of the standard oxidation potential Pt/Pt(II), E0 = 1.2 V vs. RHE, by formation
of complexes[195]:
2-

2-

PtCl6 + 2e = PtCl4 + 2Cl


2-

PtCl4 + 2e = Pt + 4Cl

0.68 V vs. RHE

(59)

0.73 V vs. RHE

(60)

After deposition of platinum within the matrix, the electrode was washed with water
and subjected to cycling in 0.5 M H2SO4 in potential range from 0 V to 1.05 V (vs.
RHE) to remove Cl- from the catalytic film. The steps followed for the electrode
preparation are shown schematically in Fig. 31.

Counter electrode
Pt flag

Anodic dissolution of
Pt counter electrode

Working
Electrode (GC)

Matrix (Cs2.5H0.5PW12O40)

Fig. 31. Scheme of the preparation catalytic layer by electrochemical method.

64

7.2 Electrochemical measurements on the Pt/C modified with


Cs2.5PW12 system prepared by mixing method
7.2.1 Cyclic voltammetry (CV)
and rotating disc voltammetry (RDE) measurements

Fig. 32 shows the cyclic voltammetric responses (recorded in argon-saturated


0.5 M H2SO4 ) of a glassy carbon electrode modified with Nafion-treated (---)
unmodified Pt10%/Vulcan XC-72 carbon (Pt10%/C) and () Pt10%/Vulcan XC-72
carbon modified with cesium salt of 12-phosphotungstic acid (Cs2.5H0.5PW12O40). The
platinum loading in both cases was 30 g cm-2.

j / mA cm

-2

-2

-4

-6
0.0

0.2

0.4

0.6

0.8

1.0

E / V vs. RHE
Fig. 32. Cyclic voltammetric response of Nafion-containing films (deposited on rotating disc
glassy carbon electrode) of () Pt10%/Vulcan XC-72 carbon modified with Cs2.5H0.5PW12O40,
and (---) unmodified Pt10%/Vulcan XC-72 carbon. Electrolyte: argon saturated 0.5 M H2SO4.
Scan rate, 50 mV s-1.

It is apparent from Fig. 32 that reduction of Cs2.5H0.5PW12O40 (in the range of potentials
from 0 to 0.3 V) tends to overlap with the so-called hydrogen adsorption peaks that
typically exist on clean bare platinum. The electroactivity of Cs2.5H0.5PW12O40 in the
hydrogen adsorption/desorption region of Pt (at potential lower than 0.35 V) is clearly
evident in Fig. 32. Further, following CV response for Cs2.5PW12 with Pt/C, the

65

voltammetric peak (at potential higher than 0.7 V) referring to the formation of Pt-oxo
(PtO or PtOH) species is shifted towards more positive potentials. Increase of the
potential range, where platinum is not covered with platinum oxide, may facilitate
adsorption and activation of hydrogen molecules during electrocatalysis.[21]
The hydrogen electrooxidation reaction on Pt in acid solution is one of the fastest
known electrochemical reactions. To evaluate electrocatalytic activity towards the
hydrogen oxidation, we have performed the diagnostic rotating disc electrode (RDE)
voltammetric measurements using a glassy carbon disc electrode modified with Nafiontreated (Fig. 33A) Pt10%/Vulcan XC72 carbon modified with Cs2.5H0.5PW12O40 in
comparison to (Fig. 33B) unmodified Pt10%/Vulcan XC72 carbon. The RDE
measurements (Fig. 33) for the hydrogen oxidation have been performed at different
rotation rates (ranging from 900 to 2500 rpm). The anodic potential was limited to 100
mV, because the diffusion limiting current for both catalytic layer reach a constant
value at ca. 70 mV, and the coupled hydrogen adsorption-electron transfer steps of the
reaction are only observed at potentials below 50 mV. The examination procedure was
the same for both systems.
It becomes obvious that current density obtained for catalytic layer modified
with cesium salt of tungsten heteropolyacid (Cs2.5H0.5PW12O40) is higher (Fig. 33A),
when compared to the corresponding current density of the bare commercial
Pt10%/Vulcan XC-72 carbon nanoparticles (Fig. 33B). The above results may imply
that modification of Pt10%/Vulcan XC-72 carbon with Cs2.5H0.5PW12O40 matrix results
in increasing dispersion of catalytic centers (higher exposing of Pt particles) on which
proceed hydrogen oxidation reaction (HOR). It can be also explained by the different
diffusion speed into the catalytic layer, what was described in the literature.[46]

66

3.0

/ rpm

2500

j / mA cm-2

2.5
2.0
900

1.5
1.0
0.5
0.0
0.00

0.03

0.06

0.09

0.12

0.15

E / V vs. RHE

3.0

/ rpm

2.5

j / mA cm

-2

2500

2.0
900

1.5

1.0

0.5

0.0
0.00

0.03

0.06

0.09

0.12

0.15

E / V vs. RHE

Fig. 33. RDE voltammograms recorded in the hydrogen saturated 0.5 M H2SO4 solution at
different rotation rates (900, 1100, 1300, 1500, 1700, 1900, 2100, 2300, 2500 rpm) using a
glassy carbon disc electrode covered with Nafion-treated (Fig. 33A) Pt10%/Vulcan XC72
carbon modified with Cs2.5H0.5PW12O40 and (Fig. 33B) unmodified Pt10%/Vulcan XC72
carbon. Scan rate, 10 mV s-1. The loading of Pt 30 g cm-2.

The above effects become clearer when we compare them at certain rotation rate
for modified and unmodified systems (Fig. 34). Moreover, based on the literature
data[27,28] we can expect that HPAs can act as redox mediators for the electrochemical

67

oxidation of CO. This could be advantageous knowing that Pt can easily poison with
CO.

3.0

Cs2.5H0.5PW12O40 with 10%Pt/Vulcan and Nafion


2
LPt = 30 g/cm

2.5

j / mA cm-2

10%Pt/Vulcan and Nafion

2.0

LPt = 30 g/cm

1.5
1.0
0.5
0.0
0.00

0.03

0.06

0.09

0.12

0.15

E / V vs. RHE
Fig. 34. Comparison of RDE voltammograms recorded in the hydrogen saturated 0.5 mol dm-3
H2SO4 solution using rotating disc glassy carbon electrode covered with films of Nafioncontaining inks of (red line) Pt10%/Vulcan XC-72 carbon modified with Cs2.5H0.5PW12O40, and
(black line) unmodified Pt10%/Vulcan XC-72 carbon Rotation rate, = 2500 rpm. Scan rate,
10 mV s-1.

Fig. 33 and Fig. 34 confirm that modification of commercial Pt10%/Vulcan XC72 by Cs2.5H0.5PW12O40 matrix increases dispersion of platinum centers which are in
contact with hydrogen.
The dependence of the RDE limiting currents versus the square root of rotation
rates (Fig. 35) shows linearity behavior, i.e. ideal behavior characteristic of a system
limited solely by convective diffusion of hydrogen in solution.

68

3.0
on
afi
N
+

j / mA cm-2

2.5

O 40
12
W
P

H 0.5

.5

2.0
C
%/
10
t
P

1.5

)
72
CX
(

s2
+C

C
%/
10
t
P

)
72
CX
(

on
afi
N
+

1.0

0.5

0.0
0

10

20

30
1/2

40

50

1/2

/ (rpm)

Fig. 35. Levich plots j vs. 1/2 prepared using the data of Fig. 33 for (red symbols) Cs2.5PW12modified GC-supported Pt10%/Vulcan XC-72 carbon nanoparticles. Currents were measured
at 0.1 V. For comparison the same plot is provided for (black symbols) GC-supported
Pt10%/Vulcan XC-72 carbon nanoparticles of the same loading (30 g cm-2).

Assuming laminar flow and the mass transport rate, the diffusion limited current
density is mathematically described by the Levich equation, as a function of the
rotational frequency of the RDE, (in radians per seconds)[196,197]:
2/3 -1/6

d = 0.62nFD

1/2

c0

= Bc0

1/2

(61)

where, D is the diffusivity of hydrogen in 0.5 M H2SO4 (D298

-5

= 3.7 x 10 cm /s,

estimated from the product of H2 diffusivity at infinite dilution and the ratio of the
dynamic viscosities of the electrolyte and pure water), n is the number of electrons in
the H2 oxidation reaction (i.e., n = 2), is the kinematics viscosity of the electrolyte
-2

(298 K = 1.07 x 10 cm /s), c0 is the solubility of H2 in 0.5 M H2SO4 (c298 K = 7.14 x 10

-3

M). In 0.5 M H2SO4, the calculated value of Levich constant, B, and the solubility, c0,
-2

-2

i.e., Bc0, at 298 K is equal to 6.54 x 10 (mA cm )rpm

-1/2

It have to be point out that in the presence of Nafion film, mass-transport limitations
through the film lowered the limiting current at each rotation speed. Thats why for the

69

Nafion-coated RDE we have additional term including hydrogen diffusion into the
layer[46]:
ifilm = nFADfcf / f

(62)
2

where, Df is the diffusion coefficient of H2 in the recast Nafion (cm s-1), A is a


geometric area of an electrode area (cm2), cf is a solubility of H2 in recast Nafion (mol
cm-3), f is a nafion film thickness.
The thickness of the Nafion film on the investigated catalytic layers was equal
0.23 m. Maruyama and coworkers[46] reported absence of the mass transfer effect when
the thickness of Nafion film varied in the range 1 to 13 m. This means that in our
case the influence of the ifilm is negligible and this element can be omission.
According to the Eq. 61, a plot of the current density at constant potential versus 1/2
(Fig. 35) ought to result in a straight line with the slope defined by Bc0. The regression,
made for ours new type of system, yielded a slope of Bc0 = 6.07 10-2 (mA cm-2) rpm-1/2
-2

-2

which is in fairly good agreement with above calculated value (6.54 x 10 (mA cm )
rpm

-1/2

) (-8%) considering the uncertainties associated with the evaluation of the

diffusivity of hydrogen in the electrolyte. Incidentally, the above values apply to the
entire potential range between 0.1 and 0.3 V. For Nafion-containing Pt10%/Vulcan XC72 carbon (Cs2.5PW12-free system showed as a comparison) the regression yielded a
slope of Bc0 = 6 10-2 (mA cm-2) rpm-1/2.
Fig. 36, presents mass transport corrected Tafel diagrams for the investigated
catalytic layers. Mass transport correction for rotation disc electrode is described as
follows

[54]

ik = id i / id i

(63)

where, i is the experimentally obtained current, id refers to the measured diffusionlimited current, and ik the mass-transport free kinetic current.. The RDE polarization
data analyzed here allow obtaining information on the kinetics of the HOR. On
polycrystalline platinum, oxidation of hydrogen involving two electrons in acidic media
can proceed according to two different pathways:

by chemical adsorption step (Tafel-Volmer mechanism)


H2 + 2M 2MH

(Tafel reaction)

(5)
70

or electrochemical adsorption step (Heyrovsky-Volmer mechanism)


H2 + M MH + H+ + e-

(Heyrovsky reaction)

(6)

followed by the hydrogen atom discharge path given by


MH M + H+ + e-

(Volmer reaction)

(7)

The rates of the reactions (5) and (6) can change depending on the electrode material
and electrolyte.[44,51] Taking attention that in our case influence of the ifilm is negligible
the equations have been derived for analysis of the RDE voltammograms for the cases
of reversible or irreversible electrochemical reaction. The kinetic equations
are[45,49,52,198]:

E = E10'

j
2.303RT
log L
nF
jL

(64)

E = E20'

j j
2.303RT
log L
nF
jL j

(65)

where, for the reversible (Eq. 64) and irreversible (Eq. 65) cases, respectively. In the
0

equations E1 and E2 are current independent constants, j is the current density, jL is


the diffusion limiting current density and is the change transfer coefficient.

71

0.0

900 rpm
1700 rpm
2100 rpm

log[(jL-j)/jL]

log[(jL-j)/jL]

0.0

-0.5

900 rpm
1700 rpm
2100 rpm

-0.5

-1.0

log[(jLx j)/(jL - j)]

log[(jLx j)/(jL - j)]

-1.0

900 rpm
1700 rpm
2100 rpm

0
900 rpm
1700 rpm
2100 rpm

-1
0.00

0.01

0.02

0.03

0.04

E / V vs. RHE

0.00

0.01

0.02

0.03

0.04

E / V vs. NHE

Fig. 36. Mass transport corrected Tafel diagrams [E ~ log(jL j / jL) and E ~ log(jL j / jL - j)]
for HOR on catalytic layer prepared from Nafion-containing Cs2.5H0.5PW12O40 with Pt10% on
Vulcan XC-72carbon, (a) equation (64) and (b) equation (65) and as a comparison catalytic
layer made from Nafion-containing Pt10% on Vulcan XC-72 carbon, (c) equation (64) and
(d)equation (65) in 0.5 M H2SO4. Rotation rates: () 900 rpm, () 1700, () 2500 rpm.
Data taken from Fig. 33.

If either condition is satisfied, according to equations (64) and (65), the plots
log(jL j / jL) vs. E should be linear with slopes independent of the rotation rates and
equal to nF/2.303 RT or nF/2.303 RT.[169,197]
As we can see in Fig. 36, for all the catalytic layers the plots are linear only if a
reversible kinetics is assumed. The reverse values of the slopes (the Tafel slope E ~
log(jL j / jL - j)), presented in Table 6, are very close to the theoretical value obtained
-1

for platinum 29 mV dec at temperature 293 K. However, there is no agreement with


the prediction coming from equation (65). In this case we should obtain slope equal 58
-1

mV dec from mass transport corrected Tafel diagram. For potentials below 0.01 V,
there is no linear relationship for the plot E ~ log(jL j / jL - j), however, if we consider
-1

slope values for E > 0.01 V, we obtain values on the level 28 - 31 mV dec what is
-1

more then two times lower in comparison to the predicted value of 58 mV dec . From
these results it may be concluded that the HOR takes places via the Tafel-Volmer
mechanism with the atom-atom recombination step (Tafel) as a rate determining step

72

(rds) at both layers. On this type of electrode, in strong acidic media, a Tafel-Volmer
mechanism, with Tafel as the rds, has also been proposed by Mello and co-workers.[44]
Exchange currents (I0) was calculated from the slope of the linear polarization response
and corrected for diffusion by using the following equation[52]:

E RT 1 1
+
=
I nF I 0 I L

(66)

where: n = 2 and IL is the limiting current. Values obtained from this equation are
presented in Table 6.

breversible
(mV
dec-1)

birreversible
(mV
dec-1)

Pt10% on Vulcan
XC-72 carbon

32

28

Cs2.5H0.5PW12O40
with Pt10% on
Vulcan XC-72
carbon

32

31

32

35

Composition of
catalytic layer

Babi at all[52].
Pt20% on Vulcan
XC-27 carbon

Theoretical
breversible
(mV dec-1)

Theoretical
birreversible
(mV dec-1)

29 (Tafel-Volmer)
118 (HeyrovskyVolmer)

58 (Tafel-Volmer,
HeyrovskyVolmer)

I0
(mA)

0.63

0.83

0.55

Table 6. Theoretical and experimental Tafel parameters, mechanism and corresponding values
of exchange currents for HOR in acid medium at 25 0C for the catalytic layer made from:
Nafion-containing Cs2.5H0.5PW12O40 with Pt10%/Vulcan XC-72 carbon and for Cs2.5H0.5PW12O40
free system (as a comparison).

In conclusion, we should note that, in both systems, hydrogen oxidation reaction


follows the Tafel-Volmer mechanism with the atom-atom recombination step (Tafel) as
rds. Calculated values of Bc0 for investigated materials are close to the theoretical value
(6.54 x 10-2 mA cm-2 rpm-1/2). Nevertheless the value of diffusion limiting current for
ours system is 12% higher than that for unmodified one. Moreover exchange current
calculated for Cs2.5PW12-containing catalytic layer is 32% higher than that for the
system containing unmodified commercial available Pt/Vulcan XC-72 carbon
nanoparticles. The value of I0 obtained for unmodified system (Pt/C) is in a good
agreement with that reported by Babi at all.[52] All these issues clearly show that our

73

catalytic layer containing Pt10%/Vulcan XC-72 carbon together with a matrix obtained
from cesium salt of 12-phosphotungstic acid (Cs2.5H0.2PW12O40) possesses many
advantages in comparison with Cs2.5PW12-free system.

7.2.2 Test of the Cs2.5H0.5PW12O40-containing anode catalyst


in working single PEM fuel cell
The mixing method was used to prepare inks to be utilized as anode catalyst in
a working fuel cell. Cs2.5H0.2PW12O40, Pt10%/Vulcan XC-72 and Vulcan XC-72 were
mixed in 99% ethanol and stirred in a close container for 24 hours. 200 l of Nafion
solution were then added to the homogeneous suspension and stirring was continued for
12 hours. The relative amounts of the different component are listed in Table 7.
Name of the component
Cs2.5H0.2PW12O40
Pt10% on Vulcan XC-72 carbon
Vulcan XC-72 carbon
Nafion

Weight in grams
0.0073
0.0059
0.0067
0.0087

Table 7. Amounts of components used for preparation anode for PMEFC.

