436

DENKI KAGAKU
Stu（1y of Oxygen Reduetion Reaction in Sulfuric Acid．on Thin Porous
              Electrod．es Composed of Carbon an（l Platinum

Marcelo L， CALEGARO，Joelma PEREZ，Auro A．TANAKA，Edson A． TICIANELLI

              and Ernesto R．GONZALEZホ

Received December14，1995，Accepted February16，1996

Inthiswork，theoxygenreductionreactionwasstudiedinO．5Msulfbricacidsolutionson
platinum dispersed on carb‘）n with10，20，30，and40％w！w Pt／C ratios，using the thin porous
coatingtec㎞que．qclicvdta㎜etUwasusedtoevaluatethePtelectrochemicalactiveareasof
the elec血’odes and steady−s惚te polahzation curves obtained with the rotating disk elec血’ode
technique were employed to study the oxygen reduction reaction・Cyclic voltammetly showed that
the activiり〆of the Pt part］icles with respect to the hydrogen adsoηンtion／desoη）tion process is
dependent on the particle size，From the combinatめn of the polarization data with the thin film−
flooded agglomcrate model it was possible to obtain the kinetic and mechanistic parameters fbr the
oxygen reduction reaction，which resulted only dependent on the catalyst nature．It was obsewed
that the mechan藍sm and重he kinetic behavior ofthe reaction were the same as those on gas（lmsion
electlodes or on smooth polyc町stalline platinum．The only diffbrence was fbund in the Tafbl slopes
of the polarization diagrams which double as a consequence of the porous nature of the dispersed
catalyst elecぱodcs．

  shown by published  Transmission Electron
            l INTRODUCTlON Micr・sc・py（EM）results5），H・wever，di働ences
    The study of the oxygen reduction reaction
  of one order of magnitude were fbund between the
（ORR）on dispersed platinum on cξlrbon catalysts has
  absolule values of the platinum areas．These
been the object of several publications 食）r over 20
  diffbrences were explained in terms of the several
years，because ofthe importance ofthese materials for
  limitations of the TEM and CV technlques and it
apPlicati・ninvari・uskinds・f釦elcellsl）Ina
previ。usw。rkc。nductedin。urlab。rat。可2），this was concluded tha町clic volta㎜et可provides
  more consistent results鉛r the evaluation of the Pt
τeactionwasstudiedinLOMNaOHsolutionsonthin   active area，when an electrochemical system is
porous coating rotating disk electrodes （TPC／R工）E）
  considered．
prepared with O，10，20and30％wlw Pt／C catalysts．
（ii）Analyses of the ORR poladzation data ob松ined
Cyclic voltammet可（CV）and steady stale pdarization
  with the TPC／RL）E with the 山in mm！flocded−
techniques were cmployed in the experimental   agglomerate model provided a simple and ade（luate
investigation．An alkaline medium was chosen
  way to evaluatc the pe血㎜ance ofthc suppo“ed
because of the reduced inter艶rence of redox processes
  catalysts，The predicted ef琵ct of』doubling of the
due to sur鉛ce fUnctional groups on the carbon
  Ta驚l slope of』the ORR on the Pt／C ca囲ysts due to
substrate，compared with acid elect】rolytes．The steady
  difhsional problems in the flooded agglomerate
s田te  oxygen  reduction  polarization  data  were
  was co㎡irmed experimenta玉1y．
analyzed using the thin猛lm／nooded agglomerate
（iii）The kinetic parameters obtained食）r the ORR．on
諜黙離姻、糊膿、黙e騰鮒   the several catalysts indicated that， in alkaline
  media and for the lower Pt／C ratios，there is a
The m＆in conclusions ofthe previolls work were：
  strong Participation of the carbon substrate in the
（i）The￠yclic voltammetric expcriments showed that
  catalysis of the reaction．
  the area per gram of the platinum particles
    In this work，the oxygen reduction reaction was
  diminishes with the incre窺se ofthe Pt／C ratio in the
  suppo宜ed catalysts，in agreement with the tendency s重udledinO5Msulhlricacldsolutionsonplatlnum
dispersed on carbon with O，10，20，30，and40％wlw
P）C ratios， using tke same techniques presented
above．As in the previous work，lhe RDE results fbr
lnstituto de Quimlca de s匪o Carlos − USP，
廿1e ORR．on the TPC爪工）E electrodes were analyzed in
Departamento de Fisico Quimica
terms of the thin film／flooded agglomerate model of
CP780，Sao Carlos，SP，CEP13560−970，Brazil
gasdi飾si・nelectr・des3・4・6。9），asmathematically
Key Words：dispersed electr㏄＆talysts，oxygen treatedby蝕istricket．al3・4）intheCa貢esia鰐stem．
reduction，electrode modeling，thin porous coating
electrode．
 437
64，No．6（1996）

