Electrochimica Acta. 1964. Vol. 9. pp. 63 to 77. Pergamon Press Ltd.

Printed in Nort hern Ireland

THE ANODI C OXIDATION OF METHANOL AND FORMIC
ACID AND THE REDUCTIVE ADSORPTION OF CO~*
J. GINER
Pratt & Whi t ney Aircraft, Di vi si on of Uni t ed Aircraft Corporat i on,
East Har t f or d 8, Conn. , U. S. A.
Abstraet---4)n t he anodi c fast-potential-sweep curve made on platinized pl at i num in acid solutions
cont ai ni ng CH, OH and HCOOH an "adsor pt i on" peak appears, t he potential of which is a strong
funct i on of t emperat ure: at 95C, approximately Eh = 400, at 25C at approxi mat el y E~ = 600 mV
(potentials against reversible H2-electrode).
This adsorpt i on peak is ascribed to the oxi dat i on of an intermediate, which was reported previously
to be also formed by reduct i on of COs and which we call "r educed COs" (possibly it is CO or COOH).
Here this species is formed by partial oxi dat i on of met hanol or formi c acid and to some extent by
decomposi t i on of these reactants at open circuit. Below the potential of the peak this species ac-
cumulates on t he electrode and blocks further oxi dat i on of the react ant ; above the potential of the
peak the species is oxidized to CO, faster t han it is being produced, freeing t he surface for continuous
oxi dat i on.
The same results apply qualitatively to bright platinum.
R6sum6--Sur la courbe anodi que de balayage rapide du platine platin6, dans des solutions acides
(CH3OH + HCOsH) , il apparai t un pie d' adsorpt i on, d6pendant fortement de la t emp&at ure (400
mV ~t 95C et 600 mV ~- 25C, par rapport ~t 61ectrode ~, hydrog/~ne). Il est attribu6 h l ' oxydat i on d' un
interm6diaire, pr6c6demment signal6 pour la r6duction de COs (peut-6tre CO ou CO, H) . La mEme
e s p / ~ serait ici due/~ l ' oxydat i on partielle de CHaOH ou de HCOsH et (dans une certaine mesure)
la d6composition de ces corps en circuit ouvert. Au dessous de la tension du pic, ces constituants
s' accumul ent sur l'61ectrode, bl oquant l ' oxydat i on ult6rieure. Au dessus, l ' oxydat i on en COs est plus
rapide que la product i on de corps oxydable, ce qui libere la surface pour un processus continu. Les
n6mes constatations peuvent ~tre faites qual i t at i vement sur le platine poli.
Zusammenfassung--Bei der anodischen Kurve, erhalten durch rasche, kontinuier!iche .~nderung des
Potentials an platiniertem Platin in sauren, CH3OH und HCOOH enthaltenden LSsungen, kann eine
"Adsor pt i ons"- Wel l e festgestellt werden, deren Potential ausserordentlich temperaturabh/ingig ist:
Bei 95C E h = c a. 400, bei 25C E h c a. - - 600 mV (gegen rev. Hs-Elektrode).
Diese Adsorptionswelle wird der Oxydat i on eines Zwischenproduktes zugeschrieben, welches
vorgfingig auch als bei der Redukt i on von CO2 gebildet beschrieben worden war, und "reduziertes
CO2" gennaut wurde (mSglicherweise CO oder COOH) . Im vorliegenden Falle wird dieser Stoff
durch partielle Oxydat i on von Met hanol oder Ameisens:]ure, zu einem gewissen Gr ade auch dut ch
Zersetzung dieser Substanzen bei offenem Stromkreis gebildet. Unt erhal b des Potentials der Welle
reichert sich der Zwischenstoff auf der El ekt rode an und verhindert weitere Oxydat i on de.r Ausgangs-
substanz; oberhalb dieses Potentials wird der Zwischenstoff rascher zu COs oxydiert ats er gebildet
wird und gibt die OberflS_che zur fortlaufenden Oxydat i on frei.
Anal oge Resultate werden qualitativ an blankem Platin gefunden.
I NT R ODUC T I ON
IN A precedi ng paper 1 it was established t hat CO2 reacts in acid solution with electro-
chemi cal l y f or med hydrogen, chemi sorbed on pl at i num, at pot ent i al s between 0 and
250 mV (Eh), and is reduced t o a chemi sorbed product . This pr oduct is oxidized again
t o CO2 at pot ent i al s f r om 400 t o 600 mV (Eh) dependi ng on condi t i ons of t emper at ur e
(95C-25C) and roughness fact or.