The ink was then spread homogeneously onto the surface of a commercial gas
diffusion layer (low-temperature ELAT GDL microporous layer on woven web, tin
configuration), purchased from E-TEK, (5x2.5 cm) previously weighted using a brush.
The resulting GDL with catalytic layer (CL) was left to dry in an oven for 30 min. at 80
0

C and weighted again to determine the amount of catalytic mixture in terms of Pt

content per cm2. Pt loading was 43 g cm-2. The same procedure was used to prepare a
Cs2.5H0.2PW12O40-free catalytic layer using commercial Pt10%/Vulcan XC-72 carbon
from E-TEK. The Pt loading for this electrode was 50 g cm-2. 2.2 x 2.2 cm portions of
the two layers were then cut to obtain the electrode to be used for preparing a MEA.
Membrane electrode assemblies (MEA) are built by hot pressing two of the
above electrodes at the opposite sides of a Nafion membrane (thick, 127 m). Nafion
Membrane 115 purchased from Ion Power Inc., (dimension) 7.5x7.5 cm, was used as a
proton conducting membrane.
Two types of MEA have been built and tested: MEA1 was prepared using the
composite electrode at one side and the commercial catalyst on the other side; MEA2, to

74

be used for comparison, had the commercial catalyst on both sides. The preparation
conditions are listed in Table 8 in the case of MEA1.
Anode electrode Cathode
electrode
Cs2.5H0.2PW12O40 Pt10%/C
Pt10%/C
Vulcan XC-72
Vulcan XC-72

Membrane Temperature Pressure Time


/ 0C
/ bar
/ min.
Nafion
125
15
3
115

Table 8. Components and conditions for the hot pressing MEA preparation.

The MEA have been tested using a 5 cm2 single cell, from Fuel Cell Technologies,
operated equipped with single serpentine flow channel as gas feeds, showed in Fig. 37.
The cells were operated using pure H2 and O2.

H2 part

B
serpentine
flow
channel
gas intlet

gas outlet

O2 part
bipolar plate

Fig. 37. Picture of the (A) single PEM fuel cell and (B) one side of PEMFC with bipolar
plate and single serpentine flow channel

Fig. 38 and Fig. 39 show the polarization curves and the power curves for both
MEA under the conditions specified in Table. 9.

75

1,0

MEA1

Cell voltage / V

0,8

MEA2

0,6

0,4

0,2
2

H2 -- LPt = 50 g/cm Pt // Pt LPt = 50 g/cm -- O2


2

H2 -- LPt = 43 g/cm Pt + Cs2.5H0.5PW12O40 // Pt LPt = 50 g/cm -- O2

0,0
0

200

400

600

800
-2

Current density / mA cm

Fig. 38. Current-voltage PEMFCs single cell performances of (red symbols) Cs2.5H0.5PW12O40containing and (black symbols) Cs2.5H0.5PW12O40-free anode: 70 0C of cell temperature, 70 0C
for both humidifiers, 3 bars of operating pressure.

Power Density / mW cm-2

400

300

200

100
2

H2 -- LPt = 50 g/cm Pt // Pt LPt = 50 g/cm -- O2


2

H2 -- LPt = 43 g/cm Pt + Cs2.5H0.5PW12O40 // Pt LPt = 50 g/cm -- O2

0
0

200

400

600

800

-2

Current density / mA cm

Fig. 39. PEMFCs single cell performances of (red symbols) Cs2.5H0.5PW12O40-containing and
(black symbols) Cs2.5H0.5PW12O40-free anode: 70 0C of cell temperature, 70 0C for both
humidifiers, 3 bars of operating pressure.

76

Catalysts and their loading


(g cm-2)
Anode
Cathode
Cs2.5H0.2PW12O40 Pt10%/C
Vulcan XC-72
Pt10%/C
50 g cm-2
Vulcan XC-72
-2
43 g cm
Pt10%/C
Pt10%/C
Vulcan XC-72
Vulcan XC-72
50 g cm-2
50 g cm-2

Feeding conditions TCell


(0C)
Anode
Cathode
H2,
O2,
70
50 ccm 50 ccm
3 bars
3 bars
H2,
50 ccm
3 bars

O2,
50 ccm
3 bars

70

TAnode TCathode
(0C)
(0C)

Electrolyte

70

70

Nafion
115

70

70

Nafion
115

Table 9. Composition of electrodes, their loadings and operation conditions of single working
PEMFC.

The polarization curves were obtained by applying 50 mA steps and recording


the cell potential after 60 sec.
As it may be seen better performances are obtained (either in terms of potential
and power) when using MEA1. In this type of fuel cells the performances are limited by
the cathode where oxygen reduction (a very sluggish electrochemical reaction) occurs.
As the cathode catalyst is the same in both cases, the better performances of MEA1
have to be ascribed to the anode side that contains a catalyst layer modified with
Cs2.5H0.5PW12O40.

Our results suggest that modification of commercial Pt10%/Vulcan XC-72


carbon with cesium salt of 12-phosphotungstic acid (Cs2.5H0.2PW12O40) leads to better
utilization of catalytic centers as apparent from Fig. 38 and Fig. 39. Similar results were
obtained by Stanis et al. where Pt/C was modified with H3PW12O40 heteropolyacid was
used as an anode in PEM fuel cell operating on pure hydrogen as a fuel.[27]
In conclusion, we should also remark that results obtained for our new system by
using single working PEM fuel cell are in agreement with previous results received by
using electrochemical methods, particularly cyclic voltammetry (CV) and rotating disc
voltammetry (RDE) methods.

77

7.3 Electrochemical measurements on the Pt/C modified with


Cs2.5H0.5PW12O40 system prepared by electrochemical method
7.3.1 Cyclic voltammetry study
Corrosion of Pt was accomplished by applying sufficiently positive potential to
-3
platinum flag counter electrode in 0.5 mol dm H2SO4 containing ions Cl (as was

described previously in chapter 7.1.2) on composite catalytic layers and layers prepared
using the commercial catalyst alone. During negative potential scans applied to the
working electrode electrodeposition take places onto catalytic layers existing on the
surface of glassy carbon RDE electrode. The voltammograms before and after
electrochemical deposition were recorded in the 0.5 mol dm-3 H2SO4 without Cl- (Fig.
40 and 41). Before recording voltammetric curve of the catalytic layer after
electrodeposition of platinum, the modified electrode was washed with water and
subjected to cycling in 0.5 M H2SO4 in potential range from 0 V to 1.05 V (vs. RHE) to
remove Cl- from the catalytic film.
4

Pt as counter electrode
after Pt corrosion
before Pt corrosion

Carbon paper as counter electrode

0.4
-2

-2
j / mA cm

j / mA cm

-2

-4

after cycling
beafore cycling

0.2
0.0
-0.2
-0.4

-6

0.0

0.2

0.4

0.6

0.8

1.0

E / V vs. RHE

-8
0.0

0.2

0.4

0.6

0.8

1.0

E / V vs. RHE

Fig. 40. Cyclic voltammetric responses of Cs2.5H0.5PW12O40 with Vulcan before (dash line) and
after (solid line) Pt corrosion from platinum counter electrode; Inset: Cs2.5PW12O40 with Vulcan
before (dash line) and after (solid line) cycling where carbon paper was used as counter
electrode; Electrolyte: argon saturated 0.5 M H2SO4. Scan rate, 50 mV s-1.

78

Fig. 40 shows the final cyclic voltammetric response of the composite catalytic
layer before and after Pt continuous cycling together with the initial cyclic
voltammograms. The final cyclic voltammogram shows the classic signature of
hydrogen adsorption/desorption on Pt.
The insert in Fig. 40 shows the cyclic voltammograms obtained under the same
conditions with the same electrode when carbon paper instead of Pt was used as counter
electrode. Apart from a slight increase of the currents in the hydrogen region, due to the
reduction of the cesium salts (chapter 6.4), the shape of the curve is practically
unaltered after prolonged cycling. The obvious conclusion that may be drawn is that the
high current increase when the counter electrode is Pt is due to deposition of Pt on the
composite electrode because of corrosion of the counter electrode.
For a comparison the same procedure has been applied to Nafion-containing
catalytic layer made from Vulcan XC-72 carbon (Cs2.5PW12-free system). Fig. 41 shows
the cyclic voltammetric response of Vulcan before and after Pt corrosion. The results
demonstrate that the procedure works also on Vulcan alone.

Vulcan before Pt corrosion


Vulcan after Pt corrosion

j / mA cm

-2

2
0
-2
-4
-6
-8
-10
0.0

0.2

0.4

0.6

0.8

1.0

E / V vs. RHE
Fig. 41. Cyclic voltammetric responses of Vulcan before (dash line) and after (solid line)
Pt corrosion from platinum counter electrode; Electrolyte: argon saturated 0.5 M H2SO4; Scan
rate, 50 mV s-1.

Again the development of the cyclic voltammetric curves with increasing number of
scan reveals the progressive grow of the characteristic hydrogen adsorption/desorption
waves close to 0 V that indicate presence of Pt on the electrode.
79

In order to obtain further evidences, beside the signature of hydrogen


adsorption/desorption, of the effectiveness of the proposed method to dope the
composite electrode (and Vulcan) with Pt nanoparticles by corrosion of a Pt counter
electrode and to have an idea of the electrochemically active area, dimensions and Pt
loading that may be obtained, alternative methods to detect Pt have been used. These
include both CO stripping and TEM. The electrochemically active area at Pt electrodes
is usually measured using the hydrogen adsorption/desorption peaks. In this case this
method can not be applied because the Cs salts is electro-active in the same potential
region and, hence, the integrated areas under the peaks contain the contributions due to
the reduction of the compound itself.

7.3.2 CO electrooxidation on catalytic layer


containing Cs2.5H0.5PW12O40 as a matrix
It is well known in the literature that CO adsorbs on Pt poisoning it and
cancelling any catalytic activity for hydrogen oxidation. Adsorbed CO can be stripped
from the Pt surface at potentials in the range 0.8 - 1 V vs. RHE. The charge
corresponding to one monolayer of adsorbed CO is equal to 0.484 mC cm-2.[199-201]
Hence, by measuring the charge under the stripping peak, after subtraction of the
background, the electrochemically active area can be obtained using the formula:

EAS = QCO / 0.484

(67)

where QCO is the measured charge.

Fig. 42 shows several voltammograms obtained at 20 mV/s using the composite


electrode under different conditions. The black continuous line is relative to the Pt
containing composite electrode as prepared, while the dashed black line shows the
voltammogram obtained after CO adsorption. The red line corresponds to the
voltammogram of the composite electrode before Pt deposition and the dashed blue line
to that obtained with the same electrode after CO adsorption. The last two
voltammograms demonstrate that there is no absorption of CO before Pt corrosion and,
hence, that no errors are introduced due to CO adsorption in the salt.

80

The peak relative to hydrogen desorption present in the pristine electrode after
activation in the hydrogen region is completely absent after CO absorption. This
testifies that the entire Pt surface is completely blocked by CO. The stripping of CO at
about 0.95 V is very well defined and sharp. The computed charge under the peak is
equal to 0.2207 mC. Using Eq. 67 this translates into an electrochemically active area of
0.456 cm2.

Cs2.5PW12 -containing system after Pt corrosion

CO-adsorption on Cs2.5PW12 - containing system after Pt corrosion


Cs2.5PW12 -containing Pt-free system

j / mA cm

-2

CO-adsorption on Cs2.5PW12 - containing Pt-free system

CO

-1
0.0

0.2

0.4

0.6

0.8

1.0

1.2

E / V vs. RHE
Fig. 42. Base voltammetry () and CO-stripping (---) on a Nafion-containing Cs2.5H0.5PW12O40
with Vulcan XC-72 carbon and corroded platinum and for a comparison base voltammetry ()
and CO-stripping (---) at a Pt-free Nafion-containing Cs2.5H0.5PW12O40 with Vulcan XC-72
carbon electrode. Electrolyte, argon saturated 0.5 mol dm-3 H2SO4. Scan rate, 20 mV s-1.

7.3.3 HRTEM characterization

Fig. 43a and b show HRTEM images of Pt nanoparticles obtained using powders
from the composite and the pure Vulcan electrodes after electrochemical Pt deposition.
The images show that the nanoparticles of electrodeposited Pt on catalytic layer
containing cesium salt of tungsten heteropolyacid are largely spherical in shape with a
diameter of about 2 nm (Fig. 43a), while for the catalytic layer containing only Vulcan
XC-72 carbon the platinum particles have diameter about 4 nm (Fig. 43b).
A likely explanation of the different particle size may be that in the case of the
Cs2.5H0.5PW12O40 containing composite Pt deposition occurs inside the nanochannels of
81

the porous tertiary structure of the salts that posses characteristic diameters while in the
case of pure Vulcan the particles grow on the surface where are more prone to grow.

(a)

(b)

Fig. 43. HRTEM image of nafion-containing catalytic layer made from: (a) Cs2.5H0.5PW12O40
with Vulcan XC-72 carbon and corroded Pt and (b) Vulcan XC-72 carbon with corroded Pt for
a comparison.

In the case of the composite catalytic layer where the surface area is known one
may attempt to compute the Pt loading by assuming uniform diameters and the absence
of bigger aggregates average. Knowing dimensions of Pt nanoparticles and assuming
theirs spherical shape we are able to calculate platinum loading into the catalytic layer
by using the following equation[52,202]:
S = (6 x 103) / d

(68)

where S is specific surface area (m2 g-1), d is the mean particle size in nm (from
HRTEM) and is the density of Pt metal (21.4 g cm-3). Assuming that all nanoparticles
have dimension ca. 2 nm as well as the absence of aggregated nanoparticles, we obtain
the surface area for one nanoparticle equal to 140.18 m2 g-1. Knowing EAS,
electrochemically active area (0.456 cm2) received from CO stripping measurements
(assuming 100% coverage) and S for one particle we are able to calculate loading of
platinum into the catalytic layer by applying following equation:

82

LPt = (EAS/ S) / A

(69)

where, A is the area of the RDE electrode (A = 0.1256 cm2). According to this equation
the calculated Pt loading was 2.6 g cm-2. This approximate calculation was made to
comment on the order of magnitude of platinum. The amounts of Pt are indeed varying
very low what means that we are able to decrease quantity of this material without
decreasing the systems performance towards hydrogen oxidation reaction (HOR).

7.3.4 Rotating disc voltammetry measurements


The kinetic data of the HOR occurring at the catalytic layers prepared by
electrochemical method has been done by applying the same type of analysis (using the
same procedure) as for the systems prepared by mixing method (chapter 7.2.1).
Fig. 44 presents the hydrogen oxidation polarization curves recorded at several
rotation speeds (1300 rpm 2500 rpm) in 0.5 mol dm-3 H2SO4 on the following
catalytic layers: (A) Cs2.5H0.5PW12O40 with Vulcan XC-72 carbon, Nafion and corroded
platinum and (B) Vulcan XC-72 carbon with Nafion and corroded platinum (for
comparison). The anodic potential limit was to 100 mV because the limiting currents
reach a constant value at ca. 80 mV in the case of both catalytic layers. Also the coupled
hydrogen adsorption-electron transfer steps of the reaction are only observed at
potentials below 50 mV. Current density obtained for catalytic layer containing
Cs2.5H0.5PW12O40 matrix is higher than that obtained for catalytic layer containing only
Vulcan XC-72 carbon.

83

/ rpm

j / mA cm-2

2.5

2500

2.0
1300

1.5

1.0

0.5

0.0
0.00

0.02

0.04

0.06

0.08

0.10

0.12

E / V vs. RHE

j / mA cm-2

/ rpm

2.5

2500

2.0
1300

1.5

1.0

0.5

0.0
0.00

0.02

0.04

0.06

0.08

0.10

0.12

E / V vs. RHE
Fig. 44. Hydrogen oxidation RDE voltammograms for several rotation speeds obtained in
0.5 M H2SO4 under H2 atmosphere on Nafion-containing catalytic layer made from (A)
Cs2.5H0.5PW12O40 with Vulcan XC-72 Carbon and corroded platinum and (B) Vulcan XC-72
Carbon with corroded platinum as a comparison, at different speed rotation, 1300 rpm
2500 rpm. Scan rate, 2 mV s-1.

84

Comparison of hydrogen oxidation RDE curves at 2500 rpm recorded for the
system containing Cs2.5PW12 matrix with corroded platinum and this unmodified one
with corroded platinum is illustrated in Fig. 45. Higher current density obtained for the
modified material could be explained by formation of smaller Pt nanoparticles not only
on the surfaces but also possibly inside the channels in micro-meso porous structure of
the matrix.