            2EXPERIMENTAL
    川though  described  previously  孟）r alkaline
electr・1巽e2），血ede田ils・ftheexpedmen回w・rking
conditions will be presented here fbr consistency．
Thin porous coating ro田ting disk electrodes were
・・
used fbr cychc voltammetry and polahzation
measurements，These weτe prepared by mixing the
catalyst powders【Vulcan XC−72carbon，and lO，20，
30，and40％w！w P》carbon（E−TEK Inc．，USA）】with
蓬〉ノ
a dilute suspension（霜2％w！w）of a Teflon emulsion
のuPont TM30） and fbllowing the procedures ≧
describedelsewherelo）．

    A   conventional  three  compartment
electr㏄hemical cell with Luggin capillaU was used in
the electrochemical experimems．A platinum fbil and 、，ワ
a saturated calomel electrode（SCE）served as counter
and −e角rcnce electrodes， respectively． In order to
avoid contamination of the working electrode

♂
compartment，a salt bridge containing the working
electrolyte was employed to connecI the refヒrence
eleclrode to the ce1L All the experiments were carried
outinO．5MH2SO4solutions，preparedfromahigh
puriり’ reagent （Merck） and water distilled  and
一〇．4 0。0 0．4 0．8 1．2
purified in a Milli−Q （Milhpore）system The
elec吐rolytes were saturated wkh purified N20r O2 E〈！vs，SCE
gases．Alhhe experiments were conduc！ed at room
Fig．l Cyclic voltamograms of TPC electrodes
temperature（25士loC）．
prepared with diffヒrent Pt／C catalysts in N2−saturated
    The cyclic vokammetη and rotating disk
O．5MH2SO4soluti〔）n．v＝5mV／s．
polarizatio皿measurements werc perfbrmed wiIh a
PARC Model273potentiostat coupled wiIh an IBM−
PC compatible microcomputer，The clectrode rotation
    3RESULTS AND DATA PROCESSING
    Figure l shows the cyclic voltammograms in
speeds werc control且ed by a AFMSRE！ASR Pine
O．5MH2SO4solutionfbrthe20and40wt，％Pt／C．In
Instmment Co．systcm All the voltammetric curves
contrast with the voltammograms obIained employing
reported in this paper correspond essentially to the
gasdi価si・nelectrωesl1）inacidmedia，aquite
stationaU rcsponses obtained on electrodes cycle（l
reasonable resolution of the platinum fヒatures was
between−0．25to l．15V vs，SCE，that is，between Ihe
fbund．For the other catalysts the vokammograms
onset of hydrogen evolution and the sta亘of ca∫bon
μesented the same quahtative features，Table l
corrosionloxygen evolution，Furthe【more， several presents the active area per gram of platinum on the
potential scan rates were employed to record the cyclic
TPC electrodes， evaluated ffom  the qchc
vGkammograms．butonlythcresponsesrecordedat5
    噸l voltammetric responses fbllowing the pr㏄edure
mV s were considered fbr quantitative analyses，The described befbre2）．For comparison，the corrcsponding
Pt active areas were evaluated fヤom the voltammetric
                                   ロ 
resuks。btainedprevi・uslyusingEM5）areais・
culves by assuming the value of210μC cm fbr the
included．
hydrogen desorption charge on smoolh Pt electrodes5）
    Figure2presents the oxygen re（luction
and面【ing into account the weight Qf the TPC layers
polahzationcurvesforseveralrotat童onratesob面ned
obtained a丘er perfbrming the electrochemical
inO，5MH2SO40ntheTPCIRDEelectrodeprepared
measureme皿ts．The oxygen reduction polarization wi｛h 20帆．％ PVC catalyst．Figure3 illustrates the
curves invoMng the TPC were recorded point・by−
point in the potentiostatic mode to avoid the high Table l Active plal．inum su㎡ace areas obtained from
capacitive cuπents associated with this 妙1）e of
一聾tric ex eriments in acid solutions・
electrode．The electrodes were polarized in both
             Acllive Area   AreaπEM
direcIions（increasing o1’decreasing the polarization）
Electr・de一
until a stable pe血rmance was obse四ed，but only the
10％Pt／C 93 47 135
polarizaIion curves obtained at increasing 215 47 100
Polarizations are prcsented． 20％Pt／C
30％Pt1C 240 36 88（a）