In this paper it will be shown t hat the same chemi sorbed pr oduct is formed when
* Manuscript received 3 Augvst 1963.
5 63
64 J. GINER
met hanol and formi c acid are part i al l y oxidized and also t o some ext ent by decom-
position at open circuit of these reactants and t hat this pr oduct blocks t he el ect rode
surface at low pol ari zat i on, st oppi ng the f ur t her oxi dat i on of t he react ant ( CH3OH or
HCOOH) t o CO 2. Onl y aft er the el ect rode has been br ought t o a pot ent i al higher
t han the oxi dat i on pot ent i al of t he chemi sorbed species is t he el ect rode freed of t he
blocking compound, and yields CO z.
Recent l y several fast pot ent i al -sweep curves for the met hanol oxi dat i on on Pt can
be f ound in t he literature. ~-'~ We will discuss these curves f r om t he poi nt of view of a
possible "r educed CO2" and its effects on t he curve. Ot her features of t he curve
such as t he effect of chemi sorbed oxygen will not be discussed here. Also t he effect
of part i al oxi dat i on f r om met hanol t o formal dehyde, f r om f or mal dehyde t o formi c
acid and f r om formi c acid t o CO 2 will not be consi dered at the moment .
EXPERI MENTAL
Pot ent i ost at i c techniques descri bed previously 1 were used in these experi ment s,
i.e. the pot ent i al of t he el ect rode was ei t her mai nt ai ned const ant or linearly varied, by
using an el ect roni c pot ent i ost at . For t he experi ment s with platinizedplatinum t he
linear pot ent i al sweeps used were so selected t hat diffusion processes were negligible
compar ed with surface processes. The following condi t i ons were selected, under which
adsor pt i on peaks are pr edomi nant :
(a) Low concent rat i on of the react ant (met hanol or formi c acid) t o avoi d maski ng by
diffusion process.
(b) Hi gh surface roughness of the electrode.
(c) Hi gh pot ent i al sweep r at e; t o be selected accordi ng t o t he surface roughness.
(d) El i mi nat i on of stirring duri ng pot ent i al sweep.
(e) Mai nt ai ni ng t he el ect rode f or specified peri ods under stirring at a pot ent i al where
t he expect ed chemi sorpt i on pr oduct is fiarmed.
To keep these condi t i ons we have used in our wor k concent rat i ons of 10 -4 t o
10 -a M; el ect rode roughness fact ors of t he or der of magni t ude of 1000; pot ent i al
sweep rates (r0) of 20-200 mV/ mi n, no stirring duri ng t he linear pot ent i al sweep, and
variable waiting times (to) of 0- 20 mi n precedi ng t he sweep at a pot ent i al (Eh0) at
which t he chemi sorbed pr oduct is f or med (for instance E h = 200 mV at 95C).
Dur i ng t he waiting time t he el ect rode was r ot at ed at 600 rev/min.
For compari son, measurement s with bright platinum el ect rodes were made using
a t echni que as descri bed by Will and Knor r . 5 The sweep rat es used were relatively
slow f or bright pl at i num ( , ~ 100 mV/sec) so t hat diffusion current s and adsor pt i on
current s were measured simultaneously.
For all t he experi ment s t he el ect rol yt e was freed of Oz by bubbl i ng Nz. The
el ect rol yt e sol ut i on was 2 N H2SO 4 and, i f not ot herwi se stated, was kept at 95C.
In each case t he condi t i ons of t he experi ment s are quot ed with t he figures. Met hanol
was spect rographi cal l y pur e and formi c acid 'was reagent grade. As reference el ect rode
a cal i brat ed pol ari zed el ect rode was used.e The pot ent i al s are referred t o t he reversible
hydrogen el ect rode under same condi t i ons (Eh).
EXPERI MENTS ON PLATI NI ZED PLATI NUM
The el ect rodes had an initial real surface, in all cases, of t he same or der of magni-
tude, correspondi ng t o 250 t o 750 mC/ cm z of hydrogen charge, measured by t he
Anodic oxidation of CH~OH and reductive adsorption of C02 65
charging curve met hod. Since a given el ect rode was used f or several experi ment s and
a physical loss of real surface occurs, surface det ermi nat i ons were made aft er the
experi ment s when a quant i t at i ve experi ment was involved. The measured real surface
(by hydr ogen charge) is quot ed with the experi ment .