3.0
Cs2.5H0.5PW12O40 + Vulcan XC-72 carbon after corrosion of Pt flag

j / mA cm-2

2.5
2.0

Vulcan XC-72 carbon after corrosion of Pt flag

1.5
1.0
0.5
0.0
0.00

0.02

0.04

0.06

0.08

0.10

0.12

E / V vs. RHE
Fig. 45. Comparison of hydrogen oxidation RDE voltammograms at Nafion-coated catalytic
layers made from: (red line) Cs2.5H0.5PW12O40 with Vulcan XC-72 Carbon and corroded
platinum and (black line) Vulcan XC-72 Carbon with corroded platinum in 0.5 M H2SO4 under
H2 atmosphere. Rotation rate, = 2500 rpm; scan rate, 2 mV s-1.

The dependence of the respective RDE limiting currents versus the square root
of rotation rates (Fig. 46) shows linearity behavior. Assuming laminar flow, the mass
transport rate and the limiting diffusional current density can be described
mathematically by the Levich equation, as a function of the rotational frequency of the
RDE, (in radians per seconds) (Equation 61).

85

2.5

j / mA cm

-2

2.0

1.5

1.0

+
O 40
12
W
P5

Cs 2

lca
Vu

a
on
arb
c
72
CX
n

-72
XC
n
a
lc
Vu

H 0.

.5

0.5

lag
tf
P
f
no
sio
o
r
or
rc
fte

ca

c
er
aft
n
rbo

orr

ag
t fl
fP
o
on
osi

0.0
0

10

20
1/2

30

40

50

1/2

/ (rpm)

Fig. 46. Levich plots j vs. 1/2 prepared using the data of Fig.44 for (red symbols)
Cs2.5H0.5PW12O40 with Vulcan XC-72 carbon and corroded platinum. Currents were measured
at 0.1 V. For comparison the same plot is provided for (black symbols) unmodified GCsupported Vulcan XC-72 carbon with corroded platinum.

The Bc0 calculated from the slope of Levich plot (Fig. 46) is equal 5.1 10-2 (mA cm-2)
-3
rpm-1/2 and is about 20% lower than the theoretical value of Bc0 in 0.5 mol dm H2SO4,

at 25 0C (6.54 10-2 (mA cm-2) rpm-1/2).


In order to overcome limitation of the technique employed, steady-state
experiments were also carried out. They are complementary to the RDE results. Steady
state data were used to prepare Tafel plots for the hydrogen oxidation reaction occurring
at the investigated electrode material and for Nafion-containing Cs2.5PW12-free system
as a reference. The Tafel diagrams for Nafion-containing catalytic layer made from
Cs2.5PW12 matrix with Vulcan XC-72 carbon and corroded platinum are presented in
[

Fig. 47. As a comparison, the same graphs were made for unmodified system. 44,45 50,51]
Like it was described previously, on polycrystalline platinum two electron HOR in
acidic media can proceed by chemical adsorption step (Tafel) or electrochemical
adsorption step (Heyrovsky), followed by the adsorbed hydrogen atom discharge step
(Volmer), as described in Eqs. (5) (7).

86

log[(jL-j)/jL]

(c)

(a)

0.0

-0.8

-1.6

(d)

(b)
log[(jLx j)/(jL - j)]

0.8

0.0

-0.8

0.00

0.02

0.04

0.00

0.02

0.04

E / V vs. RHE

Fig. 47. Mass transport corrected Tafel diagrams [E ~ log(jL j / jL) and E ~ log(jL j / jL - j)]
for HOR on catalytic layer prepared from Nafion-containing Cs2.5H0.5PW12O40 with Vulcan XC72 carbon and corroded platinum, (a) equation (64) and (b) equation (65) and as a comparison
catalytic layer made from Nafion-containing Vulcan XC-72 carbon with corroded platinum, (c)
equation (64) and (d) equation (65) in 0.5 M H2SO4. Rotation rates: () 1500 rpm,
() 2500 rpm. Data taken from Fig. 44.

The values of the Tafel slopes for reversible reaction, presented in Table 10, are
very close to theoretical value obtained for platinum 29 mV dec-1 at temperature 295 K.
Based on the experimental data reversible nature of the electrochemical hydrogen
oxidation reaction at both investigated catalytic layers is electrochemically reversible
seems experimentally supported. The HOR on investigated systems takes places via the
Tafel-Volmer mechanism with the atom-atom recombination step (Tafel) as a rate
determining step (rds).[44] Exchange currents (I0) was calculated from the slope of the
linear polarization response and corrected for diffusion by using previously showed and
described equation (66). Values obtained from this equation are presented in Table 10.
In conclusion, we should admit that the results obtained for catalytic layers
prepared by electrochemical method studied using CV and RDE method, clearly shows
that modification of the system by using insoluble cesium salt of 12-phosphotungstic
acid matrix provide to better performance towards hydrogen oxidation reaction (HOR).
87

The exchange current (I0) calculated for Cs2.5PW12-containig material is almost twice of
the value obtained for unmodified one.
breversible
(mV
dec-1)

Composition of
catalytic layer
Cs2.5H0.5PW12O40 with
Vulcan XC-72 carbon
and corroded Pt
Vulcan XC-72 carbon
with corroded Pt

birreversible
(mV
dec-1)

Theoretical
breversible
(mV dec-1)

Theoretical
birreversible
(mV dec-1)

I0
(m
A)
0.98

31

28

31

28

29 (TafelVolmer)
118 (HeyrovskyVolmer)

58 (Tafel-Volmer,
HeyrovskyVolmer)
0.5

Table 10. Theoretical and experimental Tafel parameters, mechanism and corresponding values
of exchange currents for HOR in acid medium at 22 0C for the Nafion-containing catalytic layer
made from: Cs2.5H0.5PW12O40 with Vulcan XC-72 carbon

and corroded Pt and for

Cs2.5H0.5PW12O40 free system (as a comparison).

7.4 Comparison of catalytic layers containing Cs2.5PW12


matrix prepared by mixing and electrochemical methods
Table 11 presents summary of results obtained for Cs2.5H0.5PW12O40-containing
systems prepared by mixing method and by electrochemical method.

Composition of
catalytic layer
Pt10% on Vulcan XC72 carbon

breversible
(mV
dec-1)
32

Theoretical
breversible
(mV dec-1)

I0
(mA)
0.63

29 (TafelVolmer)

Cs2.5H0.5PW12O40 with
Pt10% on Vulcan XC72 carbon

32

Cs2.5H0.5PW12O40 with
Vulcan XC-72 carbon
and corroded Pt

31

118
(HeyrovskyVolmer)

0.83

0.98

Table 11. Summary table containing mechanistic parameters and corresponding values of
exchange currents for HOR in acid medium at 22 0C for the Nafion-containing catalytic layer
made from: Cs2.5H0.5PW12O40 with 10% Pt/C, Cs2.5H0.5PW12O40 with Vulcan XC-72 carbon and
corroded Pt and 10% Pt/C (for comparison).

88

The mechanism of the hydrogen oxidation reaction is the same for all
investigated electrode materials.
The value of exchange currents (I0) calculated for the system containing
Cs2.5PW12-matrix is higher than that obtained for Cs2.5PW12-free catalyst. Furthermore,
the catalyst prepared by electrochemical deposition appears to be more active, towards
hydrogen oxidation than that prepared by mixing method.
Catalytic layer, prepared by mixing method, containing Cs2.5H0.5PW12O40 matrix
was tested as an anode in single working PEM fuel cell operating on pure hydrogen as a
fuel. Advantage of this method is its simplicity. Results obtained from this
measurements confirm that the modification of the commercial available Pt/C by using
Cs2.5H0.5PW12O40 matrix provide to better performance of the system towards HOR
what is in agreement with RDE measurements.
It is important to underscore that results described in this chapter being the
part of the Italian and international patent.[203,204]

89

8. Methanol oxidation reaction (MOR) on the catalytic layers


containing Keggin-type heteropolyacid salts as a matrix
Methanol oxidation reaction is a very important reaction from a practical point
of view. This small organic molecule has attracted considerable attention due to the
development of direct liquid fuel cells that require highly reactive fuels with high
energy density. However, the formation of strongly adsorbed intermediates species such
as (CO)ads on the Pt catalyst, which is the most active metal for methanol oxidation,
results in high oxidation overpotentials, usually far from the thermodynamic limit.
Therefore this chapter is devoted to optimize of Pt-based electrocatalysts, by applying
new type of matrices with high porosity, strong acidic properties and high ionic
conductivity.
New systems have been characterized with respect to their electrochemical
properties ( voltammetry, CO stripping) and their electrocatalytic activity for methanol
oxidation. The stability of catalytic properties will be also discussed.
The chapter is divided into two parts related to
Keggin-type heteropolyacid salts (Cs+ or Rb+)

the cation present into the

used as a matrix for commercial

Pt/Vulcan XC-72 carbon. Methanol oxidation reaction on the unmodified catalytic layer
(Nafion-containing Pt/Vulcan XC-72 carbon) is shown for a comparison.

8.1 Preparation of the catalytic layers


The electrocatalyst layer was prepared by mixing via the following procedure.
Calculated amounts of commercial Pt40%/Vulcan XC-72 carbon and of cesium or
rubidium salt of Keggin-type heteropolyacid matrix were mixed in 1:1 ethanol - water
mixture (proportion 1:1) and

stirred for 24 h. A measured volume of Nafion (5%

alcoholic solution) was then added and the stirring continued for additional 12 h to
obtain a homogenous dispersion. The mass ratio between Pt40%/Vulcan XC-72 :
heteropolyacids salts : pure Nafion solution was 1:1.5:0.3, respectively. The resulting
ink was dropped with a micropipette the surface of a glassy carbon disk electrode (
0.071 cm2 surface area) . The thin film

catalytic layer was dried at room temperature

for 20 minutes. For comparison, heteropolyacid salts-free ink of Pt40%/Vulcan XC-72


carbon and Nafion was also prepared. The platinum loading in each system is equal to
100 g cm-2.
90

8.2 Electrochemical measurements


at the Pt40%/C modified with Cs2.5-HPAs matrix

8.2.1 Cyclic voltammetry (CV) study

Fig. 48 shows the cyclic voltammetric responses (recorded in argon-saturated


0.5 mol dm-3 H2SO4) of the glassy carbon electrode modified with Nafion-treated pure
Pt40%/Vulcan XC-72 carbon (Pt40%/C) and Pt40%/Vulcan XC-72 carbon modified
with matrix made from cesium salts of Keggin-type heteropolyacids: Cs2.5H0.5PW12O40,
Cs2.5H0.5PMo12O40, Cs2.5H1.5SiW12O40 and Cs2.5H1.5SiMo12O40. The platinum loading in
all investigated electrocatalytic films was equal to 100 g cm-2. The voltammetric peaks
appearing at about 0.46 V (Fig. 48, light-blue line) and 0.43 V (Fig. 48, green line)
should be attributed to the reduction of Cs2.5H1.5SiMo12O40 and Cs2.5H0.5PMo12O40,
respectively, while Cs2.5H1.5SiW12O40 (Fig. 48, dark-blue line) is electroactive at
potential lower ca. 0.1 V. Cs2.5H0.5PW12O40 becomes electroactive (Fig. 48, red line) at
the more negative potentials and its reduction overlaps with the so-called hydrogen
adsorption peaks that typically exist on clean bare platinum at potentials lower than 0.35
V.
The presence of cesium salts of Keggin-type heteropolyacids (particularly Cs2.5PMo12
and Cs2.5SiMo12) causes a shift of the voltammetric peaks (at potential higher than 0.8
V) relative to the formation of Pt-oxo (PtO or PtOH) species towards more positive
potentials.

91

0.6

j / mA cm

-2

0.3

0.0

-0.3

-0.6

-0.9
0.0

0.2

0.4

0.6

0.8

1.0

E / V vs. RHE
Fig. 48. Cyclic voltammetric responses of Nafion-containing films (deposited on glassy carbon
electrode) of () Pt40%/Vulcan XC-72 carbon modified with Cs2.5H0.5PW12O40, ()
Pt40%/Vulcan XC-72 carbon modified with Cs2.5H0.5PMo12O40, () Pt40%/Vulcan XC-72
carbon modified with Cs2.5H1.5SiW12O40, () Pt40%/Vulcan XC-72 carbon modified with
Cs2.5H1.5SiMo12O40 and () unmodified Pt40%/Vulcan XC-72 carbon. Electrolyte: argon
saturated 0.5 mol dm-3 H2SO4. Scan rate, 10 mV s-1. Temperature, 240C.

To investigate the influence of the matrix in the catalytic

behavior towards

methanol oxidation reaction (MOR), cyclic voltammetric measurements (Fig. 49) were
carried out on four kinds of systems (Pt40%/C with Cs2.5PW12, Pt40%/C with
Cs2.5PMo12, Pt40%/C with Cs2.5SiW12 and Pt40%/C with Cs2.5SiMo12) and on
commercial unmodified electrocatalyst (Pt40%/C) as a reference. Because the slow
kinetics, methanol oxidation reaction occurs at high oxidation overpotentials, far from
the thermodynamic limit (E0 = 0.02 V).[84]
In Fig. 49, for all investigated materials we observe two characteristic
irreversible current peaks (A and B) during the electrooxidation of methanol. The peak
obtained in the forward scan (peak A) at around 0.85 V is typically attributed to the
methanol electrooxidation and the backward peak (peak B) at ca. 0.73 V is known to be
due to the oxidation reaction on the Pt of residual intermediate species such as CH2OH,
CH2O,HCOOH and CO.[205,206]

92

35

30

j / mA cm

-2

25
20
15
10
5
0
0.0

0.2

0.4

0.6

0.8

1.0

E / V vs. RHE
Fig. 49. Cyclic voltammetric responses of Nafion-containing films (deposited on glassy carbon
electrode) of () Pt40%/Vulcan XC-72 carbon modified with Cs2.5H0.5PW12O40, ()
Pt40%/Vulcan XC-72 carbon modified with Cs2.5H0.5PMo12O40, () Pt40%/Vulcan XC-72
carbon modified with Cs2.5H1.5SiW12O40, () Pt40%/Vulcan XC-72 carbon modified with
Cs2.5H1.5SiMo12O40 and () unmodified Pt40%/Vulcan XC-72 carbon. Electrolyte: argon
saturated 0.5 mol dm-3 CH3OH + 0.5 mol dm-3 H2SO4. Scan rate, 10 mV s-1. Temperature, 240C.

Moreover, Fig. 49 clearly show that modification of commercial Pt40%/C by


cesium HPA salts matrix increases noticeably the electrocatalytic activity of the system
for MOR. The highest current densities were obtained for the catalytic layers containing
Cs2.5H0.5PMo12O40 and Cs2.5H1.5SiW12O40 as a matrix.
It is also important to note that methanol oxidation reaction starts at more negative
potentials for all modified systems in comparison to unmodified catalytic layer
containing commercial Pt40%/C. This indicates that the presence of the matrix can
increase the kinetics of methanol oxidation by lowering the onset potential for this
reaction.
The reaction mechanism was investigated on the basis of the Tafel plot analyses.
Fig. 50 shows the Tafel plots for the methanol oxidation obtained from the cyclic
voltammograms at the scan rate 5 mV s-1 for the systems modified by cesium salts of
Keggin-type heteropolyacids and, as a comparison, for the unmodified catalytic layer.

93

-1

106 mV dec

-1

95 mV dec-1
95 mV dec

log j / mA cm-2

region 1
0

-1

93 mV dec

88 mV dec-1

-1

region 2
-2

-3
0,3

0,4

0,5

0,6

0,7

E / V vs. RHE
Fig.50.Tafel plots of methanol oxidation at the Nafion-containing (--) Pt40%/Vulcan XC-72
carbon modified with Cs2.5H0.5PW12O40, (--) Pt40%/Vulcan XC-72 carbon modified with
Cs2.5H0.5PMo12O40, (--) Pt40%/Vulcan XC-72 carbon modified with Cs2.5H1.5SiW12O40, (--)
Pt40%/Vulcan XC-72 carbon modified with Cs2.5H1.5SiMo12O40 and (--) unmodified
Pt40%/Vulcan XC-72 carbon. Temperature, 240C.

The reverse of the slopes (RT/nF) of the Tafel lines (1 / b, expressed in mV dec1

) change at ca. 0.45 V, indicating the presence of two different reaction mechanisms.