40％Pt1C 366 35 80
一1，Cata1・即es鵬ci五cati・n．
438
DENKI KAGAKU
1、5
x 3600rpm    X × XXX
2500rpm x X                  ワワワ
◇ 1．0             ▽▽Xムムム
x
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X
1．2
o 900rpm       ム    O        口0回
    ▽   O     ロ ロ
ム 625rpm X     ◇O◎◇◇Q     A o      口
   ▽        口
   o o 0，8     o
▽ 400rpm
 o
        回
  ワ
×
▽合 。
PげC20％    ◇   合
        X
                 O ロ ロ ロO回 ワ
0，9 合 ロ
                口
       x O   D O   0．6
      x。◇ロ 回      ▽ム
｛ 蓬       o  ロ   ▽  PツC40％
    ▽ム  “    ム  P》C30％
＝       ◇ロ。。・…。。。。。 ≧
     o ロ     o  Pt／C20％
0．6
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         さ
   マム   ロP》CIO％
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0．3     9▽
    1▽ 0，2   ワム 回
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  奪唇
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 △                            禦寮

0．0
 葦
0．0
90・ロ
鰹業選触騨慨一
0，8    0，6    0，4    0．2    0．O 0．8 O．6     0．4     0．2 0．0

          E l V vs，SCE     E／V vs．SCE

Fig． 2 Sleady−state polarization curves at di舳rent Fig 3 Steady−state poladzation curves 藪）r oxygen
elec吐rode ro訟tion rates R）r oxygen reduction on20％ reduction o皿TPC・RDE prepared wiIh di働fent Pt1C
Pt／C TPC・RDE in O．5MH2SO4solution． catalysts in O．5MH2SO4soluIion．∫＝1600rpm．

ef亜ct of catalyst composition fbτa constant rotation constant at the reversible potential（k’AvLy），k’is the
rate Qf the electrode（1600rpm）．To compare the rate constant on the catalyst at the∫eversible potential，
sp㏄ific pe㎡bmnance of the catalysts with respect to Av is the catalyst area per unit volume，C＊is the bulk
“｝e ORR the values of cun’ent obtaine〔i at O．6V in reactant concentration，b is the Ta蛋el slope of the ORR

thepolahzationcuπveswerenomlalizeddividingby in the catalyst，Da is the d曲sion coe茄cient of
the su血ce area of platinum in the electrodes，using oxygen in the agglomerate，and Df is the d㎞sion
the TEM and CV values。The resuks of such c㏄mcient ofoxygen in the thin fi且m
calculations are presented in Table2．     Two limiting3’4）stnlctural ef騰cts are predicted