I f not otherwise stated, t he el ect rode was act i vat ed by polarizing for 2 rain -at
E h = 1800 mV (t o oxidize impurities and displace impurities f r om t he Pt surface by
oxygen) followed by 2 mi n at E h = - - 50 mV (t o reduce chemi sorbed oxygen). Aft er
this pre-t reat ment ei t her the pot ent i al was br ought t o a fixed pot ent i al and kept at
this pot ent i al f or pre-set time, aft er which an anodi c i(E) curve was taken, or was
br ought directly to a given fixed pot ent i al val ue and flOE curves were taken.
Methanol
The adsorption peak on the i(E)-sweep curve. In the following it is shown t hat a
cur r ent peak appears on t he i(E)-sweep curve. The electric charge consumed duri ng
t he peak and t he i ndependence of this charge on t he sweep rat e show t hat this peak is
6 O O
~ a b
4 OO
2 0 C
4
mA,/crn2
FIG. 1. i(E)-sweep on platinized Pt/2 N H,SO4, 10 -'J M CHtOH, N2 at 95C. Effect of
sweep rate (ro) on adsorption peak (to = 15 min, E~n = 200 mV); r0 (in mV/min):
(a) 20, Co) 200, (c) 50, (d) 100.
an adsor pt i on peak. This is confi rmed by t he fact t hat the peak is obt ai ned in absence
of stirring, under condi t i ons at which diffusion peaks shoul d be negligible. Compar i ng
the pot ent i al of the peak obt ai ned aft er CO2-reduct i on I and t hat obt ai ned by CH3OH
part i al oxi dat i on, and t he effect of sweep rat e, and t emperat ure, on these peaks, it is
concl uded t hat in bot h cases t he same pr oduct is formed. This is confi rmed by the
fact t hat gas evol ut i on f r om t he el ect rode is observed when the current peak is reached
and by compari ng t he effect of t he adsor pt i on pr oduct s f or med by CO2-reduct i on and
by part i al met hanol oxi dat i on on t he cur r ent of tile met hanol oxi dat i on.
Fi gure 1 shows t he i(E)-sweep curve obt ai ned with pot ent i al sweeps of different
rates af t er keepi ng the el ect rode at const ant t i me of 15 min under stirring at E h =
200 mV.
The electrical charge consumed in the peak depends onl y on t he change of surface
with ageing of t he el ect rode and not on the pot ent i al sweep rate as Tabl e 1 shows.
Tabl e 1 summarizes values obt ai ned f r om curves such as those of Fig. 1.
66 J. GINER
TABLE I
Run Sweep rate Peak charge Hydrogen charge
sequence mV/min mC/cm 2 mC/cm 2
740 before - - - -
1 20 330
2 200 :270
3 50 250
4 100 :240
5 200 175
after - - - - 200
The experiment was made as follows: The electrode was pre-polarized at Eh = 1800 mV for
2 rain and afterwards at Eh = --50 mV for 2 more minutes. After this it was brought to Eh = 200
mV, and after a waitifig time of 15 min under stirring, the stirring was discontinued and the anodie
linear potential sweep impressed, starting at Eh = 200 mV. The experiments were made in the
sequence indicated in Fig. 1 and Table 1.
The cur r ent peak is di spl aced t o more positive values wi t h i ncreasi ng pot ent i al
sweep rate, as coul d be expected for an irreversible process. Thi s behavi our is i dent i cal
to t hat of the anodi c adsor pt i on peak obt ai ned after CO2-reduct i on (see Fig. 8 of
Reference 1). Dur i ng t he peak at high pot ent i al sweep rate (200 mV/ mi n) gas evol u-
t i on was observed from the electrode. Thi s can be i nt erpret ed as CO~ evolved when
the rate of pr oduct i on of CO 2 begi ns to exceed the rate of diffusion of it from the
el ect rode to t he electrolyte bul k.
>
E
6 o o
4OO
600
>
E
400
ILl
200
0 2
mA ~c m 2

1:
t ~
i 50* C
6 0 0
C
4 0 0
1:
LIJ
L i . . . .
2 C
r n A / c m ~
200
95* C
,(
f
2
r nA/ / c m 2
FIG. 2. i(E)-sweep on platinized Pt/2 N H~:SO4, 10 -:3 M CH3OH, N2, 95C. Effect of
temperature and prepolarization potential (E^o) on adsorption peak (r 0 = 50 mV/min)
Eh0 in mV, at 25C (a) 500, (b) 200; at 50~C: (c) 400, (d) 200, (e) 25; at 95C:
(f) 200, (g) 25.