The Tafel slope in region 1 is strongly dependent on the concentration of methanol as


well as the reaction time[85] and this does not allow to draw conclusions on the kinetic
equation in region 1. Since the Tafel slope in region 2 is unchanged with the
concentration of methanol and reaction time a kinetic parameters at a given reaction
time can be determined from this region.[85]
The main slope, in the region 2, for unmodified 40% Pt/C is 88 mV decade-1.
The

Tafel

slopes

for

the

catalytic

layers

containing

Cs2.5H0.5PW12O40,

Cs2.5H0.5PMo12O40, Cs2.5H1.5SiW12O40 and Cs2.5H1.5SiMo12O40 matrix were estimated, in


the same manner as for the pure Pt40%/Vulcan XC-72 carbon system, to be 93, 95, 106
and 95 mV decade-1, respectively. Those results are in good agreement with those
reported by Inada and co-workers.[85] They obtained Tafel slope of the methanol
oxidation at the Pt electrode to be 96 10 mV decade-1 in the potential range of 0.55
0.7 V vs. RHE at room temperature[85], which well agrees with the result of Fig. 50.
Thus, it is postulated that the number of electrons involved in the electrode reaction n is
94

ca. 1 (n 1) at 240C. The methanol electrooxidation pathway is considered as


follows[85]:
CH3OH (CHnO)ads + (4 n) H+ + (4 n) e-

(70)

H2O (OH)ads + H+ + e-

(71)

(CHnO)ads + (OH)ads CO2 + n (H)ads

(72)

(H)ads H+ + e-

(73)

where methanol is oxidized via the strongly adsorbed species (CHnO)ads. If (CHnO)ads is
(COH)ads, step (72) is written as
(COH)ads + (OH)ads (CO)ads + H2O

(74)

Reaction described in equation (70) (methanol dissociative adsorption) occurs around


0.1-0.3 V vs. RHE at Pt[84,85] and it is not include to the rate-determining process (Tafel
slop is observed at 0.45 0.66 V). Therefore, the rate determining step is step showed
in Eq. (71) or (72); although Eq. (71) is reported to be rate determining process only by
several workers.[83,84,207]

8.2.2. Staircase voltammetry (SV) measurements

For a better insight of the system reactivity towards methanol oxidation reaction
staircase voltammetry has been used. Fig. 51 shows

dependencies of staircase

voltammetric responses (step period of 50 s recorded every 25 mV) of methanol


oxidation on catalytic layers containing Nafion treated Pt40%/Vulcan XC-72 carbon
and cesium salts of Keggin-type heteropolyacids (Cs2.5PW12, Cs2.5PMo12, Cs2.5SiW12,
Cs2.5SiMo12) as a matrix and on commercial unmodified electrocatalyst (Pt40%/Vulcan
XC-72 carbon) for a comparison. For all materials containing Keggin-type cesium salts
as a matrix a significant increase of electrocatalytic currents was observed. This can be
rationalized in terms of the relative ability, potential mutual interactions, and the
existence of sufficient numbers of Pt centers for efficient oxidation of methanol.
Presence of Cs2.5H0.5PMo12O40 and Cs2.5H1.5SiW12O40 salts in the system results in some
increase of methanol electrocatalytic currents (compare curves for unmodified and
modified systems in Fig. 51).

95

25

j / mA cm

-2

20

15

10

0
0.4

0.6

0.8

1.0

E / V vs. RHE
Fig. 51. Staircase voltammetric current densities for the methanol (0.5 mol dm-3) oxidation
recorded every 25 mV (between 0.25 and 1.07 V) following application of 50-s potential steps at
the

Nafion-containing

layer

of

(--)Pt40%/Vulcan

XC-72

carbon

modified

with

Cs2.5H0.5PW12O40, (--) Pt40%/Vulcan XC-72 carbon modified with Cs2.5H0.5PMo12O40, (--)


Pt40%/Vulcan XC-72 carbon modified with Cs2.5H1.5SiW12O40, (--) Pt40%/Vulcan XC-72
carbon modified with Cs2.5H1.5SiMo12O40 and (--) unmodified Pt40%/Vulcan XC-72 carbon.
Electrolyte: argon saturated 0.5 mol dm-3 H2SO4..Temperature, 240C.

Fig. 52 presents dependencies of staircase voltammetric responses (step period


of 50 s recorded every 25 mV) of methanol oxidation on the same layers as in Fig. 51
but in a shorter potential range (from 0.43 to 0.65 V). An important issue of the data of
Fig. 52 is that the methanol oxidation currents densities tend to appear at less positive
potentials than on bare Pt. The best performances are shown by a catalytic layer
containing Cs2.5H0.5PMo12O40 salt as a matrix. The methanol oxidation reaction starts at
potential c.a. 20 mV less positive than for the unmodified system containing Nafiontreated Pt40%/Vulcan XC-72 carbon. This enhancement effect and also the increased
current densities, may originate from the fact that PMo12 (in Cs2.5PMo12), added to
platinum, increase the CO tolerance of Pt-based system.

96

j / mA cm

-2

0
0.45

0.50

0.55

0.60

0.65

E / V vs. RHE
Fig. 52. Staircase voltammetric current densities for the methanol (0.5 mol dm-3) oxidation
recorded every 25 mV (between 0.43 and 0.65 V) following application of 50-s potential steps at
the

Nafion-containing

layer

of

()Pt40%/Vulcan

XC-72

carbon

modified

with

Cs2.5H0.5PW12O40, () Pt40%/Vulcan XC-72 carbon modified with Cs2.5H0.5PMo12O40, ()


Pt40%/Vulcan XC-72 carbon modified with Cs2.5H1.5SiW12O40, () Pt40%/Vulcan XC-72
carbon modified with Cs2.5H1.5SiMo12O40 and () unmodified Pt40%/Vulcan XC-72 carbon.
Electrolyte: argon saturated 0.5 mol dm-3 H2SO4.. Temperature, 240C.

8.2.3 Chronoamperometry (CA) measurements

To further evaluate the reactivity of our electrocatalytic systems towards the


methanol oxidation, current-time measurements at different constant potentials (0.47 or
0.52 V) were performed (Fig. 53). As expected, the largest currents densities are
observed at the more positive applied potential (Fig. 53B). As observed in Fig. 53, when
investigated materials are polarized at constant potential (0.47 V or 0.52 V) in methanol
solutions, the current density decays continuously indicating a pronounced loss in
activity. The current density reaches almost stationary state after 800 seconds (Fig.
53A) and 600 seconds (Fig. 53B). The factor causing the decay of current density is
apparently, a blockage of the surface by some organic residue, which is slowly formed
and can only be oxidized at high anodic potentials.[84] The impregnation of cesium salts

97

of Keggin-type heteropolyacids matrix with commercial Pt40%/Vulcan XC-72 carbon


results in an increase of the methanol electrooxidation current densities.

j / mA cm-2

0.3

0.2

0.1

0.0
0

200

400

600

800

1000

t/s

B
j / mA cm-2

0.6

0.4

0.2

0.0
0

200

400

600

800

1000

t/s
Fig. 53. Chronoamperometric curves recorded for the methanol oxidation at the Nafioncontaining layer of ()Pt40%/Vulcan XC-72 carbon modified with Cs2.5H0.5PW12O40, ()
Pt40%/Vulcan XC-72 carbon modified with Cs2.5H0.5PMo12O40, () Pt40%/Vulcan XC-72
carbon modified with Cs2.5H1.5SiW12O40, () Pt40%/Vulcan XC-72 carbon modified with
Cs2.5H1.5SiMo12O40 and () unmodified Pt40%/Vulcan XC-72 carbon upon application of (A)
0.47 V and (B) 0.52 V. Electrolyte: argon saturated 0.5 mol dm-3 H2SO4.. Temperature, 240C.

98

At both studied constant potentials, catalytic layers containing Cs2.5H0.5PW12O40 and


Cs2.5H1.5SiMo12O40 shows only small difference in current densities in comparison to
unmodified platinum (at 0.47V current decreased to the same level with that of pure Pt).
The highest activity in both potentials (0.47 V and 0.52 V) is displayed by the system
containing Cs2.5H0.5PMo12O40 salts as a matrix. We have to state that we not have
produced a practically more active catalyst here. The systems activity here is due to the
higher number of the Pt active site which the methanol molecules reached to CO2 per
second, per surface site, but not to the mass of platinum used.

8.2.4 Electrochemical impedance spectroscopy


for methanol electrooxidation
In order to further compare the activity of methanol electrooxidation on a
different electrochemically polarized catalysts and to investigate the reaction
mechanism, electrochemical impedance spectroscopy (EIS) was carried out at different
potentials. Fig. 54 shows Nyquist plots of methanol electrooxidation for different
electrochemically polarized catalysts modified by cesium salts of Keggin-type
heteropolyacid matrix (Pt40%/C-Cs2.5HPA) and for unmodified Pt40%/Vulcan XC-72
carbon catalyst as a reference, at potentials of 0.50, 0.65 and 0.75 V.
The EIS results indicate that the methanol electrooxidation on Nafion-containing
Pt40%/Vulcan XC-72 carbon with cesium salts of HPAs (Cs2.5PW12, Cs2.5PMo12,
Cs2.5SiW12, Cs2.5SiMo12) matrix at various potentials shows different impedance
behaviors. In order to analyze reaction mechanism of methanol electrooxidation on
Pt/C-Cs2.5HPAs catalysts, a simple two-step model for methanol electrooxidation can be
assumed[209]:
I1
CH 3OH
COads + 4 H + + 4e

(75)

I2
COads + H 2O
CO2 + 2 H + + 2e

(76)

I1 is the rate leading to the adsorbed surface intermediates COads. I2 is the rate for
oxidation of COads. IF is the Faradaic current and stand for net rate of charge transfer. In
this assuming, we just consider only one intermediate COads in methanol
electrooxidation.

99

I 1 = k1cm (1 CO )
I 2 = k 2 CO OH ,

(77)

I F = I1 + I 2

(78)

where CO and OH are the fractional surface coverage of COads and OH, respectively.
For simplifying the analysis, the variation of OH is assumed to have little effect on
impedance behavior of methanol electrooxidation, defined as
=

d
F
=
( I1 I 2 ) = K ( I1 I 2 )
dt qCO

(79)

where qco is the quantity of charge needed to complete a full coverage of CO on the
electrocatalyst.[209]
According to the kinetic theory derived by Harrington and Conway[218] and Cao[219] for
reactions involving intermediate adsorbate, in the electrode process of methanol
electrooxidation, the Faradaic current depends on the electrode potential E and one
other state variable CO varying with E and affecting the Faradaic current.[209]
So the Faradaic admittance of methanol electrooxidation is[209]
YF =

1
B
+
Rct a + j

(80)

where Rct = (E/IF)SS is charge transfer resistance of the electrode reaction and is the
only circuit element that has a simple physical meaning describing how fast the rate of
charge transfer during methanol electrooxidation changes with changing electrode
potential when the surface coverage of the intermediate is held constant. The subscript
ss denotes steady state. Rct also can be defined as Rct = lim0 Re{Zf} where Re{Zf}
is the real component in complex plots (Nyquist plots, Fig. 54), the circular frequency

= 2f. So Rct can be obtained directly from Nyquist plots.[209]


In Eq. 80, a = (/)SS > 0 a is the always positive for a stable steady process
and with a dimension of s1, defined as B = mb where m = IF/, b = (/E)SS =
d/dE, and B with dimensions of 1 cm2 s1.
The impedance Nyquist plots can be classified according to the sign of B value.
When B > 0, Eq. 80 can be rewritten as follows[209]:
YF =

1
+
Rct

1
1
1
=
+
a + j
Rct R0 + jL
B
B

(81)

100

The dimension of R0 is cm2 and of L is cm2. Thus there will be an inductive


component involved in Faradaic impedance. The impedance Nyquist plot will be a
capacitive arc in the high frequency range and an inductive arc in the low frequency
range.
When B < 0, in this case:
YF =

B
1

Rct a + j

(82)

The Faradaic impedance can be rewritten as

Rct2 B
Ra
1
ZF =
= Rct +
= Rct +
YF
a Rct B + j
1 + jRa C a

(83)

with Ra = Rct 2|B|/a Rct|B|, Ca = 1/Rct2|B|.


The dimension of Ra is cm2 and of Ca, F cm2. In this group there are still two cases,
which can be classified.[209]
When a Rct|B| > 0, then Ra > 0, two capacitive arcs will be displayed on the
first quadrant of Nyquist plot. When a Rct|B| < 0, then in this case Ra < 0, and the
capacitive arc in low frequency range will enter into the second quadrant of Nyquist
plot.[209]
According to above analysis, for methanol electrooxidation on Pt/C-Cs2.5HPAs
catalysts, the impedance parameters from Eqs. 77 and 78 can be deduced and are as
follows[209]:

[K ( I 1 I 2 )]
F

[k1cm (k1cm + k 2 OH ) CO ]
b=
=K
=
E
RT
E SS

(84)

( I1 I 2 )
I
m= F =
= k 2 OH k1cm

SS

(85)

1 When methanol electrooxidation at low potential range (0.5 V), assumes


reaction (1), methanol dehydrogenation is rate-determining step, then k1 k2. So, when
k2OH > k1cm, According to Eqs. 84 and 85, thus b < 0, and m > 0, namely B < 0.
From Eq. 83, Nyquist plots of EIS at 0.4V (Fig. 54A) should show capacitive
behaviors. Moreover, in this case, a Rct|B| > 0, so two overlapped capacitive
semicircles should exist in Nyquist plot and signify a reaction with one adsorbed
intermediate.[209]

101

6000

-Zimag / ohm

5000
4000

Fig. 54. Nyquist plots


recorded in Ar saturated

3000

0.5 mol dm-3 CH3OH +


2000

0.5 mol dm-3 H2SO4

1000

aqueous solution for


Nafion-containing

0
0

1000

2000

3000

4000

(--) Pt40%/Vulcan XC-72

5000

carbon modified with

Zreal / ohm

-Zimag / ohm

500

Cs2.5H0.5PW12O40,
(--) Pt40%/Vulcan XC-72

400

carbon modified with

300

Cs2.5H0.5PMo12O40,

200

(--) Pt40%/Vulcan XC-72

100

carbon modified with


Cs2.5H1.5SiW12O40,

0
-100

(--) Pt40%/Vulcan XC-72

-200

carbon modified with

-300

Cs2.5H1.5SiMo12O40 and
(--) unmodified Pt40%/Vulcan

-400
0

200

400

600

800

1000

Zreal / ohm

different potentials: (a) 0.50 V;


(b) 0.65 V; (c) 0.75 V.

300
200

XC-72 carbon catalysts at

The frequency range is from


0.05Hz to 100kHz.

-Zimag / ohm

100

Each electrode contained 100 g


0

cm-2 of the platinum.

-100
-200
-300
-400
-500

-400

-300

-200

-100

100

Zreal / ohm

102

The analyses from EIS indicate that, at low potential region , reaction (I1) might be ratedetermining step, and means the oxidation of COads with the OHads is fast.[208,209]
2. When methanol electrooxidation at intermediate potential range (0.65 V), with
an increase of potential, the rate of reaction (75) is increasing, but is not enough to
exceed the rate of reaction (76) obviously. So in this case the rate-determining step of
methanol electrooxidation is in transition region[209,210]. Thus maybe has following
relationship[209]:
k2 OH CO + k1 cm CO > k1 cm > k2 OH
From Eqs. 84 and 85, b < 0, and m < 0 can be deduced and then B = mb > 0.
According to Eq. 81 an inductive arc in low frequency range will be exhibited in
Nyquist plot. The inductive behavior from theoretical analysis is also observed in our
experiments shown in Fig. 54B. In general, the condition of occurrence of an inductive
behavior in Nyquist plot is mb > 0. This means, if the variation of the electrode potential
causes a variation of the Faradaic current density not only through its effect on the
strength of the electric field in the double layer but also through its effect on another
variable X and the both effects act in the same direction, an inductive component will be
involved in the Faradaic impedance.[219] According to impedance parameters, b and m,
inductive behavior in methanol electrooxidation reveals the COads coverage decreases
with increasing potential (b < 0), and the decreasing COads lead to an increase of
Faradaic current (m < 0). A reasonable explanation is with potential increasing, the large
amounts of OHads are formed on Cs2.5HPAs (particularly tungsten containing HPAs)
sites and react with COads and decrease its coverage. Meanwhile, the decreasing surface
coverage of COads will contribute to adsorption of methanol on Pt and enhance the
Faradaic current. So at the intermediate potential range, with an increase of potential
from 0.5 to 0.65 V, the transition from capacitive behavior to inductive behavior
indicates that the rate-determining step maybe is changing.[209,217] The similar inductive
behavior in EIS at about 0.65V was also observed by Wang and co-workers.[217]
3. When methanol electrooxidation at high potential range (0.75 V), in this case,
reaction (76) can be assumed as rate-determining step.[209,217]
Thus, k1 k2 and then k2OH < k1cm.
According to Eqs. 84 and 85, b > 0 and m < 0 can be deduced, then B < 0.
Moreover, in this case a Rct |B| < 0. The capacitive arc at low frequency in Nyquist
plot will flips to the second quadrant with the real component of the impedance

103

becoming negative. The theoretical analyses agree well with the experimental results
shown in Fig. 54C. This means that resistance Ra becomes negative resulting from
passivation of electrode surface.[221] Melnick et al[220] indicated that the passivation of
the Pt electrode during methanol electrooxidation is probably due to the reversible
formation of oxide species. Meanwhile, due to reaction (76) is rate-determining step, the
oxidation of COads with OH is very slow, so the passivation at higher potentials can be
explained by the formation of a large amount of COads and OH on surface of Pt/CCs2.5HPAs catalyst. Therefore, adsorption of methanol on Pt sites is inhibited due to an
increase of coverage of COads and OH on Pt sites and the electrooxidation rate is almost
no obvious increase.[209] From the EIS analyses, reaction (76) as ratedetermining step
at high potential range can well explain experimental results.[209,217]
Impedance
electrochemically

spectroscopy
polarized

of

the

Pt/C-Cs2.5HPAs

electrooxidation
catalysts

of

indicates

methanol
that

on

cathodic

polarization leads to an enhancement for methanol oxidation. The reaction proceeds


with one adsorbed intermediate of appreciable surface concentration and lifetime. The
different impedance behaviors in three different potential regions reveal that the
mechanism and rate-determining step in methanol electrooxidation vary with potentials.
At low potential range (0.50 V), methanol dehydrogenation is rate-determining step
while at high potential range (0.75 V), the oxidation and removal of COads became ratedetermining step. Meanwhile, at intermediate potential region(0.65 V), the ratedetermining step in methanol electrooxidation is maybe in transition range.[209,217]
In spite of the different impedance behaviors at different potentials, the
diameters of the primary semicircle of the Nafion-containing Pt40%/C with Cs2.5PMo12
and Pt40%/C with Cs2.5SiW12 catalysts are always smaller that of the Nafion-containing
Pt40%/C with Cs2.5PW12, Pt40%/C with Cs2.5SiMo12 and unmodified Pt40%/C systems.
This behavior means that the lowers charge transfer resistances for the electrode
reaction can be obtained on the Pt40%/Vulcan XC-72 carbon modified by
Cs2.5H0.5PMo12O40 or Cs2.5H1.5SiW12O40 matrix.