    The RDE results fbr the ORR on the TPC
e1㏄αodes were analyzed in tems of the thi面lm−
flooded agglomerate model origimlly developed fbr
gas dif釦sion electrodes3’4）． The several aspects
stressing  the conrespondence between  the  thin
mm／flooded agglomerate modcl an（l the TPC lotating
disk electrode were presented befbre2）．According to
thisthe・reticalm・de124），thereducedcuπentde皿si嬢
（J）passing from the agglomerate into the solu“on can
be vπitten as：
                 tan φexp（μ12）
           exp（μ）
（1）
」＝，／，＝  φexp（μ12）
     。7＋Fexp（μ）tan哩ΦeXl）（μ12）1
                      φexp（μ12）
where i is the actual cuπent density，五〇is the
exchangecm・entdensi砂（nFkoC＊），μ量sthereduced
倉om the ana星yses of Eq，（1）fbr the polarization
behavioroftheTPCeleclrode：（i）1argevaluesofφ
（larg叫）1eadtoaduplicationofthesloP“oftkeμvs・
ln J plot at且arger values of J（orμ）；（ii）1arge values of
r（1argeδ）1eadtotheapPearanccoflimiting
di価sional cun’ent in thc plot．
    Substitution ofμ，φ，and r in Eq．（1）gives the
theoretical dependence of the cuπent densi呼 as a
hnction of the electrode potential and the several
physic㏄hemical and electr㏄hemical parameters of
the system：Da，D6Ly，δ，Cホ，io，b and n。
    Paramethzation of the theoretical equation was
pe㎡bmcd by using the depth value of the electrode
cavity，Ly≡0．034cm，measu【e（l with a digital
micrometer，tabulated values fbr the d曲sion
臨農12）噌，＝Sl翌評。詳、腿葛x、瀞
       ．3
mole cm，respectively，and values of the thin film
di伽si・nparameter・btained丘・mmEequati・ns13），