Fi gure 2 shows t hat the t emperat ure has a doubl e effect. I n the first place the
lower the t emper at ur e is, the hi gher the pol ari zat i on pot ent i al whi ch is necessary to
obt ai n a given coverage after a given fixed pol ari zat i on time. Secondly, the adsor pt i on
Anodic oxidation of CH3OH and reductive adsorption of CO2
67
peak is di spl aced t o hi gher pot ent i al s with decreasi ng t emper at ur e. The t emper at ur e
effect on the peak pot ent i al is t he same as shown in Fig. 9 of reference 1 for the
anodi c peak obt ai ned in an acid sol ut i on sat ur at ed wi t h CO 2.
To obtain the curves of Fig. 2 the electrode was activated (2 min at Eh = + 1800 mV followed by
2 min at Eh = --50 mV) and then kept at the selected potential under stirring for 15 min. After
this time the stirring (motor and N2-bubbling) was discontinued and the anodic sweep impressed
beginning from the selected polarization potential.
8 0 0
600
400
25Oc
>
E
LO
2OO
l i
0 4 0 4 8
mA/cm 2 ~A/cm 2
Fro. 3. i(E)-sweep on platinized Pt/2 N H,SO4, 10- ' M CHsOH, N~ Effect of open
circuit wait on adsorption peak ( t o = 15 min, r o = :ZOO mV/min) 25C: (a) Eh0 = open
circuit potential (OCP), (b) Eho = 500 mV; 95C (c) Eho -- OCP (d) E~o = 200 mV.
60O
4OO d
Fi gure 3 shows t hat at 95C t he a mount of adsor bed pr oduct f or med dur i ng a
wai t i ng t i me of 15 mi n at open circuit is consi derabl y smal l er t han t hat obt ai ned under
pol ar i zat i on at E h ---- 200 mV, but is nevertheless significant. At r oom t emper at ur e
the amount of chemi sor bed pr oduct f or med at open circuit is still much smal l er
t han t hat f or med at a pol ar i zat i on of E h ---- 500 mV ( compar e also wi t h t he results of
Fig. 2). These results l ead us t o believe t hat the chemi sor bed pr oduct which causes the
adsor pt i on peak is pr oduced by part i al oxi dat i on of met hanol by a react i on such as
CHa OH + Pt - ~ P t - - CO + 4H + 4-- 4e- (1)
i f we assume t hat t he chemi sor bed pr oduct is CO. Taki ng in account the
equi l i bri um pot ent i al of react i on
CHa OH+ H2 0 ~ CO 2 ~-6H ' ~ + 6 e - (2)
(Eh = 0-02 V) and t he pot ent i al at which a react i on such as
Pt + CO 2 + 2H + + 2 e - - ~ P t - - CO + H2 0 (3)
can occur (where CO has been t aken onl y as exampl e of a reduct i on pr oduct of CO2),
which accordi ng t o t he previ ous measur ement s I ihappens al ready to a small ext ent at
E h = 250 mV, it can be concl uded t hat a react i on such as (1) can occur at a pot ent i al
as negat i ve as E h = - - 1 0 0 mV. Thi s means t hat at open circuit a chemi cal
68 J. GINER
react i on such as
CH3OH --~ COads + 2H2 (4)
is t her modynami cal l y possible.
Thi s react i on can be visualized as t he current l ess combi nat i on of an anodi c react i on
(as eq. 1) and a cat hodi c react i on as
H + + e- - ~- ~H 2. (5)
Equat i ons (1) (3) (4) can be wri t t en wi t h anot her reduct i on chemi sor pt i on pr oduct of
CO s such as
O
f
P t - - C
\
OH.
React i ons ot her t han (5) as cat hodi c por t i on of the current l ess react i on (4) are al so
concei vabl e.
I n Fig. 3 it is i nt erest i ng t hat at open circuit t he peak is di spl aced to a hi gh pot ent i al
with respect t o the peak obt ai ned under pol ari zat i on. I t seems t hat when the cover age
is very low a t i ght l y bonded chemi sor pt i on occurs which causes a hi gh peak pot ent i al ;
i ncreasi ng t he coverage anot her peak at less posi t i ve pot ent i al s appears. When the
cover age is ver y hi gh t he peak at less posi t i ve pot ent i al s becomes very large and masks
the smal l peak at mor e posi t i ve pot ent i al al t hough some i ndi cat i on of it still exists.
Exact l y t he same behavi our has been observed wi t h t he peak obt ai ned aft er reduci ng
CO2"; t her ef or e the shape of t he peak confi rms t hat the adsor pt i on pr oduct f or med
by part i al oxi dat i on of met hanol is t he same as f or med by par t i al r educt i on of CO 2.
The experiments of Fig. 3 were made as follows: The electrode was anodically polarized at
Eh = 1200 mV for 2 rain followed by 2 min at Eh = --50 mV (the anodic polarization of 1200 mV
instead of 1800 mV was selected to avoid O~ evolution which could falsify the open circuit results).