104

8.2.5 CO stripping voltammetry study


at Pt/C-Cs2.5HPAs
Fig. 55 shows cyclic voltammograms obtained with catalytic layers modified by
cesium salts of Keggin-type heteropolyacids (Cs2.5PW12, Cs2.5PMo12, Cs2.5SiW12 and
Cs2.5SiMo12) and with unmodified system from pure Pt40%/Vulcan XC-72 carbon with
a CO adsorbed ad-layer. An insert is put into the figure to emphasize the difference
between the potential of CO oxidation in the first anodic cycle for all investigated
systems. It is clear that the first anodic cycle is different from the second anodic cycle in
that a peak between 0.632 and 0.89 V exist in the first anodic cycle in each
voltammogram. The peak between 0.632 and 0.89 V is the oxidation of adsorbed CO.
For all the layers CO-adsorbed on the Pt surfaces is oxidized already in the first anodic
cycle, which is confirmed by the absence of peak in the second anodic cycle at
potentials between 0.632 and 0.89 V. Moreover, for the CO oxidation peaks, important
information such as onset and peak potential for CO oxidation is summarized in Table
12.
Catalyst
Pt/C
Pt/C-Cs2.5PW12
Pt/C-Cs2.5PMo12
Pt/C-Cs2.5SiW12
Pt/C-Cs2.5SiMo12

Onset potential Peak potential


(V)
(V)
0.743
0.813
0.665
0.792
0.692
0.817
0.665
0.784
0.632
0.733

Table 12. Onset and peak potentials for oxidation of adsorbed CO with the four modified
systems and for pure Pt/C as a reference.

Among the Pt/C, Pt/C-Cs2.5PW12, Pt/C-Cs2.5PMo12, Pt/C-Cs2.5SiW12 and Pt/CCs2.5SiMo12 catalysts, the Pt/C-Cs2.5SiMo12 system has the lowest onset and peak
potentials for CO oxidation, while the Pt/C has the highest ones. CO starts to be
oxidized with the Pt/C-Cs2.5SiMo12 electrode at a potential of 0.632 V which is 111 mV
lower than with the Pt/C electrode. The addition of others cesium salts of Keggin-type
heteropolyacids (Cs2.5PW12, Cs2.5PMo12, Cs2.5SiW12) also results in shifting of the onset
potential of CO oxidation in to a lower values (Table 12). These results suggest that the
HPA cesium salts behave as a redox mediator for the CO oxidation reaction with Pt
present in the system. The proposed mechanism proceeds via the following reaction[27]:
105

HPA + CO + H2O CO2 + H2HPA

(86)

H2HPA HPA + 2H+ + 2e-

(87)

This mechanism is considered particularly for the molybdenum containing


heteropolyacids, in which oxidation potential is shifted to the more positive values of
potentials

in

comparison

to

the

tungsten

containing

heteropolyacids.[19,21]

5
j / mA cm

-2

j / mA cm

-2

3
0
0,6

0,7

0,8

E / V vs. RHE

1
0
-1
0,0

0,2

0,4

0,6

0,8

1,0

1,2

E / V vs. RHE

Fig. 55. Cyclic voltammograms in the potential range 0.025 to 1.125 V vs. RHE on the Nafioncontaining layer of ()Pt40%/Vulcan XC-72 carbon modified with Cs2.5H0.5PW12O40, ()
Pt40%/Vulcan XC-72 carbon modified with Cs2.5H0.5PMo12O40, () Pt40%/Vulcan XC-72
carbon modified with Cs2.5H1.5SiW12O40, () Pt40%/Vulcan XC-72 carbon modified with
Cs2.5H1.5SiMo12O40 and () unmodified Pt40%/Vulcan XC-72 carbon with (first anodic cycle)
and without (second anodic cycle) a CO adsorbed ad-layer. Electrolyte, argon saturated 0.5
mol dm-3 H2SO4. Scan rate, 20 mV s-1. Temperature 24 0C.

The catalytic enhancement of the layer with cesium salt of tungsten containing
heteropolyacids (Cs2.5PW12, Cs2.5SiW12) as a matrix may be due to the synergistic effect
between Pt and PW12 (or SiW12). Assuming that this enhancement effect may originate
from the fact that tungsten containing heteropolycompound is analogous to the parent
tungsten oxide[74,211], tungsten units may provide additional -OH groups or radicals

106

capable of facilitating oxidation of passivating intermediates (COads)[26,74,222] on Pt. This


reaction can be described as follows[222]:
CO + OH CO2 + H+ + ePt

(88)

WO3

Alternatively, introduction of PW12 (or SiW12) may induce morphological


differences and lead to better Pt catalyst utilization.[74]

8.2.6 Electrochemical stability of investigated materials


containing Cs2.5-HPAs matrix
Electrochemical stability, that is a very important factor in the application to
practical fuel cells, was tested using long-term CV (Fig. 56) for methanol oxidation
reaction under argon flow. Current densities where obtained from the forward peak of
the last cycle (9th cycle) of methanol oxidation recorded in argon saturated 0.5 mol dm-3
H2SO4 containing 0.5 mol dm-3 CH3OH solution at 50 mV s-1. The gap between
measurements was 20 min. As Fig. 56 shows, the electrochemical stability of the system
containing Cs2.5H1.5SiW12O40 and Cs2.5H1.5SiMo12O40 as a matrix are fairly good,
indicating that the catalytic layers are stable in these conditions.
Moreover, also Cs2.5H0.5PW12O40 and Cs2.5H0.5PMo12O40 containing systems
are quite stable during long-term stability test. It is important to note that for all
modified systems the current densities of MOR are higher than for unmodified catalytic
material containing Nafion treated Pt40%/Vulcan XC-72 carbon. The reduction of
currents densities during long-term stability test may result not only from accumulation
of poisonous species (such as COads) on the surface of Pt particles but also because of
methanol consumption during the successive scans and change of the surface structure
of the Pt particles. Nevertheless, the best results (the highest current densities) during
long-term

stability test

were

obtained

for

the

catalytic

layers

containing

Cs2.5H1.5SiW12O40 and Cs2.5H0.5PMo12O40 salts as a matrix.

107

30

jp / mA cm

-2

25

20

15

10

0
0

200

400

600

800

t / min
Fig. 56. Long-term stability test of the Nafion-containing (--) Pt40%/Vulcan XC-72 carbon
modified with Cs2.5H0.5PW12O40, (--) Pt40%/Vulcan XC-72 carbon modified with
Cs2.5H0.5PMo12O40, (--) Pt40%/Vulcan XC-72 carbon modified with Cs2.5H1.5SiW12O40, (--)
Pt40%/Vulcan XC-72 carbon modified with Cs2.5H1.5SiMo12O40 and (--) unmodified
Pt40%/Vulcan XC-72 carbon electrodes in argon saturated 0.5 mol dm-3 H2SO4 containing 0.5
mol dm-3 CH3OH solution at 50 mV s-1. Temperature, 240C. Same Pt loadings mounted in all
cases (LPt = 100 g cm-2).

8.3 Electrochemical measurements


at system containing Rb2.5-HPAs matrix
At the beginning of this subsection we have to mark that the interest of the
rubidium salts of Keggin-type heteropolyacids were much lower than theirs cesium
equivalents. Nevertheless they seem to be very attractive in point of view theirs future
application as a matrix in anode materials for the alcohol fuel cells.

8.3.1. Cyclic voltammetry (CV) measurements


Fig. 57 illustrates cyclic voltammetric responses of a glassy carbon electrode
modified with Nafion-treated pure Pt40%/Vulcan XC-72 carbon (Pt40%/C) and
Pt40%/Vulcan XC-72 carbon modified with a matrix made from rubidium salts of

108

Keggin-type heteropolyacids (Rb2.5H0.5PW12O40, Rb2.5H0.5PMo12O40, Rb2.5H1.5SiW12O40


and Rb2.5H1.5SiMo12O40) recorded in argon-saturated 0.5 mol dm-3 H2SO4 at room
temperature. The platinum loading in all investigated materials was equal to 100gcm-2.

0.6

j / mA cm

-2

0.3

0.0

-0.3

-0.6

-0.9
0.0

0.2

0.4

0.6

0.8

1.0

1.2

E / V vs. RHE
Fig. 57. Cyclic voltammetric response of Nafion-containing films (deposited on glassy carbon
electrode) of () Pt40%/Vulcan XC-72 carbon modified with Rb2.5H0.5PW12O40, ()
Pt40%/Vulcan XC-72 carbon modified with Rb2.5H0.5PMo12O40, () Pt40%/Vulcan XC-72
carbon modified with Rb2.5H1.5SiW12O40, () Pt40%/Vulcan XC-72 carbon modified with
Rb2.5H1.5SiMo12O40 and () unmodified Pt40%/Vulcan XC-72 carbon. Electrolyte: argon
saturated 0.5 mol dm-3 H2SO4. Scan rate, 10 mV s-1. Temperature, 240C.

The most positive potential of anodic peak (0.46 V, Fig. 57 light-blue) is due to
the reduction of Rb2.5H1.5SiMo12O40 salt. The voltammetric peak appearing at about
0.43 V (Fig. 57, green line) should be attributed to the reduction of Rb2.5H0.5PMo12O40
salt, while Rb2.5H1.5SiW12O40 (Fig. 57, dark-blue line) and Rb2.5H0.5PW12O40 (Fig. 57,
red line) salts becomes electroactive at a less positive potential of ca. 0.35 V. The
presence of rubidium salts of Keggin-type heteropolyacids (particularly Rb2.5PMo12)
leads to shift of the voltammetric peaks referring to the formation of Pt-oxo (PtO or
PtOH) species toward more positive potentials. Cyclic voltammetric responses of the

109

systems containing rubidium salts of HPAs matrix are very similar to these obtained for
their cesium equivalents.
To investigate the influence of the matrix in the catalytic layer on the behavior
towards methanol oxidation reaction (MOR) cyclic voltammetric measurements (Fig.
58) were carried out with four kinds of systems containing Nafion treated
Pt40%/Vulcan XC-72 carbon modified by rubidium salts of Keggin-type HPAs
(Rb2.5PW12, Rb2.5PMo12, Rb2.5SiW12 and Rb2.5SiMo12) matrix and a commercial
unmodified electrocatalyst (Pt40%/C) as a reference.
In the Fig. 58 for all investigated materials we observe two characteristic
irreversible peaks (A and B) during the methanol electrooxidation. Forward scan peak
A, at potential ca. 0.85 V, is the oxidation current density that involves the formation of
intermediates.[205,206] As it was mention previously, it is certain that (CO)ads is a poison
to platinum catalyst for further oxidation of methanol. The backward peak B at ca. 0.73
V, correspond to the oxidation of the intermediates created during forward cycle.

j / mA cm

-2

40

30

20

10

0
0.0

0.2

0.4

0.6

0.8

1.0

E / V vs. RHE
Fig. 58. Cyclic voltammetric response of Nafion-containing films (deposited on glassy carbon
electrode) of () Pt40%/Vulcan XC-72 carbon modified with Rb2.5H0.5PW12O40, ()
Pt40%/Vulcan XC-72 carbon modified with Rb2.5H0.5PMo12O40, () Pt40%/Vulcan XC-72
carbon modified with Rb2.5H1.5SiW12O40, () Pt40%/Vulcan XC-72 carbon modified with
Rb2.5H1.5SiMo12O40 and () unmodified Pt40%/Vulcan XC-72 carbon. Electrolyte: argon
saturated 0.5 mol dm-3 CH3OH + 0.5 mol dm-3 H2SO4. Scan rate, 10 mV s-1. Temperature, 240C.

110

Moreover, Fig. 58 clearly shows that modification of commercial Pt40%/C by rubidium


HPA salts matrix increases noticeably electrocatalytic activity of the system for MOR,
what can be attributed to the better Pt catalyst utilization. The highest current density
was obtained for the catalytic layer containing Rb2.5H1.5SiW12O40 as a matrix.
Nevertheless the current densities obtained for materials containing Rb2.5H0.5PMo12O40
and Rb2.5H1.5SiMo12O40 are only 7% lower from this obtained from the layer containing
Rb2.5SiW12. Furthermore the onset potential of methanol oxidation on all modified
catalytic layers is shifted to less positive values of potential in comparison to
unmodified catalytic layer containing commercial Pt40%/C. This indicates that addition
of the new type of matrix can facilitate oxidation of methanol and produce passivating
intermediates during this process.
The reaction mechanism was investigated on the basis of the Tafel plot analyses.
The Tafel plots for the methanol oxidation obtained by cyclic voltammograms at the
scan rate 5 mV s-1 at the systems modified by rubidium salts of Keggin-type
heteropolyacids and for the unmodified catalytic layer made from Pt40%/Vulcan XC-72
carbon are showed in Fig. 59.
The main slope, in the region 2 (1/b, expressed in mV dec.-1), for unmodified
Pt40%/C is 88 mV decade-1. The other Tafel slopes for the catalytic layers containing
Rb2.5H0.5PW12O40, Rb2.5H0.5PMo12O40, Rb2.5H1.5SiW12O40 and Rb2.5H1.5SiMo12O40
matrix were estimated, in the same manner as for the pure Pt40%/Vulcan XC-72 carbon
systems, to be 106, 102, 106 and 113 mV decade-1, respectively. These results are in
good agreement with those reported by Inada and co-workers.[85] Small deviations are
observed for the system containing Nafion treated Pt40%/C with Rb2.5H1.5SiMo12O40
matrix.
For the slope in the shown range, it is postulated that the number of electrons
involved in the electrode reaction n is c.a. 1 (n 1) at 240C[82] and that the rate
determining process is the step in which CO from Pt surfaces is oxidized by the OH
groups to CO2.[85] In spite of this Eq. (71) showed previously is reported to be rate
determining process only by several workers.[83,84,207]

111

-1

-1
106 mV dec 113 mV dec
-1
102 mV dec
-1
106 mV dec

log j / mA cm-2

region 1

-1

88 mV dec

region 2

-1

-2

-3
0,3

0,4

0,5

0,6

0,7

E / V vs. RHE
Fig. 59.Tafel plots of methanol oxidation at the Nafion-containing (--) Pt40%/Vulcan XC-72
carbon modified with Rb2.5H0.5PW12O40, (--) Pt40%/Vulcan XC-72 carbon modified with
Rb2.5H0.5PMo12O40, (--) Pt40%/Vulcan XC-72 carbon modified with Rb2.5H1.5SiW12O40, (--)
Pt40%/Vulcan XC-72 carbon modified with Rb2.5H1.5SiMo12O40 and (--) unmodified
Pt40%/Vulcan XC-72 carbon. Temperature, 240C.

