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
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
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.
7.1
7.1.1
Mixing method..62
7.1.2
Electrochemical method63
7.2.2
7.3.2
7.3.3
HRTEM characterization..81
7.3.4
7.4
Among other important issues related to electrocatalysis are their ability to undergo
30]
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
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
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.
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.
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)
(3)
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.
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
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]:
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
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]
13
(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-
(8)
(9)
(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
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]
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:
(11)
Cathode reaction:
3
(12)
Overall reaction:
(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)
(18)
-
(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.
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)
(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
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]
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)
O2 + 4 H+ + 4 e- 2 H2O
(23)
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)
(25)
MCHOHCH3 MCHOCH3 + H+ + e-
(26)
MCHOCH3 MCOCH3 H + e
(27)
(28)
M + H2O MOH + H+ + e-
(29)
(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)
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).
(HPAs)
are
complex
proton
acids
that
incorporate
24
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]
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]
27
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
(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.
30
Primay
structure
Secondary
structure
W3O13
the
H+ (H2O)n, Cs2+,
Cu2+, K+, Mg2+, ect.
cubic
of
H3PW12O406H202,
with
sites,
called
to
the
of
the
micocrystallites.
Aggregates
microcrystallites
called
the
are
tertiary
structures corresponding.
[14, 164]
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.
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
33
4. Experimental techniques
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.
37
i=
nFAD( c o c )
(38)
(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.
40
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).
sinusoidal
current
signal
of
amplitude
IAC
(amps)
and
frequency
(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:
(44)
(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
(46)
Z = Z + Z
(47)
where,
Z = Re(Z) = |Z|cos
(48)
Z = Im(Z) = |Z|sin
(49)
Z = ( Z ) 2 + ( Z ) 2
magnitude of impedance
(50)
and,
= tan-1 (Z/Z)
(51)
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
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
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
(52)
E = h0( + )
(53)
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]:
(54)
In the thesis infrared spectroscopy was used as an established tool for the
structural characterization of heteropolyacids salts (Chapter 6.2).
47
48
D) Experimental conditions:
49
50
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
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]
54
55
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).
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
3-
(55)
3-
VI
(56)
4-
VI
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
-0.3
j / mA cm
-2
em
-0.6
0.2
0.0
-0.2
fn
-0.4
0.2
0.4
0.6
0.8
-2
E / V vs. RHE
j / mA cm
0.02
go
-0.04
0.3
0.4
0.5
0.6
0.7
0.8
E / V vs. RHE
59
4-
VI
4-
(58)
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
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
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-
PtCl4 + 2e = Pt + 4Cl
(59)
(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)
64
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
2.5
j / mA cm-2
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)
-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
-3
M). In 0.5 M H2SO4, the calculated value of Levich constant, B, and the solubility, c0,
-2
-2
-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
-2
which is in fairly good agreement with above calculated value (6.54 x 10 (mA cm )
rpm
-1/2
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:
(Tafel reaction)
(5)
70
(Heyrovsky reaction)
(6)
(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
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
-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
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).
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.
Weight in grams
0.0073
0.0059
0.0067
0.0087
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
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
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
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.
400
300
200
100
2
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
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.
77
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
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.
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
(67)
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.
j / mA cm
-2
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.
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).
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
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,
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
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
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.
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
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.
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.
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.
Tafel
slopes
for
the
catalytic
layers
containing
Cs2.5H0.5PW12O40,
(70)
H2O (OH)ads + H+ + e-
(71)
(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)
For a better insight of the system reactivity towards methanol oxidation reaction
staircase voltammetry has been used. Fig. 51 shows
dependencies of staircase
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
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
97
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
(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
1
+
Rct
1
1
1
=
+
a + j
Rct R0 + jL
B
B
(81)
100
B
1
Rct a + j
(82)
Rct2 B
Ra
1
ZF =
= Rct +
= Rct +
YF
a Rct B + j
1 + jRa C a
(83)
[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)
101
6000
-Zimag / ohm
5000
4000
3000
1000
0
0
1000
2000
3000
4000
5000
Zreal / ohm
-Zimag / ohm
500
Cs2.5H0.5PW12O40,
(--) Pt40%/Vulcan XC-72
400
300
Cs2.5H0.5PMo12O40,
200
100
0
-100
-200
-300
Cs2.5H1.5SiMo12O40 and
(--) unmodified Pt40%/Vulcan
-400
0
200
400
600
800
1000
Zreal / ohm
300
200
-Zimag / ohm
100
-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
104
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
(86)
(87)
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
(88)
WO3
stability test
were
obtained
for
the
catalytic
layers
containing
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).
108
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
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.
Rb2.5SiW12,
Rb2.5SiMo12)
matrix
and
unmodified
electrocatalyst
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
of
HPAs.
The
best
performance
shown
catalytic
layer
containing
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
() Pt40%/Vulcan XC-72
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
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
2000
1000
Nafion-containing
0
1000
2000
3000
4000
5000
Zreal / ohm
400
-Zimag / ohm
200
Rb2.5H1.5SiW12O40,
(--) Pt40%/Vulcan XC-72
-200
-400
0
200
400
600
800
1000
Zreal / ohm
200
-Zimag / ohm
100
0.05Hz to 100kHz.
Each electrode contained 100 g
-200
-300
-400
-400
-300
-200
-100
Zreal / ohm
117
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
(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.
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
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.
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.
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.
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
124
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.
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
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.
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
It
is
clearly
shown
that
the
layers
containing
Cs2.5H0.5PW12O40,
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
acid
(Cs2.5H0.5PW12O40),
12-phosphomolybdic
acid
130
(Pt40%/Vulcan
XC-72
carbon)
as
reference.
Presence
of
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.
(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).
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
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.
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
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 %
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
Rb2.5H0.5PW12O40,
Cs2.5H0.5PMo12O40,
Rb2.5H0.5PMo12O40,
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
140
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