After this activation, the electrode was kept at open circuit for 15 min or at the given polarization,
under stirring. After this waiting time the stirring was discontinued and the potential sweep (200
mV/min) impressed, starting at Eh = 200 mV when working at 95C or at 500 mV when working at
25C. A blank experiment with no waiting time showed no measurable adsorption of reactant or
intermediate during the anodic and cathodic prepolarization.
To st udy t he r at e f or f or mat i on of adsor pt i on pr oduct at E n -~ 200 mV with
different met hanol concent rat i ons, the el ect rode was kept f or t he specified vari abl e
t i me at 250 mV and i mmedi at el y af t er war ds the stirring was di scont i nued and a
pot ent i al sweep of - - 200 mV/ mi n i mpressed. In Tabl e 2 the charges represent i ng
the ar ea under the peak for different times obt ai ned under these condi t i ons are
t abul at ed. The t abl e i ndi cat es t hat wi t h 10 -a M met hanol t he f or mat i on of the
poi soni ng pr oduct , wi t h t he charact eri st i cs of "r educed COz" is very fast ; 60 per
cent of t he sat ur at i on val ue is al r eady obt ai ned aft er 1 mi n. The coverage of the
el ect rode with chemi sor bed pr oduct at sat ur at i on cor r esponds roughl y t o a monol ayer .
Wi t h 5 . 1 0 -a M CHz OH, sat ur at i on is reached at the same fast rat e as wi t h 10 -a M
CH3OH sol ut i on, but it seems t hat the sat ur at i on coverage is less compl et e.
A quant i t at i ve t r eat ment is difficult becau,~e the real surface decreases dur i ng t he
exper i ment by physical di si nt egrat i on or si nt eri ng and al so because of t he er r or in
det er mi ni ng t he charge under the peak and the hydrogen charge of the el ect rode.
* Unpublished results.
An o d i c o x i d a t i o n o f CH3 OH a n d r e duc t i ve a d s o r p t i o n o f CO2 69
I n Tabl e 2 t he val ues of the real surface before st art i ng and af t er finishing t he experi -
ment are t abul at ed. I t can be seen t hat in t he exper i ment wi t h 10 -3 M CHa OH t he
real surface expressed in mC/ c m ~ of hydr ogen charge aft er t he exper i ment is smal l er
t han t he " pe a k char ge" whi ch was measur ed j ust before di scont i nui ng t he experi ment .
Thi s i nconsi st ency shows t hat no concl usi on about absol ut e val ues shoul d be derived.
The t abl e shows al so t hat in 5.10 4 M sol ut i on t he concent r at i on of t he peak cur r ent
is al ways l ower t han wi t h 10 -3 M and al so l ower t han t he hydr ogen charge corre-
spondi ng t o t he real ar ea aft er finishing t he experi ment .
TABLE 2
Hy d r o g e n c h a r g e Pe a k c h a r g e a f t e r t mi n
C Hs OH ( mC / c m z) ( mC / c m0
oonc.
( M) i ni t i al af t er e x p e r i me n t t = 1 t = 2 t = 4 t = 15 t = 20
10 - a 880 520 450 450 500 750
5. 10 - 4 800 620 290 350 380
The current decay during the methanol oxidation at constant potential (at low
polarization) and the adsorption of"reduced CO2". Since it has been shown by vari a-
t i on of t he condi t i ons t hat duri ng CH3OH oxi dat i on at pot ent i al s of about E h = 200
mV, a chemi sor bed pr oduct is f or med whi ch at 95C is oxi di zed at about E h = 400
mV, and it is seen t o be pl ausi bl e t hat this pr oduct is t he same as t hat obt ai ned by
CO 2 reduct i on, it has t o be shown f ur t her t hat t he f or mat i on of this pr oduct is i m-
por t ant in t he mechani sm of CH3OH oxi dat i on at l ow pot ent i al s.
,o [
~E
I.C -
c o'
I ]
o .5 )o i 5 20
t, rain
FIG. 4. Po t e n t i o s t a t i c c u r r e n t de c a ys o n pl at i ni zed Pt / 2 N Ha SO, , C Hs OH, Nz a t 95 C
a n d E~ = 200 mV. Ef f ect o f C Hs OH c o n c e n t r a t i o n : (a) 10 - 8 M, Co) 10 -~ M, (c) 6-10 - 4
M, ( d) 0 M; a t , b t , c t , c o r r e s p o n d t o a, b, c, a f t e r 12 s e c a t E , = 450 mV.