8.3.2 Staircase voltammetry (SV) measurements


Reactivity of the Pt/C modified with Rb2.5-HPAs towards methanol oxidation
was also examined by using staircase voltammetry method. Fig. 60 present
dependencies of staircase voltammetric responses (step period of 50 s recorded every 25
mV) of methanol oxidation on catalytic layers containing Nafion treated Pt40%/Vulcan
XC-72 carbon and rubidium salts of Keggin-type heteropolyacids (Rb2.5PW12,
Rb2.5PMo12,

Rb2.5SiW12,

Rb2.5SiMo12)

matrix

and

unmodified

electrocatalyst

(Pt40%/Vulcan XC-72 carbon) as a reference.


For all materials containing Keggin-type rubidium salts matrix a significant
increase of electrocatalytic currents was observed. This can be rationalized in terms of
the relative ability, potential mutual interactions, and the existence of sufficient numbers
of Pt centers for efficient oxidation of methanol. The highest current densities for

112

methanol electrooxidation were obtained for catalytic layers containing rubidium salts
of 12-silicotungstic and 12-silicomolybdic acid as a matrix.

25

j / mA cm

-2

20

15

10

0
0.4

0.6

0.8

1.0

E / V vs. RHE
Fig. 60. Staircase voltammetric current densities for the methanol (0.5 mol dm-3) oxidation
recorded every 25 mV (between 0.25 and 1.07 V) following application of 50-s potential steps at
the

Nafion-containing

layer

of

(--)Pt40%/Vulcan

XC-72

carbon

modified

with

Rb2.5H0.5PW12O40, (--) Pt40%/Vulcan XC-72 carbon modified with Rb2.5H0.5PMo12O40, (--)


Pt40%/Vulcan XC-72 carbon modified with Rb2.5H1.5SiW12O40, (--) Pt40%/Vulcan XC-72
carbon modified with Rb2.5H1.5SiMo12O40 and (--) unmodified Pt40%/Vulcan XC-72 carbon.
Electrolyte: argon saturated 0.5 mol dm-3 H2SO4..Temperature, 240C.

Fig. 61 present dependencies of staircase voltammetric responses of methanol


oxidation on the same layers as in Fig. 60 but in a shorter potential range (from 0.43 to
0.65 V). An important issue of the data of Fig.60 is that the methanol oxidation currents
densities tend to appear at less positive potentials than on bare Pt, the same as for Cs+
salts

of

HPAs.

The

best

performance

shown

catalytic

layer

containing

Rb2.5H1.5SiW12O40 salt as a matrix. The onset potential of methanol oxidation is ca. 25


mV less positive than for the unmodified system containing Nafion-treated
Pt40%/Vulcan XC-72 carbon. However, it is important to underline that the onset
potentials for the catalytic layers modified by the residue rubidium salts of 12phosphotungstic acid, 12-phosphomolybdic acid and 12-silicomolybdic acid are also
shifted to the less positive values of potential. This enhancement effect, as well as the
113

increasing of current densities, may originate from the fact that rubidium salts of
Keggin-type heteropolyacids matrix added to platinum increase the CO tolerance of Ptbased system.

j / mA cm

-2

0
0.45

0.50

0.55

0.60

0.65

E / V vs. RHE
Fig. 61. Staircase voltammetric current densities for the methanol (0.5 mol dm-3) oxidation
recorded every 25 mV (between 0.43 and 0.65 V) following application of 50-s potential steps at
the

Nafion-containing

layer

of

()Pt40%/Vulcan

XC-72

carbon

modified

with

Rb2.5H0.5PW12O40, () Pt40%/Vulcan XC-72 carbon modified with Rb2.5H0.5PMo12O40, ()


Pt40%/Vulcan XC-72 carbon modified with Rb2.5H1.5SiW12O40,

() Pt40%/Vulcan XC-72

carbon modified with Rb2.5H1.5SiMo12O40 and () unmodified Pt40%/Vulcan XC-72 carbon.


Electrolyte: argon saturated 0.5 mol dm-3 H2SO4.. Temperature, 240C.

8.3.3 Chronoamperometry (CA) measurements


To further evaluate the reactivity of our electrocatalytic systems for the methanol
oxidation, current-time measurements at different constant potentials (0.47 or 0.52 V)
were performed (Fig. 62). As observed in Fig. 62, when investigated materials are
polarized at constant potential (0.47 V or 0.52 V) in methanol solutions, the current
density decays continuously indicating a pronounced loss in activity. The current
density reaches almost stationary state after 600 seconds (Fig. 62A) and 400 seconds
(Fig. 62B). As it was mentioned before the factor causing the decay of current density is

114

apparently, a blockage of the surface by some organic residue, which is slowly formed
during methanol oxidation process.[84] In Fig. 62B, for the Rb2.5SiW12 containing
catalytic layer the initial current decay is greater than for the others catalysts. This
behavior can be addressed to the greater extent of the surface coverage with partially
oxidized intermediates, than for other layers.

j / mA cm-2

0.3

0.2

0.1

0.0
0

200

400

600

800

1000

t/s
1.0

B
j / mA cm-2

0.8

0.6

0.4

0.2

0.0
0

200

400

600

800

1000

t/s
Fig. 62. Chronoamperometric curves recorded for the methanol oxidation at the Nafioncontaining layer of ()Pt40%/Vulcan XC-72 carbon modified with Rb2.5H0.5PW12O40, ()
Pt40%/Vulcan XC-72 carbon modified with Rb2.5H0.5PMo12O40, () Pt40%/Vulcan XC-72
carbon modified with Rb2.5H1.5SiW12O40, () Pt40%/Vulcan XC-72 carbon modified with
Rb2.5H1.5SiMo12O40 and () unmodified Pt40%/Vulcan XC-72 carbon upon application of (A)
0.47 V and (B) 0.52 V. Electrolyte: argon saturated 0.5 mol dm-3 H2SO4.. Temperature, 240C.

115

All catalytic layers modified with rubidium salts of Keggin-type heteropolyacids


matrix exhibit higher methanol electrooxidation current densities (at constant potential
0.47 or 0.52 V) during all experiment time in comparison to unmodified system
(Pt40%/C). The highest activities in both constant potentials are displayed by systems
containing Rb2.5H0.5PMo12O40, Rb2.5H1.5SiW12O40 and Rb2.5H1.5SiMo12O40 salts as a
matrix. This can be explained by the increasing Pt active surface area, which can be
reached by methanol molecules and increment the CO tolerance of Pt-based system.

8.3.4 Electrochemical impedance spectroscopy measurements

In order to further compare the activity of the catalysts containing rubidium salts
of HPA`s matrix for methanol oxidation, electrochemical impedance spectroscopy (EIS)
were carried out at different potentials in 0.5 mol dm-3 H2SO4 and CH3OH aqueous
solutions. The Nyquist plots for the corresponding Pt40%/C-Rb2.5HPAs systems and for
unmodified one, as a reference, recorded at 0.50, 0.65 and 0.75 V are showed in Fig. 63.
It is clearly seen that EIS of the methanol electrooxidation on investigated electrode
materials at various potentials shows different impedance behavior. The polarization
resistance can be measured from diameter of the primary semicircle. As it was in the
case of Cs2.5-HPAs modified catalytic layers, at low potentials range of methanol
electrooxidation Pt/C-Rb2.5HPA electrode interface is dominated by adsorption and
electrical double layer at low potential range.[208] The Nyquist plots of electrochemical
impedance spectroscopy should show capacitive behaviors, which could be seen in Fig.
63A. At intermediate potentials range (Fig. 63B) the rate-determining step of MOR is in
transition region. The inductive behaviors observed in our experiments shown in Fig.
63B are in agreement with the literature data.[209,210]
When EIS are performed at high potential range (Fig. 63C), the oxidation and removal
of COads become rate-determining step. The capacitive arc at low frequency in Nyquist
plot reverses to the second and third quadrants, with the real component of the
impedance becoming negative[209], which is shown in Fig. 63C.

116

4000

-Zimag / ohm

3000

Fig. 63. Nyquist plots


recorded in Ar saturated

2000

0.5 mol dm-3 CH3OH +


0.5 mol dm-3 H2SO4

1000

aqueous solution for


0

Nafion-containing
0

1000

2000

3000

4000

5000

(--) Pt40%/Vulcan XC-72

Zreal / ohm

carbon modified with


Rb2.5H0.5PW12O40,

400

(--) Pt40%/Vulcan XC-72

-Zimag / ohm

carbon modified with


Rb2.5H0.5PMo12O40,

200

(--) Pt40%/Vulcan XC-72


carbon modified with
0

Rb2.5H1.5SiW12O40,
(--) Pt40%/Vulcan XC-72
-200

carbon modified with


Rb2.5H1.5SiMo12O40 and

-400
0

200

400

600

800

1000

Zreal / ohm

(--) unmodified Pt40%/Vulcan


XC-72 carbon catalysts at
different potentials: (a) 0.50 V;

200

(b) 0.65 V; (c) 0.75 V.

The frequency range is from

-Zimag / ohm

100

0.05Hz to 100kHz.
Each electrode contained 100 g

cm-2 of the platinum.


-100

-200

-300

-400
-400

-300

-200

-100

Zreal / ohm

117

The electrochemical impedance spectroscopy of methanol electrooxidation


presented in Fig. 63 shows that the mechanism and rate-determining step vary with
potentials. At low, intermediate and high potentials range the rate-determining steps of
methanol electrooxidation are methanol dehydrogenation, transition range and oxidation
and removal of COads, respectively.
Moreover the diameters of the primary semicircle of the Nafion-containing
Pt40%/C with Rb2.5SiW12 and Pt40%/C with Rb2.5SiMo12 catalysts are always smaller
than that of the Nafion-containing Pt40%/C with Rb2.5PW12, Pt40%/C with Rb2.5PMo12
and the unmodified Pt40%/C systems in all electrochemical impedance spectroscopy
(EIS) measurements, performed at different potentials
This behavior can be explained by the lower charge transfer resistance of the
electrode reaction on the Pt40%/Vulcan XC-72 carbon modified by Rb2.5SiW12 and
Rb2.5SiMo12 matrix.

8.3.5 CO stripping voltammetry study


at Pt/C modified with Rb2.5-HPAs
The cyclic voltammograms obtained on Nafion containing catalytic layers
modified by rubidium salts of Keggin-type heteropolyacids (Rb2.5PW12, Rb2.5PMo12,
Rb2.5SiW12 and Rb2.5SiMo12) and on unmodified system (Pt40%/Vulcan XC-72 carbon),
as a comparison, with a CO adsorbed ad-layer are shown in Fig. 64. An insert is put into
the figure to emphasize the difference between the potential of CO oxidation in the first
anodic cycle for all investigated systems. For all the layers, CO-adsorbed on the Pt
surfaces, is oxidized already in the first anodic cycles, as confirmed by the absence of
peak in the second anodic cycles at potentials between 0.63 and 1 V. Moreover, for the
CO oxidation peaks in the first anodic cycles onset and peak potentials for CO oxidation
are summarized in Table 13.

118

5
4

j / mA cm

-2

j / mA cm

-2

3
2

0
0.6

0.8

E / V vs. RHE

1
0
-1
-2
0.0

0.2

0.4

0.6

0.8

1.0

1.2

E / V vs. RHE
Fig. 64. Cyclic voltammograms in the potential range 0.025 to 1.125 V vs. RHE on the Nafioncontaining layer of ()Pt40%/Vulcan XC-72 carbon modified with Rb2.5H0.5PW12O40, ()
Pt40%/Vulcan XC-72 carbon modified with Rb2.5H0.5PMo12O40, () Pt40%/Vulcan XC-72
carbon modified with Rb2.5H1.5SiW12O40, () Pt40%/Vulcan XC-72 carbon modified with
Rb2.5H1.5SiMo12O40 and () unmodified Pt40%/Vulcan XC-72 carbon with (first anodic cycle)
and without (second anodic cycle) a CO adsorbed ad-layer. Electrolyte, argon saturated 0.5
mol dm-3 H2SO4. Scan rate, 20 mV s-1. Temperature 24 0C.

Catalyst

Onset potential Peak potential


(V)

(V)

Pt/C

0.743

0.813

Pt/C-Rb2.5PW12

0.679

0.831

Pt/C-Rb2.5PMo12

0.656

0.790

Pt/C-Rb2.5SiW12

0.656

0.780

Pt/C-Rb2.5SiMo12

0.632

0.750

Table 13. Onset and peak potentials for oxidation of adsorbed CO with the four modified
systems and for pure Pt/C as a reference.

From the Table 13 we can easily calculate that the catalytic enhancement toward CO
oxidation is on the order of 64 110 mV in comparison to the unmodified
Pt40%/Vulcan XC-72 carbon electrode. The lowest onset potential of oxidation of CO119

adsorbed on the Pt surfaces was recorded for the system containing Rb2.5SiMo12 matrix.
This shift to less positive values of potential is in well agreement with the onset
potential obtained for catalytic layer containing Cs2.5SiMo12 salt as a matrix. These
results suggest that the salts containing SiMo12 heteropolycompound can provide the
best protection of the Pt surface against poisoning by CO, moreover they can help
oxidize strongly adsorbed CO, e.g. by weakening the Pt-CO bond. For the others
catalytic layers modified by rubidium salts of Keggin-type heteropolyacids matrix
(Rb2.5PW12, Rb2.5PMo12, Rb2.5SiW12) we also obtain lower value of the onset potential
for CO oxidation (Table 13). This shift of potential on the modified catalyst could be
attributed to the presence of oxygenated species on Rb2.5-HPAs at lower potentials
compared to platinum. According to the bifunctional mechanism[212], these oxygenating
species allow the oxidation of CO into CO2 at lower potentials.
These results, obtained in this subchapter, suggest that the presence of POMs
anions (attend in the rubidium salts of Keggin-type heteropolyacids) might facilitate the
electrooxidation of intermediate species such as the CO that adsorbed on the Pt catalyst
surfaces[27], leading to suppression of the poisoning effect on Pt catalysts by CO or COlike intermediates. The catalytic enhancement of the layer containing Rb2.5SiW12 matrix
may be due to the synergistic effect between Pt and SiW12. This behavior can be
explained by assuming that tungsten units may provide additional -OH groups or
radicals capable of facilitating oxidation of passivating intermediates (COads) on Pt (like
in the parent WO3).[74,211] Tungsten containing salts may also induce morphological
differences and lead to better Pt catalyst utilization.

8.3.6 Electrochemical stability of investigated materials


containing Rb2.5-HPAs matrix
The long-term stability of Nafion treated Pt40%/Vulcan XC-72 carbon modified
by Rb2.5-HPAs matrix systems in 0.5 mol dm-3 H2SO4 containing 0.5 mol dm-3 CH3OH
aqueous solution has been investigated by cyclic voltammetry and the corresponding
results are shown in Fig. 65. Long-term stability test for unmodified system (Pt40%/C)
is presented as a reference.

120

30

jp / mA cm

-2

25

20

15

10

200

400

600

800

t / min

Fig. 65. Long-term stability test of the Nafion-containing (--)Pt40%/Vulcan XC-72 carbon
modified with Rb2.5H0.5PW12O40, (--) Pt40%/Vulcan XC-72 carbon modified with
Rb2.5H0.5PMo12O40, (--) Pt40%/Vulcan XC-72 carbon modified with Rb2.5H1.5SiW12O40, (--)
Pt40%/Vulcan XC-72 carbon modified with Rb2.5H1.5SiMo12O40 and (--) unmodified
Pt40%/Vulcan XC-72 carbon electrodes in argon saturated 0.5 mol dm-3 H2SO4 containing 0.5
mol dm-3 CH3OH solution at 50 mV s-1. Temperature, 240C. Same Pt loadings mounted in all
cases (LPt = 100 g cm-2).

The current densities were read from the forward anodic peak of the last cycle (9th
cycle). The gap between measurements was 20 min. The most stable performances
during long-term test are shown by catalytic layers containing Rb2.5H0.5PW12O40 and
Rb2.5H0.5PMo12O40, in which drop of the current densities was equal 23% and 27%
respectively. However, the best results (the highest current densities) during long-term
stability tests were obtained for the catalytic layers containing Rb2.5H1.5SiW12O40 and
Rb2.5H1.5SiMo12O40 salts as a matrix. We should also mention that, during all stability
tests, the current densities of methanol electrooxidation on modified systems were
higher that that for Nafion treated Pt40%/Vulcan XC-72 carbon electrode. The
reduction of currents densities during long-term stability tests may result not only from
accumulation of poisonous specious (such as COads) on the surface of Pt particles but
also because of methanol consumption during the successive scans and change of the
surface structure of the Pt particles.