羅離1徽i蹴，職糖n辣
the thin film difhsion parameter（δko！Df），皿is the
number ofclectrons tmnsfbrred，ko is the ef琵ctiveτate
         一3         −3         ，3          −3
δ＝3．OxlO，2。4xlO，2．Ox10，1，5x10，1．2x
  ・3      甲3
10，1・O x10 cm fbHotation lates400，625，900，
1600，2500，and3600ψm，respccIivcly，The value of
64， No，6 （1996）
Table2Specmc cun’ent densities R）r the ORR」br the
several catalysts at an electrode potential of O．6 V．
The areas ofPt we【e those presented in Table l R）r the
TEMand CVresults．
Electrode  Cuπent Current densiり〆pcr
（幅．％P∀C）  at O．6V   unit area of Pt
             （mA）     （mA cm−2）
TEM      CV
10 0．l l
4．l x10 1．2x lOり
20 O．25 5．4x lO4 L2xlO’3
30 0．29 4．9xlO’4 1．2xlO冒3
40 0．39 4．7xlO層4 Llx1σ3
Da， the difhsion coe伍cient in the flooded
agglomerate，was assumed to be the same as in the
bulk electrolyte，th＆t is，Da≡Df This approximation
dld not introduce m司or changes in the rcsults since
small variations in Da were evalu飢ed to havc
negligible effbct on the simulated c皿ves，
    Iteration to ob頓in the best values of io，b，and n
is necessa可and it was executed con6idering that the
Ta免l slope of the ORR is dependent on the coveragc
of oxygen on the platinum surf血ce which jbllows a
Temkin isothc㎞  at high electrode potentials
（〉【◎．55V），and a Langmuir isotherm at lower
electrωep・tentials14）（＜司、55V）．Fi副res4and5
show examples of the application of Eq．（1）to the
cxpcrimental results，indicating the ve曜good quality
Qf the五ttings．Thc aveτage（藪）r al置rQtation rates）
values of io，b，and n obta藍ned from these fi1tings for
the ORR．in the several cata直ysts are presented in
Table3」br the two Gonditions ofoxygen covcrage。
    Finally，thepolarizationdatawereamlyzedin
terms of mass transport corrected Ta斜diagrams
obtained by plotting the experimental data as E vs．log
器、謁醜血1蹄脇錨、識i器。綴
the apPropriated parametrization for each situation
and taking the thin film di飾sion parameter r＝O in
Eq．（1）．Examples of such Tafd plols arc presented in
Figure6．
              41）ISCUSSION
    The results in Table l show that the total CV
area increases輌th the increase of the PげC weight
ratio．The same behavior can be obselved from the io
values presented in Table3．Both facts are related to
the increase of the Pt loading on the TPC electrodes
wkh the increase of P》C ratio，since the cavity is
filled wkh an approximately constant volume of the
materials to form the active layer．A more close
correlation between the predictions of CV and the
values of io cannot bc established because of the l8rge
unce血in嬢in the abso藍ute values of io introduced by
the mo（lehng analysis an（1by the extrapolation to
reach the ORR standard poteptiaL
439
    On the other hand，it can be observed in Table l
that the CV sur飴ce area per gram of plalimm
presents a tendency to decrease with the increase of
the Pt／C mtio．As also observed in alkaline media2）
and from the TEM results5），this ef陀ct can be
attdbuted to an in（ンrease of the Pt pa質icle size輌th
the increase ofP》C ratio．However，it is observed that
the CV v81ues of specmc area are ca．40％of those
obtained with TEM。Since the electrode is completely
filled with the electrolyte， the reasons fbr these
discrepanciescanbediscussedinte㎜softheseveral
l㎞itations that the CV and TEM techniques present
恥nhedeteminali。n・ftheRarea2）．F・呵clic
voltamme吐ry， 重he limiting factors may be：
（i）impe㎡ヒct electric contact belween lhe catalyst
particles，which gives underestimated currents in the
recorded cyclic vol1．ammograms and（ii）the presence
of impurities，1eading to a partial blocking of the
hydrogen adsorption／deso甲tlon process，For the TEM
technique， the fbllowing limitations can be
consideredl（i）itisassumedasphericalgeometrylor
the platinum particles， which is a rough
approximation fbr the real system and（ii）the total