To show this, the pl at i ni zed el ect rode was pol ari zed f or 2 mi n at E h = 1800 mV
fol l owed by 2 rai n at E h = - - 50 mV, in an aci d sol ut i on 1 0 - 3 M in met hanol , and
sat ur at ed wi t h Nv Aft er this pr e- t r eat ment , t he el ect rode was br ought t o 200 mV
and t he cur r ent r ecor ded as shown in curve a of Fig. 4. Thi s cur r ent was subst ant i al l y
7 0 J . G I N E R
higher t han the cur r ent obt ai ned under similar condi t i ons wi t hout CHa OH present in
sol ut i on (see curve d of Fig. 4), and decayed cont i nuousl y.
An increase of met hanol concent r at i on t o 10 -x M causes, compar ed wi t h t he
10 - a M curve, a shar p i ncrease of current (not visible on gr aph) some seconds aft er
act i vat i on, but also a fast er decay (curve b of Fig. 4); likewise a l ower concent r at i on
of 6 . 1 0 -4 M leads t o less steep decay (curve c of Fig. 4). Thi s agrees wi t h t he curves of
Fig. 6 which i ndi cat es a hi gher coverage wi t h poi son at hi gher CHa OH concent r at i on.
Fi gure 4 shows t hat , if aft er 10 mi n of pol ar i zat i on at E h = 200 mV, t he current
havi ng decayed consi derabl y, t he pot ent i al is ldrought t o E h -----450 mV f or 12 sec
(a pot ent i al mor e posi t i ve t han t hat o f " CO~- p e a k " at 90C but definitely not posi t i ve
enough t o cause any oxygen deposi t i on on Pt), an act i vat i on of t he el ect rode occurs.
Aft er the 12 sec at E n ---- 450 mV t he pot ent i al of En = 200 mV was i mpr essed
again. The current decay pl ot t ed in curve a' of Fig. 4 was obt ai ned. Thi s is very
si mi l ar t o t hat represent ed in curve a. The process was r epeat ed several t i mes and
every t i me an al most compl et e recovery of cur r ent was observed.
.
1. 0
E
k
0 c
L I
0 5 I 0
I, rain
FIG. 5. Potentiostatic current decays on platinized Pt]2 N H~SO~, 10 -8 M CH~OH, at
95C and Eh0 = 200 inV. Effect of "reduced COs" (a) and (b) CO2-saturated solution,
(c) N~
To relate t he poi soni ng pr oduct closely to t he adsor pt i on pr oduct f or med when
CO s is reduced on Pt an el ect rode wag act i vat ed as above, but in sol ut i on sat ur at ed
with CO s. Cur ve a of Fig. 5 shows t he current decay when the el ect rode was pol ari zed
at E h ~ 1800 mV f or 2 mi n, fol l owed by 2 rain at Eh = - - 50 mV and i mmedi at el y
aft erwards the pot ent i al of Eh ~ 200 mV is impressed.
Compar i ng this curve wi t h curve c of Fig. 5 obt ai ned wi t hout CO 2 but N~ bubbl i ng,
it can be seen t hat t he curve of the cur r ent decay wi t h CO 2 present falls below t he
curve obt ai ned under N 2 bubbl i ng. The expl anat i on is t hat at E h = - - 50 mV, CO s is
reduced and t he "r educed COs " poi sons the electrode. When t he "r educed CO2" is
pr oduced by part i al oxi dat i on of met hanol , mor e t i me is requi red t o cause the same
effect.
The poi soni ng by reduced COs is mor e pr onounced when aft er t he regul ar
act i vat i on the el ect rode is kept at E h = 50 mV for 2 addi t i onal mi n (curve b of
Fig. 5).
An o d i c oxi da t i on o f C H, OH a n d rexluctiv a d s o r p t i o n o f CO~ 71
I f aft er havi ng been poi soned by CO=-reduct i on t he el ect rode is kept f or 12 sec at
E~ = 450 mV and t hen br ought back t o E~, = 200 mV, react i vat i on is observed.
I n ot her wor ds t he same poi soni ng and t he same react i vat i on is obt ai ned i f the
ehemi sor bed pr oduct has been f or med by reduct i on of CO s or par t i al oxi dat i on of
met hanol .