121

8.4. Summary and conclusions


1) The values of peak current densities of methanol electrooxidation obtained from
cyclic voltammetry measurements, as a function of electrode composition are presented in
Fig. 66. Our result clearly shows that the modification of commercial Pt catalyst by Cs+
or Rb+ salts of HPAs increase electrocatalytic activity of the system towards methanol
electrooxidation. Based on this results we can conclude that the presence of Cs2.5-HPAs
or Rb2.5-HPAs matrix into the catalytic layer may facilitate the electrooxidation of
intermediate species such as the CO that is adsorbed on the Pt catalyst surfaces leading
to suppression of the poisoning effect on Pt catalysts by CO or CO-like intermediates.

jp / mA cm

-2

30

20

10

0
12

o
Si
M
2.

/C
0%
Pt
4

40

/C

-R

-R

2.

5
2.

12

Si
W

12

PM

12

16

-R
/C
0%
Pt
4

Pt

b
-R
/C

0%

12

2.
5

PW

/C
0%

12

Pt
4

2.

/C

-C

2.
5

0%

Pt
4

PW

12

PM

12

Pt
4

Pt
4

0%

/C

-C
/C

0%

-C

5
2.

s
-C

Pt
4

/C
%
40
Pt

2.
5

Si
W

12

Si
M

Fig. 66. Peak current densities obtained from forward scan of methanol electrooxidation on the
investigated materials recorded in argon saturated 0.5 mol dm-3 CH3OH + 0.5 mol dm-3 H2SO4.
Data taken from Fig.49 and 58.

2) The kinetic data of the methanol electrooxidation on investigated catalytic materials


obtained from the Tafel plot analyses shows that, in all cases, the rate determining step
is the step in which CO from Pt surfaces is oxidized by the OH groups to CO2.

122

Catalyst

Tafel slope
b / mV dec

Catalyst

Tafel slope

-1

b / mV dec-1

Pt/C

88

Pt/C + Rb2.5PW12

106

Pt/C + Cs2.5PW12

93

Pt/C + Rb2.5PMo12

102

Pt/C + Cs2.5PMo12

95

Pt/C + Rb2.5SiW12

106

Pt/C + Cs2.5SiW12

106

Pt/C + Rb2.5SiMo12

113

Pt/C + Cs2.5SiMo12

95

Table 14. Tafel slope values for all investigated catalytic materials.

3) The results received from staircase voltammetry (Fig. 67), which were used to better
insight into the systems reactivity, clearly shows that the onset potential of the methanol
oxidation reaction is lower for almost all modified materials. Only in the case of
Cs2.5PW12 and Cs2.5SiMo12 modified layers onset potential is not change in comparison
to the Pt/C electrode. These results are very important in a point of view of theirs
practical application as an anode materials for the fuel cells.

Eonset / V vs. RHE

0,56

0,54

0,52

0,50
12

12

Si

Si
-R

2.

5
2.

-R

/C

/C
Pt

40

%
40
Pt

%
40
Pt

12

5
2.

b
-R
/C

/C
%

16

PM

12

PW
5

-R

2.

%
40
40
Pt

%
40
Pt

12

/C

12

Pt

s
-C
/C

2.

PM

PW

12

s
-C
%

40
Pt

%
40
Pt

2.

Si
5

/C

-C

2.

Si
5

/C

2.

-C
/C
%
40
Pt

12

12

Fig. 67. Onset potential of methanol electrooxidation on the investigated materials recorded in
argon saturated 0.5 mol dm-3 CH3OH + 0.5 mol dm-3 H2SO4. Data taken from Fig. 52 and 61.

Based on the results obtained by Samant et al.[7] we can conclude that the
superior oxidation kinetics in presence of zeolites matrix could be due to the preferential
formation of CO clusters on platinum that are limited by the steric constraints imposed

123

by the zeolites framework, followed by facile oxidation to CO2 by interaction with the
surface or bridged hydroxyls of the zeolites species.

4) Chronoamperometry tests on catalytic layers (Fig. 68) confirm earlier obtained


results that modification of commercial Pt/C with ours zeolite matrix increase catalytic
activity of the system towards methanol oxidation. The best performance after 1000
seconds of polarization at constant potentials (0.47 and 0.52 V) is obtained with the
system modified with Rb2.5SiW12 matrix. Nevertheless, the layers containing
Cs2.5PMo12, Cs2.5SiW12, Rb2.5PW12, Rb2.5PmO12 and Rb2.5SiMo12 salts also exhibit
higher current densities than the unmodified Pt/C electrode at both studied constant
potentials.

0 ,0 6

A
0 ,0 4

j / mA cm

-2

0 ,0 2

0 ,0 0

B
0 ,3 0

0 ,1 5

o
iM

12

12
2.

S
5
2.

-R
/C

/C
P

t4

0%

0%
t4
P

16

iW

o
M

P
5

-R

2.

-R
/C
0%
t4

12

12

W
5

b
/C

0%
t4
P

2.

-R

t4
P

12

/C

12

0%

P
5
2.

P
5

-C
/C

0%
t4
P

12

12

S
5
2.

/C

t4

0%

/C
0%
t4

-C

S
5

-C

2.

-C
/C
P

0%
t4
P

2.

iW

o
iM

12

0 ,0 0

Fig. 68. Current densities of methanol electrooxidation as a function of electrode composition.


The data were obtained from chronoamperometric curves (Fig. 53 and 62) after 1000 seconds
of electrodes polarization at (A) 0.47 V and (B) 0.52 V in argon saturated 0.5 mol dm-3 CH3OH
+ 0.5 mol dm-3 H2SO4. T = 24 0C

124

5) The CO stripping voltammetry is a very important method, because CO is one of the


main poisoning intermediate products during methanol electrooxidation. Therefore the
studies on increasing resistance of the system towards this strongly adsorbed
intermediate species were made. The results presented in Fig. 69, clearly shows that the
onset potential of the CO oxidation is shifted to the lower value of potentials for the
systems modified with cesium and rubidium zeolite matrix.
Our results confirm that the system modification increase tolerance towards CO. The
PMo12 or SiMo12 containing materials behave as a redox mediator for the CO oxidation
reaction with Pt present in the system, while the PW12 and SiW12 materials may provide
additional hydroxide groups which facilitate oxidation of passivating intermediates
(COads) on Pt.

Eonset / V vs. RHE

0,75

0,70

0,65

0,60

12

o
M
b

-R

2.
5

Si

Si
2.
5

b
-R

/C

/C
Pt

40

%
40
Pt

16

12

12

o
PM
2.
5

b
-R

Pt

40
%

/C

/C
%
40

Pt

12

12

PW
2.
5

-R

40
%

/C

12

Pt

PW
s

-C
/C
%

40
Pt

2.
5

PM
s

-C
/C

Pt

40

/C
%
40
Pt

2.
5

Si
-C

2.
5

Si
s

2.
5

-C
/C
%
40
Pt

12

12

12

0,55

Fig. 69. Onset potential of methanol electrooxidation on the investigated materials recorded in
argon saturated 0.5 mol dm-3 CH3OH + 0.5 mol dm-3 H2SO4. Data taken from Fig.55 and 64.

6) The results of the cyclic voltammetry long-term stability test on investigated


electrode materials are placed in Fig. 70. The peak current densities obtained at the
forward scan were read at 600 minutes of the test.

125

jp / mA cm

-2

20

15

10

5
12

o
Si
M
5

-R
b

2.

Si
W

/C

Pt
40
%

/C
-R
40
%
Pt

2.
5

5
2.

b
/C
-R

12

16

12

PM
o

12

PW

12

5
2.

b
-R

Pt
40
%

12

/C
/C
Pt
40
%

5
2.

s
/C
-C

Pt
40
%

PW

12

PM
5

Pt
40
%

-C
s
/C

2.

5
2.

Pt
40
%

-C

5
2.

Pt
40
%
/C

/C
-C
40
%
Pt

12

Si
W

12

Si
M

Fig. 70. Peak current densities obtained at 600 minute of long-term stability test of methanol
electrooxidation on the investigated materials recorded in argon saturated 0.5 mol dm-3 CH3OH
+ 0.5 mol dm-3 H2SO4. Data taken from Fig. 56 and 65.

For all the modified catalytic layers the values of the peak current densities of methanol
electrooxidation were higher in comparison to the platinum electrode. The highest value
of jp was obtained for the Rb2.5SiMo12 containing material. However, the most stable
during long-term cyclic voltammetry stability test appears to be the catalytic layers
modified with Rb2.5PW12 and Rb2.5PMo12 matrix.

126

9. Ethanol oxidation reaction (EOR) on


the Pt40%/Vulcan XC-72 carbon
modified with Cs2.5-HPAs
Among the small organic molecules, ethanol, being a renewable biofuel, is a
promising candidate for a fuel cell. Compared with methanol, ethanol has many merits:
less toxic, better stability, lower permeability across proton exchange membrane.
Ethanol is safer than other hydrocarbons, and the energy density of ethanol is higher
than that of methanol (1325.31 and 702.32 kJ mol-1 for ethanol and methanol,
respectively). Nevertheless, the process of the oxidation of ethanol is more difficult than
that of methanol with is necessity to break the C-C bond to obtain its complete
oxidation. However, the formation of strongly adsorb intermediates species such as
(CO)ads on the Pt catalyst, which is usually considered as the best single metal to adsorb
organic molecules and break intermolecular bond, reflect in high oxidation
overpotentials. Therefore the aim of the present chapter is to investigate the influence of
the modification of Pt nanoparticles for the electrooxidation of ethanol.
Studies of the electrooxidation of ethanol in acidic media on the new systems
prepared by mixing method were carried out using different electrochemical techniques
such as cyclic voltammetry, staircase voltammetry, chronoamperometry, A.C.
Impedance and Tafel plots. The stability of catalytic properties will be also discussed.
Cyclic voltammograms of the systems modified by Keggin-type heteropolyacid
salts as a matrix recorded in argon saturated 0.5 mol dm-3 H2SO4 as well as CO
stripping of these layers will be not presented because of the great similarity to the
voltammograms obtained previously in chapter 8.2.1 and 8.2.5, respectively.

9.1 Cyclic voltammetry (CV) measurements


In order to compare the electrocatalytic capabilities of all four electrodes studied
(and Pt40%/C electrode as a reference), all the steady cyclic voltammograms of the
electrooxidation of ethanol in argon saturated 0.5 mol dm-3 C2H5OH in 0.5 mol dm-3
H2SO4 aqueous solution are presented in Fig. 71. In the forward scan, ethanol oxidation
produced a prominent symmetric peak (A) around 0.89 V. In the reverse scan, an anodic
peak current density (B) is detected at around 0.79 V. This peak is due to the oxidation

127

of all adsorbed carbonaceous species (e.g. Pt-OCH2CH3, Pt-CHOH-CH3, (Pt)2=COHCH3, Pt-COCH3 and Pt-CO).

A
25

j / mA cm

-2

20

15

10

0
0.0

0.2

0.4

0.6

0.8

1.0

E / V vs. RHE

Fig. 71. Cyclic voltammetric response of Nafion-containing films (deposited on glassy carbon
electrode) of () Pt40%/Vulcan XC-72 carbon modified with Cs2.5H0.5PW12O40, ()
Pt40%/Vulcan XC-72 carbon modified with Cs2.5H0.5PMo12O40, () Pt40%/Vulcan XC-72
carbon modified with Cs2.5H1.5SiW12O40, () Pt40%/Vulcan XC-72 carbon modified with
Cs2.5H1.5SiMo12O40 and () unmodified Pt40%/Vulcan XC-72 carbon. Electrolyte: argon
saturated 0.5 mol dm-3 C2H5OH + 0.5 mol dm-3 H2SO4. Scan rate, 10 mV s-1. Temperature,
240C.

It is noticeable in Fig. 71 that the Nafion-treated Pt40%/Vulcan XC-72 carbon


modified with Cs2.5H0.5PMo12O40 matrix shows the highest positive scan peak current
density for ethanol electro-oxidation among the catalysts investigated here. It is quite
apparent from the figure that backward anodic current density peak (jb) is greater for an
electrode where forward anodic current density peak (jf) is grater. Moreover, the ratio of
the forward anodic peak current density (jf) to the reverse anodic peak current density
(jb), jf / jb, can be used to describe the catalyst tolerance to carbonaceous species
accumulation. These results as well as peak currents densities and corresponding peak
potentials of the forward and backward scan are listed in Table 15. Low jf / jb ratio
indicates poor oxidation of ethanol to carbon dioxide during the anodic scan, and
extensive accumulation of carbonaceous residues on the catalyst surface. High jf / jb
ratio shows the converse case.

128

Forward peak
Catalysts

potential /

jf /
mA cm

Backward peak
-2

jb /

potential / V vs. mA cm

V vs. RHE

jf/jb
-2

RHE

Pt40%/C

0.894

16.60

0.796

14.77

1.12

Pt40%/C-Cs2.5H0.5PW12O40

0.897

21.62

0.800

18.44

1.17

Pt40%/C-Cs2.5H0.5PMo12O40

0.897

25.43

0.804

22.09

1.15

Pt40%/C-Cs2.5H1.5SiW12O40

0.898

20.30

0.802

19.14

1.06

Pt40%/C-Cs2.5H1.5SiMo12O40

0.898

19.31

0.798

17.00

1.14

Table 15. CV results of the investigated catalysts (24 0C).

It

is

clearly

shown

that

the

layers

containing

Cs2.5H0.5PW12O40,

Cs2.5H0.5PMo12O40 and Cs2.5H1.5SiMo12O40 salts as a matrix have higher ability to


oxidize ethanol to CO2 (particularly Pt-(CO)ads to CO2 ) in comparison to the platinum
electrode (higher value of jf / jb).

1.0
-1

log j / mA cm

-2

162 mV dec

0.5

0.0

-0.5

-1.0
0.4

0.5

0.6

0.7

E / V vs. RHE
Fig. 72. Tafel plots of ethanol oxidation at the Nafion-containing (--) Pt40%/Vulcan XC-72
carbon modified with Cs2.5H0.5PW12O40, (--) Pt40%/Vulcan XC-72 carbon modified with
Cs2.5H0.5PMo12O40, (--) Pt40%/Vulcan XC-72 carbon modified with Cs2.5H1.5SiW12O40, (--)
Pt40%/Vulcan XC-72 carbon modified with Cs2.5H1.5SiMo12O40 and (--) unmodified
Pt40%/Vulcan XC-72 carbon. Temperature, 240C.

129

Moreover, Fig. 71 clearly show that modification of commercial Pt40%/C by cesium


HPA salts matrix increases noticeably electrocatalytic activity of the system for EOR
(higher current densities were obtained for all modified catalytic layers). This enhanced
activity could be attributed to the increased surface area of the catalytic sites created by
high dispersion of Pt.
A very convenient way of comparing the performance of different electrode materials
for an ethanol electro-oxidation process is the use of steady-state polarization curves
and the corresponding Tafel plots. This innovative procedure allows a clear and
pictorial view of two important parameters, namely the starting potential and the current
density value for the systems under investigation. Thus, Fig. 72 shows the Tafel plots
carried out in the potentiostatic mode for ethanol oxidation process at the Nafioncontaining (red symbols) Pt40%/Vulcan XC-72 carbon modified with Cs2.5H0.5PW12O40,
(green symbols) Pt40%/Vulcan XC-72 carbon modified with Cs2.5H0.5PMo12O40, (dark
blue) Pt40%/Vulcan XC-72 carbon modified with Cs2.5H1.5SiW12O40, (light blue)
Pt40%/Vulcan XC-72 carbon modified with Cs2.5H1.5SiMo12O40 and (black symbols)
unmodified Pt40%/Vulcan XC-72 carbon as a reference. For the oxidation of ethanol on
the investigated Pt - Cs-HPAs composite electrodes and for the unmodified Pt/C system
the b (slope) value is ca. 162 mV dec-1. However, the existing mechanism[124] is
extremely complex and not allow for the establishment of the rite determining step (rds)
for theoretical calculations of the Tafel slope value (b). It is clear that the current
density related to the active surface area (at constant value of potential) increases with
platinum dispersion by shifting the Tafel plot cathodically: e.g. at 0.5 V the current
density for modified layers (particularly for the systems containing Cs2.5PW12 and
Cs2.5SiW12 matrix) is much higher that this for pure system (Pt40%/C). Nevertheless,
the same value of b shows that there is no change in the reaction mechanism,
particularly the rate determining step. These results suggest a weaker poisoning for the
electrodes modified by Cs2.5-HPAs matrix.

9.2 Staircase voltammetry (SV) measurements


Fig. 73 present dependencies of staircase voltammetric responses (step period of
50 s recorded every 25 mV) of ethanol oxidation on catalytic layers containing Nafion
treated Pt40%/C and cesium salts of Keggin-type heteropolyacids, particularly12phosphotungstic

acid

(Cs2.5H0.5PW12O40),

12-phosphomolybdic

acid
130

(Cs2.5H0.5PMo12O40), 12-silicotungstic acid (Cs2.5H1.5SiW12O40) and 12-silicomolybdic


acid (Cs2.5H1.5SiMo12O40), respectively, as a matrix and commercial unmodified
electrocatalyst

(Pt40%/Vulcan

XC-72

carbon)

as

reference.