area of Pt loaded on lhe carbon is considered in the
calculation， theref（》re， including the area partiaIly
bl㏄kedasaconsequenceofanchoringthePtonthe
carbon substrate，the area ofPt which is not in contact
with the carbon pal↑icles and also the area of a large
amounI of too sman or too largc platinum particles
which may presenI reduced voltammelric activity。
    O．8
      ン：
0．6
  0．4 口 3600rpm
8
ゆ
o 2500rpm
璽 ム 1600rpm
∼o．2 ▽ 900rpm
LI ◇ 625rpm
X 400rpm
0．O
Pt1C30％
一〇．2
O．01 0．1 1
11mA
Fig．4Experimentill（symbols）and simulated（solid
lines）Ta角l plots fDr oxygen reduction o皿30％Pt／C
electτode in O．51》I H2SO4 solution fbr di焼rent
electrode rotation rIltes．
440
O．8
▽
o 0。7
0．6
 0．4
四
〇
口 Pt！C10％
ω o Pt1C20％
望 ム Pt1C30％
≧0．2 ▽ Pt1C40％
u』
卜1600rpm
O．0
一〇．2
0．01 0．1 1 一2  −1  0   1  2
                 11mA
Fig、5Experimenta1（剛mbols）and simulated（solid
hnes）Tafel plots for oxygen reduction on dif驚rent
HIC catalysts inO．5MH2SO4solution．∫＝1600Φm．
   This重ast point has been used to explain the
changeofthespec面cactivityoftheplatinum
crysωlites wiIh respect to the OR1しas a f㎞nction of
the particle size which reaches a maximum fbr
pa血cle sizes close to2・3nml5’16）．In the present case，
thisc・πesp・ndst・thecatalystwith20帆，％PσC5〉．
The resuhs in Table2show thaI the specific curren1
dcnsi呼obtained by nomalizing the cuπent aI O．6V
using the TEM Pt area also reaches a maximum fbr
this catalyst，ind量cating that the same tendency
pr・凶sedprevi・us畳yl5）f・rthecatalystactM嫁ls
obse【ved herc when the TEM sur鉛ce area is
considered．
   On thc other han（1，the resuks of Table2show
that the speci丘c activily is independent of the catalyst
（or p肛ticle size）when the cu∬ent is norm紐hzed using
the CV area．This is a ve剛重mp（レrta飢observation
since i1implies that the sam￠tendency fbund in the
ac丘vi呼fbrtheORRwithrespecttopa丘iclesize，
holds for the hydrogen adso“）tion／dlesoΦtion process
in the cyclic vohammet可．
   Thc polarization diagrams presented in Figure3
clear監y show the ve剛low activity of the purc carbon
                              ド 
catalyst fbr the ORR．Kouteck夕一Lcvich plots（i vs．
fl／2）c・nstmcted負Qmtheexpedment＆旦P・la亘zati・n
data at several electrode pote皿tials p【escnt straight
pa」rallel Iines」br all PげC catalysts．This behavior is an
indication that the ORR，is五rst order with respect to
the oxygen concentration and1he number of electrons
DENKI KAGAKU
0．8
ム
A Pt1C40％
  Ptlc30％
  Pt1C20％
0．6
  Pt1C10％
  0．5
山
oの
  0、4
ω
》
＞
、0．3
田
0．2
0．1
0．0
    Logl（ldxly（ld−1）1
Fig．6Mass−transpo貢coπected Tafd plots fbr oxygen
reduction o皿di飾rent PヅC catalysts in O。5M H2SO4
solution．∫＝1600τpm，Solid line：simulated Ta飴I
plot with r＝O in Eq。1，
involved in the reaction is constant，independent of
theelectrodcpoten“alandofthecatalystPVC
composition，Taking血e slopes of such lines and
usこngthevalues・fD㎝dC＊presented臨re，v’2）＝
1．2xlO−2cms−1，F＝96，487Cm。r1，andA＝
      2
9撫認13膿鑑灘），論51錨盤
catalysts．The resuhs of Table3also show a value of
n＝40btained丘om the fitting of the theoretical thin
film−flooded agglomerate equation fbr the ORR．in all
catalysls．Thus，i皿this respecI，the behavior of the
dispersed catalysts with the several Pt／C ratios in the
TPC electrodes is the same as that fbr the ORR in acid
濫畠．識cl謄1，標罰tinum1貴12’1生’7）・r輌thgas
   Tab星e3 shows that the Ta免l slopes ob⑫ined
from the fittings have thevalues exp㏄tedf6r the ORR
on the platinum catalyst．For smootk polycWstamne
platinum and gas difhsion electrodes，two Tafd
fegions，with slopes of60and l20mV deca91（at
250C）fbr low and high overl）otentials，respectively，
have been obseτved f≧）r the ORR in acid soluIions．The
exislence of two slopes is explained in terms of the
coverageoftheelectrodesu血cebyadsorbedoxygen，
which fbliows a Temkin isothem  at low
overpotenti＆ls and a Langmuir isothemh at1亘gher