Formic acid
The CO s adsorption peak. The resul t s obt ai ned wi t h f or mi c aci d ar e si mi l ar t o
t hose obt ai ned wi t h met hanol . However , t here is a difference. Wi t h f or mi c acid,
9 5 * C
6 0 0 6 0 0
f
7- 4 0 0
uJ ~ 400
2 0 0 2 0 0
i I ; I l ; i l 1
0 2 4 6 8 0 2 4 6 8 I 0
r~A/cm 2 mA/cm 2
Fxo. 6. i (E) cur ves o n pl a t i ni z e d Pt / 2 N HsSO4, 5.10 -4 M HC( X) H, Na r = 200
mV/ mi n . Ad s o r p t i o n pe a k at 25 C: (a) Eh, == 500 mV (to = 5 r ai n) E ~ ---- OC"P
(to = 5 r ai n) (c) Eho - - OCP (to = 15 rni n), ( d) Eh, = 500 mV (to = 15 rai n), a n d
at 95C: (e) EA, = 2 0 0 mV (to = 200 mV) (t0 = 15 mi n) ( f ) Eho = OCP (to = 15 rai n).
at 95C, t he chemi sor bed pr oduct is f or med mor e readi l y at open circuit t han under
cur r ent flow at E h = 200 inV. Cur ve f of Fig. 6 shows t he adsor pt i on peaks obt ai ned
aft er wai t i ng t i me of 15 mi n at open circuit. Compar i ng wi t h t he adsor pt i on peaks
obt ai ned af t er 15 rai n wai t i ng t i me at E h = 200 mV (curve e) it can be obser ved t hat
t he f or mat i on of t he chemi sor bed pr oduct is fast er at open circuit t han under current
flow at En = 200 inV.
F o r t he s e e xpe r i me nt s t h e s a me s t a n d a r d pr oc e dur e was us e d; af t er e l e c t r oc he mi c a l a c t i va t i on
(2 mi n at E~ = 1200 mV f ol l owe d by 2 r ai n a t Eh = - - 5 0 mV) t h e e l e c t r ode wa s l ef t e i t he r at o p e n
ci r cui t , o r a t f i xed pot e nt i a l Eh = 200 mV, u n d e r s t i r r i ng ( r ot at i ng e l e c t r ode a n d Nt - bubbf i ng) .
After 15 min waiting time all agitation was discontinued and the potential sweep of 200 mV/min was
forced. The curves were taken in the sequence indicated in the figure.
The expl anat i on f or t he behavi our shown in Fig. 6 can be t hat t he react i on
HCOOH -~. COz -k Hs (6)
is spont aneous, and at t he very low open-ci rcui t pot ent i al CO= f or med by react i on (6)
72 J. GINER
can be reduced accordi ng to a react i on such as eq. (3) as al ready shown 1 to give the
chemi sor bed product . The possibility of direct decomposi t i on accordi ng to an
equat i on such as
Pt 4- HCOOH --~ F' t - - CO + H20 (7)
or
O
//
Pt 4- HCOOH ~ Pt - - C + H 2 (8)
\
"OH
is even mor e pr obabl e.
I t is i nt erest i ng t o not e (Fig. 7) t hat when decreasi ng the t emper at ur e t o 25C
chemi sor bed pr oduct is f ound significantly onl y under pol ari zat i on, i.e. when current
flows (curves a and d) while little chemi sor bed pr oduct is f or med at open circuit
(curves b and c).
To expl ai n the pot ent i al effect at r oom t emper at ur e we have first t o assume t hat
react i on (6) is inhibited, since we have f ound ~ t hat react i on (3) is r easonabl y fast at
r oom t emper at ur e. Fur t her , since no anodi c react i on can be written wi t h CO pr oduc-
tion f r om HCOOH, the pot ent i al effect at r oom t emper at ur e suggests t hat t he
chemi sor bed pr oduct is one which is pr oduced by par t i al oxi dat i on of HCOOH such
as COOH, which accor di ng to equat i on
O
/ /
Pt -~- HCOOH --~ Pt ---C H + e - (9)
OH
can be st rongl y influenced by t he el ect rode pot ent i al .
I t seems t hat wi t h 10 -3 M f or mi c acid at E~, = 200 mV t he coveri ng of the el ect rode
wi t h chemi sor bed pr oduct is sl ower t han wi t h 10 - s M met hanol and less compl et e.
Tabl e 3, obt ai ned f or an el ect rode of high real surface under similar condi t i ons as
Tabl e 2, shows this poi nt al so:
TABLE 3
Hydrogen charge Peak charge after t-min
HCOOH (mC/cm2) ( mC/ cm ~)
conc.
(M) initial after exper, t = 2 t ~ 4 t ~ 8 t = 15 t = 20
10 -3 930 520 275 325 400 425 425
Her e the physi cal decay of the real surface does not al l ow at the present t i me an
absol ut e concl usi on about the coverage.