Presence

of

Cs2.5H0.5PMo12O40 matrix in the system results in some increase of ethanol


electrocatalytic currents (compare curves for unmodified and modified systems in Fig.
73).
12

j / mA cm

-2

10
8
6
4
2
0
0.4

0.6

0.8

1.0

E / V vs. RHE
Fig.73. Staircase voltammetric current densities for the ethanol (0.5 mol dm-3) oxidation
recorded every 25 mV (between 0.25 and 1.07 V) following application of 50-s potential steps at
the Nafion-containing layer of (--) Pt40%/Vulcan XC-72 carbon modified with
Cs2.5H0.5PW12O40, (--) Pt40%/Vulcan XC-72 carbon modified with Cs2.5H0.5PMo12O40, (--)
Pt40%/Vulcan XC-72 carbon modified with Cs2.5H1.5SiW12O40, (--) Pt40%/Vulcan XC-72
carbon modified with Cs2.5H1.5SiMo12O40 and (--) unmodified Pt40%/Vulcan XC-72 carbon.
Electrolyte: argon saturated 0.5 mol dm-3 H2SO4..Temperature, 240C.

It is important to note that electrocatalytic activities (shown as the current densities at


corresponding peaks) for all modified electrode materials are higher than that of Cs2.5HPAs - free system. To express more clearly, the mass activity (MA, mA mg-1), defined
by peak current density per unit of catalyst loading, was used to evaluate the
electrocatalytic activity of the system for ethanol electrooxidation. The MA was
calculated according to the following equation[213]:
MA = jp/md x 103

(89)

131

where jp (mA cm-2) is the peak current density and the md (g cm-2) is the loading mass
of Pt. The obtained values are presented in Table 16.

jp /

LPt /

MA /

mA cm-2

mg cm-2

mA mg-1

Pt40%/C

8.770

100

87.70

Pt40%/C-Cs2.5H0.5PW12O40

10.13

100

101.3

Pt40%/C-Cs2.5H0.5PMo12O40

12.02

100

120.2

Pt40%/C-Cs2.5H1.5SiW12O40

10.73

100

107.3

Pt40%/C-Cs2.5H1.5SiMo12O40

9.570

100

95.70

Catalysts

Table 16. The mass activity of the investigated catalysts (24 0C).

The highest MA value was obtained for catalytic layer modified by


Cs2.5H0.5PMo12O40 zeolite type matrix (Table 16). The mass activity value for this
system is almost 40% higher in comparison to platinum electrode (Pt40%/C) while for
the other investigated electrode materials the MA value was from 9 to 22 % higher than
for unmodified system. This can be explained by the more exposed nanoparticles of Pt
in the zeolite matrix (Cs2.5-HPAs), which result in increasing specific surface and also
effect in higher electrocatalytic activity of Pt/C-zeolite (Cs2.5-HPAs) catalyst. Moreover,
zeolite material with special porous structure provides relatively high permeability and
good micromedia for ethanol oxidation.[7] We should to point out that for Pt/C - Cs2.5HPAs catalyst, Pt act as the main catalyst for catalyzing the dehydrogenation of ethanol
during the oxidation reaction and the oxygen containing species can be provided by the
framework oxygen sites or surface hydroxyls of the zeolite particles. Whats more these
oxygen-containing species strongly react with CO-like intermediate species on Pt
surface to release the active sites for further ethanol oxidation.[7]

9.3 Chronoamperometry (CA) measurements


Chronoamperometric experiments were carried out to observe the stability and
possible poisoning of the catalysts under short-time continuous operation. Fig. 74 shows
the current-time curves recorded for the several Pt containing electrode systems in
argon saturated 0.5 mol dm-3 C2H5OH + 0.5 mol dm-3 H2SO4 solutions at a fixed
potential of 0.47 V versus RHE. The initial current density decay can be addressed to a
132

great extent to the increasing surface coverage with partially oxidized intermediates.[214]
Meanwhile, that initial decay was much less pronounced in the case of ethanol
oxidation for Pt40%/C-Cs2.5PW12 composite suggesting less poisoning of the electrode
surface than for the other electrode materials.

0.6

j / mA cm-2

0.5

0.4

0.3

0.2
0

200

400

600

800

1000

E / V vs. RHE
Fig. 74. Chronoamperometric curves recorded for the ethanol oxidation at the Nafioncontaining layer of () Pt40%/Vulcan XC-72 carbon modified with Cs2.5H0.5PW12O40, ()
Pt40%/Vulcan XC-72 carbon modified with Cs2.5H0.5PMo12O40, () Pt40%/Vulcan XC-72
carbon modified with Cs2.5H1.5SiW12O40, () Pt40%/Vulcan XC-72 carbon modified with
Cs2.5H1.5SiMo12O40 and () unmodified Pt40%/Vulcan XC-72 carbon upon application of (A)
0.47 V. Electrolyte: argon saturated 0.5 mol dm-3 H2SO4.. Temperature, 240C.

Most of the current densities present a quasi-stationary behavior after 400 seconds of
polarization. This slow decay of the current densities is due to the poisoning of the
material during the advance process.[215] However, it is important to note that the current
density for the layer containing Cs2.5PMo12 zeolite matrix after initial decay start to
increases with time what suggest that the presence of PMo12 into the system help to
cleaning Pt surface from CO-like intermediate species.

133

0,30
0,29

j / mA cm

-2

0,28
0,27
0,26
0,25
0,24
0,23

40

40

O
12

o
Si
M
H

2.
5

2.
5

Pt
40
%

/C

-C

-C
/C
Pt
40
%

1.
5

Si
W
1.
5

10

12

40

12

5
0.

H
2.
5

Pt
40
%

/C

-C

-C
/C
Pt
40
%

PM

12

2.
5

0.
5

PW

/C
Pt
40
%

40

0,22

Fig. 75. Current densities of ethanol electrooxidation as a function of electrode composition.


The data were obtained from chronoamperometric curves after 1000 seconds of electrodes
polarization at 0.47 V in argon saturated 0.5 mol dm-3 C2H5OH + 0.5 mol dm-3 H2SO4.
Temperature, 24 0C.

Values of the current density for ethanol oxidation measured after 1000 second at 0.47
V are plotted against the electrode composition in Fig. 75. It can be observed that
electrodes with Cs2.5H1.5SiW12O40 and Cs2.5H1.5SiMo12O40 matrix exhibit lower activity
than unmodified system. Layer containing cesium salt of 12-phosphotungstic acid after
1000 seconds of oxidation of ethanol at 0.47 V shows the same current densities like
unmodified Pt40%/C electrode. The highest current density for EOR was found for
Pt40%/Vulcan XC-72 carbon containing Cs2.5PMo12 salt as a matrix, which is in good
agreement with CV and SV results.

9.4. Electrochemical impedance spectroscopy


for ethanol electrooxidation
In order to understand the characteristics of the electrocatalysis reaction on
modified electrodes, additional analysis of the ac impedance behaviour was carried out.
The electrochemical impedance spectra of Pt modified electrodes recorded in argon
saturated 0.5 mol dm-3 H2SO4 + 0.5 mol dm-3 C2H5OH at 0.75 V are shown in Fig. 76.

134

-Zimag / ohm

900

600

300

-300
0

500

1000

1500

2000

Zreal / ohm
Fig. 76. Nyquist plots recorded in Ar saturated 0.5 mol dm-3 C2H5OH + 0.5 mol dm-3 H2SO4
aqueous solution for Nafion-containing (--) Pt40%/Vulcan XC-72 carbon modified with
Cs2.5H0.5PW12O40,(--) Pt40%/Vulcan XC-72 carbon modified with Cs2.5H0.5PMo12O40, (--)
Pt40%/Vulcan XC-72 carbon modified with Cs2.5H1.5SiW12O40, (--) Pt40%/Vulcan XC-72
carbon modified with Cs2.5H1.5SiMo12O40 and (--) unmodified Pt40%/Vulcan XC-72 carbon
catalysts at 0.75 V. The frequency range is from 0.05Hz to 100kHz. Each electrode contained
100 g cm-2 of the platinum.

The diameters of the semicircles (Fig. 76.) decreased in order Pt40%/C > Pt40%/C +
Cs2.5SiMo12 > Pt40%/C + Cs2.5SiMo12 > Pt40%/C + Cs2.5SiMo12 > Pt40%/C +
Cs2.5PMo12 > Pt40%/C + Cs2.5PW12. This behavior can be related to the charge transfer
resistances, which decrease with increasing effective surface area for the charge transfer
reaction. A significantly different x-axis intercept were observed for the Pt40%/C and
Pt40%/C-Cs2.5SiMo12. This behavior is due to the higher film resistivity for these
samples in comparison to the others investigated materials. The impedance data from
Fig. 76 suggest inductive behavior of the spectrum, which has been well studied by
several researchers.[208,216] They showed that an inductive loop appeared if the reactions
step of an intermediate species is the rate determining. It is considered that CO forms on
the electrocatalyst as a strongly adsorbed intermediate and that the electro-oxidation of
COads to CO2 is a rate determining step.

135

9.5 Electrochemical stability of investigated materials


containing Cs2.5-HPAs
Electrochemical stability of the catalytic layers containing Cs2.5-HPAs zeolite
matrix during long-term ethanol oxidation was shown in Fig. 77.

30

jp / mA cm

-2

25

20

15

10

0
0

200

400

600

800

t / min
Fig. 77. Long-term stability test of the Nafion-containing (--) Pt40%/Vulcan XC-72 carbon
modified with Cs2.5H0.5PW12O40, (--) Pt40%/Vulcan XC-72 carbon modified with
Cs2.5H0.5PMo12O40, (--) Pt40%/Vulcan XC-72 carbon modified with Cs2.5H1.5SiW12O40, (--)
Pt40%/Vulcan XC-72 carbon modified with Cs2.5H1.5SiMo12O40 and (--) unmodified
Pt40%/Vulcan XC-72 carbon electrodes in argon saturated 0.5 mol dm-3 H2SO4 containing 0.5
mol dm-3 C2H5OH solution at 50 mV s-1. Temperature, 240C. Same Pt loadings mounted in all
cases (LPt = 100 g cm-2).

As a reference stability test for unmodified Nafion treated Pt40%/Vulcan XC-72 carbon
electrode is also presented. It is evident that the worst performance shows system
containing Cs2.5SiMo12 as a matrix. The final current density for this electrode material
at the end of the test was 32% lower than the onset potential.
The drop of the current densities during long-term stability test for ethanol
electro-oxidation on the investigated layers is presented in Table 17.

136

Catalysts

Current
density drop

Pt40%/C

22.3 %

Pt40%/C-Cs2.5H0.5PW12O40

13.5 %

Pt40%/C-Cs2.5H0.5PMo12O40

22.8 %

Pt40%/C-Cs2.5H1.5SiW12O40

29.7 %

Pt40%/C-Cs2.5H1.5SiMo12O40

32.4 %

Table. 17. Current density drops during long-term stability test.

The data obtained from the stability test indicate that the best performance
towards ethanol oxidation in the long term shows catalytic layer modified by the
Cs2.5PW12. However, the highest current densities values during all experiment were
obtained for the Nafion-containing Pt40%/Vulcan XC-72 carbon modified with
Cs2.5PMo12 matrix.

137

Conclusions

This thesis is focused on the development of stable, proton highly-conductive,


meso-microporous matrices for Pt that can be used to increase the CO tolerance of
PEMFC, DMFC, and DEFC anodes.
In the first experimental part of this thesis (Chapter 6), the IR spectra clearly
show that the primary Keggin structure remains unaltered even when the protons form
parental heteropolyacid are substituted by the cesium or rubidium cations. This is
important from the point of view of the systems CO tolerance that shall be attributed to
the presents of tungstate and molybdenum units in the structure. The SEM results
presented here clearly suggest that morphology of heteropolyacids changes dramatically
when the protons in heteropolyacid are substituted by cesium or rubidium cations. This
substitution supports the existence of small spherical particles. The cyclic
voltammograms recorded for investigated materials deposited on the glassy carbon
electrodes show that some of the heteropolyacid salts exhibit behavior similar to that
characteristic of their analogues in solution. This phenomenon can be explained in terms
of the partial solubility in solution, particularly ammonium salts. On the basis of the
results obtained in Chapter 6, the salts of Keggin-type heteropolyacids containing 2.5
moles of cesium and rubidium cations in 1 mole of the heteropolyacid salt (such as
Cs2.5H0.5PW12O40,

Rb2.5H0.5PW12O40,

Cs2.5H0.5PMo12O40,

Rb2.5H0.5PMo12O40,

Cs2.5H1.5SiW12O40, Rb2.5H1.5SiW12O40, Cs2.5H1.5SiMo12O40, Rb2.5H1.5SiMo12O40) can be


applied as matrices for Pt catalysts.
The next part of the thesis (Chapter 7) is devoted to the hydrogen oxidation
reaction on the Pt/Vulcan catalysts modified with Cs2.5H0.5PW12O40 prepared by two
methods (mixing and electrochemical deposition).
We demonstrate that incorporation and activation of catalytic Pt centers in these
conductive high-surface-area zeolite-type robust matrices is feasible. Immobilization of
platinum nanoparticles within the micro-mesoporous hybrid material was achieved
through electrochemical deposition of platinum by corrosion of Pt counter electrode.
HRTEM investigation shown that the particles have spherical sizes and their diameters
range 1 2 nm and 3 - 4 nm for Cs2.5PW12 modified and free system, respectively. The
difference in particle size may be due to fact that Pt deposition, on the Cs2.5H0.5PW12O40
containing composite, occurs inside the nanochannels of the porous tertiary structure of

138

the salts that posses characteristic diameters, while in the case of pure Vulcan the
particles grow on the surface where are more prone to grow. The electrochemically
active area obtained from CO stripping voltammetry combined with the results from
HRTEM allows estimating the loading of Pt, ca. 2.6 g cm-1.
Comparison was made to the electrocatalytic system produced by simple mixing
of Vulcan XC-72 supported platinum (10 wt %) nanoparticles with the cesium
heteropolytungstate salt. In both cases, regardless the method of preparation and the
nature of immobilization of Pt sites, clear enhancement of the platinum activity were
observed during hydrogen oxidation.
The next chapter of the thesis (Chapter 8) deals with the applications of the
cesium and rubidium salts of the Keggin-type heteropolyacids as matrices for Pt/Vulcan
during methanol oxidation reaction. The results obtained with cyclic voltammetry and
staircase voltammetry methods clearly show that the modification of commercial Pt/C
with cesium and rubidium salts of HPAs significantly increases the electrocatalytic
currents (compare to unmodified Pt/C), and shifts the onset potential of the methanol
oxidation reaction to the less positive values. This suggests that the presence of Cs2.5HPAs or Rb2.5-HPAs matrix into the catalytic layer may facilitate the electrooxidation
of intermediate species such as the CO that is adsorbed on the Pt catalyst surfaces
leading to suppression of the poisoning effect on Pt catalysts by CO or CO-like
intermediates.
The results are also consistent with the data obtained from CO stripping
voltammetry, where the modification of Pt catalyst by the Cs2.5-HPAs or Rb2.5-HPAs
results in shifting onset potential of CO oxidation to the less positive values. An
important issue is that, among all examined catalysts, the Pt/C-Cs2.5SiMo12 and Pt/CRb2.5SiMo12 shows the lowest onset and peak potentials for CO oxidation, while the
Pt/C exhibits the highest parameters, respectively. Long-term stability test confirm
earlier obtained results that modification of commercial Pt/C with zeolite matrix
increase catalytic activity of the system towards methanol electro-oxidation. The highest
value of the jp (peak current densities of methanol electrooxidation) was obtained for the
Rb2.5SiMo12 containing catalytic layer. However, the most stable during long-term
cyclic voltammetry stability test is the system modified with Rb2.5PW12 and Rb2.5PMo12
matrices.
The results presented in chapter 9 clearly show that the Pt/C modified with Cs2.5HPAs catalysts studied display electrocatalytic activity with respect to ethanol oxidation
139

as evidence by the voltammetric and chronoamperometric measurements. The data


obtained from the stability test indicate that the best performance towards ethanol
oxidation (in the long term experiment) is exhibited by the catalytic layer modified by
the Cs2.5PW12. However, the highest current densities values during all experiment were
obtained for the Pt40%/Vulcan XC-72 carbon modified by Cs2.5PMo12 system.
The results presented in the thesis suggest that cesium and rubidium
heteropolyacids salts should be considered as good matrices for anodes in the low
temperature fuel cells (PEMFC, DMFC, DEFC). It is reasonable to expect that the
amounts of precious Pt (or Ru) can be somewhat diminished during practical
applications.
We should to admit that the all experiments presented in the thesis were reproducible
within 5-7% in different measurements.
The results presented in Chapter 7 of the thesis are the part of the Italian and
international patent.[203,204]

140

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