・ve㈱tentialsl4），The changes・fads・Φ“・n
conditionscanbebetterunderstoodusingthecyclic
voltammograms obtained in the absence ofdisso星ved
64，No．6（1996）
Table 3 Fitting parameters obtained fbr oxygen
reduction onPt／C catal sts in O．5MH2SO4at250C，
Low cun・enI High currenI
  densi   densi
Pt！C    且o   b（mV  io（A  b（mV  n
（％） Acm’2 deca’I cm’2 deca響1
10 5xlO− 56 24xlO層 120 4 clearly obsenゾed；
20 4xlO−10 57 74xlO’6 120 4 （iii）Asinalkalinemedia2），analyses・ftheOm
30 9xlO’lo 57 94xlO甲6 120 4．1
40 l5xlO’10 57 14xlOF5 120 4．1
oxygen（Figure l）．In the region abovc ca．0．55V vs・
SCE，the platinum s皿face is covere（l with adsorbed
oxygenated species，while bclow this value the oxides
are reduced．Experimentally，it has been observed th＆t
lhe ORR prese齪s Ta琵1s】opes of60mV deca冒10n lhe
oxide covered Pt regio皿and l20mV deca40n the
。xide−heeregi・n14）．
    It is important to observe th飢the above values of
Tafel slopcs could be obtained only with the support
of the modeling analysis of experimental data，It is
see皿thaUhe experimental polnts of the Tafヒl plots
presentedinFigure6nUhetheoreticallinewitha
slope of60mV deca冒10nly fbr a few points located in
the highest vokage region of the diagram At lower
potentials，a region with a l20mV deca’1slope is
defined，and then a240mV deca’1slopc−is clearly
seen．According to the model，the inte㎜e（liate region
wiIh a slope of l20mV deca曹I arises as a consequence
of structural eHbcts in the electrodes which lead to the
doubhng of the ef琵ctive Ta飴l slope of the reaction on
the considered cataIyst in th垂s range of potentiaL This
behavior is consistent with the cyclic voltammograms
ofFig皿e l，since the l20mV deca’1slope appears in
aregionofpotentialinwhichthccatalystiscovered
to a large exten〔 with oxide． Following thls
interpretation，the240 mV  deca−1Ta血l slope
observedinFigure6correspondstothedoublingof
the ef驚ctive value（120mV deca’1）in the oxide flee
reglon・
             5CONCLUSlONS
    Taking into account the behavior of the ORR on
thedispersedcatalysts，severahmpo質antobservations
can be made from the results ofthe present work：
（i）Asinalkalinemedia2），鋸clicv・1tammetワsh・wed
that the measured area of the platinum catalysts
diminishes with the increase of the Pt／C ratio，
However，the resuks in acid media show tha巨hls
trend can be rel＆te（l to the speci行c activity of the
dispersed platinum crystallites with respect to the
hydrogen adsoη）tion／desoq）tion process which is
（lepen（lent on the particle size． In this sense the
actMty for hydrogen adsorption／desorption is similar
to that obseIved R）r the specinc activity of the
platinum crystallites fbr the ORR，which reaches a
m腿imumf・r卿iclesizescl・set・2−3nm15）．
441
（ii）The polarizatioll curves and thc kinetic parameters
obtained fbr the ORR．on the several catalysts show a
negligible pa宜icipation of the carbon substrate in the
ca田lysis of the realction in acid solution．This is in
contrast with the1・esults in alkaline media2），where
the pa貢icipation of carbon through a2（ブpathway was
po監arization da田 （レbtained with the TPC−RDE with
the thin film／fIooded−agglomeraIe model provided a
simple and adequal．e way to evaluate the perfbmlance
of the supported cξltalysts．From this analysis it was
poss孟ble to obtain the real Ta琵l slopes of the ORR in
the materials which resulted60mV deca91fbr the
oxide covered electrode and120mV deca’1fbnhe
oxide free surface．As predicted by the model the
doubLing of the above Ta食l slopes due to the
structural influence of the porous electrodes is clear監y
observed．
    The authoτs wish to thank Funda⑫o de Amparo
a Pesquisa do Estado de Sao P＆ulo （FAPESP），
Conselho Naciona丑de Desenvolvimento Cient面co e
Tecno16gico（CNPq）and Financiadora de Estudos e
pr（オelos（FINEP），」br丘nancia監suppo【ts，
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