The f or m of the cur r ent decay curve for f or mi c acid is very si mi l ar to t hat of
met hanol (Fig. 4) and react i vat i on is also observed by i mpressi ng a pot ent i al of
450 mV (at 95C) f or a few seconds.
Cor r es pondi ng to a sl ower f or mat i on of the chemi sor bed pr oduct with 10 -3 M
f or mi c aci d as compar ed to 10 -z M met hanol (see Tabl es 2 and 3) a sl ower decay of
current is obser ved with 10 -3 M formi c acid l han with 10 -3 M met hanol (Fig. 4).
Anodic oxidation of CH=OH and reductive adsorption of CO= 73
FAST POTENTI AL SWEEP ON BRI GHT PLATI NUM
Some experi ment s with bright pl at i num have been made t o check the results
obt ai ned by us with platinized pl at i num and t o discuss t he results of the literature on
bright Pt f r om t he poi nt of view of chemi sorpt i on of "r educed COs. "
Met hanol
Curves a, b, c of Fig. 7 are t he i ( E) cur ves f r om hydr ogen evol ut i on t o oxygen
evol ut i on obt ai ned wi t h t he system bri ght -Pt / 2 N H2SO a, 1 M CHaOH wi t hout
stirring f or t hree t emperat ures (25, 50, 95C), at a pot ent i al sweep rat e of 300 mV/sec.
Curves similar to this, especially for r oom t emperat ure, have been described in t he
literature. ~-4
2 0 0 0 ( o ) 200~
; 0 0
- . tOOC
0 4
lo' m A / c m 2
Cb)
J I r
0 I 0
i a, m A / c m 2
2 0 0 0 ,
i o 0 0
k d
( c )
?
I
A
0
la,
?
i I
2 0 O
m A / c m 2
Fic. 7. i(E) curves on bright Pt/2 N H=SO,, 1 M CHaOH, N~ re = 300 mV/sec;
(a) 25C; (b) 50C; (c) 95"C.
In t he anodi c di rect i on t wo waves are not ed: t he first corresponds t o pot ent i al s
at which still no oxygen l ayer is possibly f or med and t he second which al t hough due t o
oxi dat i on of met hanol is rel at ed t o t he f or mat i on of an oxygen adsor pt i on layer.
Gi l man and Brei t er a when worki ng with l ow pot ent i al sweeps (30 mV/sec) observed
t hat t he first wave of curve a has a pre-wave. The pre-wave responds t o t he criteria
of adsor pt i on and t hey assume t hat it is caused by oxi dat i on of adsorbed met hanol .
The sudden dr op of cur r ent with increasing pot ent i al s which defines t he first
wave is caused by adsor pt i on of oxygen in mi nut e amount s. ~
The most interesting feat ure of t he first wave is t hat t he cat hodi c sweep is displaced
t o negative pot ent i al s compar ed with t he anodi c sweep, i.e. at low pot ent i al s met hanol
is oxidized fast er in t he cat hodi c sweep t han in t he anodi c sweep. This fact is equivalent to
a hi gher activity duri ng t he cat hodi c sweep and has been r epor t ed by different authors.~-4
The i nt erpret at i on of this di spl acement differs f r om aut hor t o aut hor. Vielstich ~ pro-
poses an oxygen coverage duri ng t he positive sweep at pot ent i al hi gher t han 850 mV
and reduct i on duri ng t he negative sweep as cause of activation. Thi s oxygen coverage
is sufficient to cause act i vat i on as has been observed in ot her el ect rode reactions ;8 how-
ever, oxygen deposi t i on is not necessary t o cause activation, as Gi l man and Breitet a
poi nt out f r om unpubl i shed experi ment s with formi c acid, * where an act i vat i on also
occurs i f t he pot ent i al is reversed before a significant amount of oxygen can be deposited.
* M. W. BRE1TER Electrochim. Acta 8, 447 and 457 (1963) (added in proof).
74 J. GINER
Our experiments at several temperatures confirm this point also for methanol.
Curves a and b of Fig. 8 obt ai ned at room temperature show t hat reversing the sweep
direction at potentials of 750 mV (a potential lower t han the potential necessary for
oxygen deposition) causes an increase of current in the cat hodi c sweep compared
to the anodi c sweep, The potential to cause regeneration at 50C is as low as E h = 680
mV (curve d) and E h = 480 mV at 95C (curve f). These potentials are completely
out of the range of oxygen deposition, the potential of which does not change much
with t emper at ur e) So even a mi nut e deposition of oxygen on the active centres is
6 0 0
>
E
30O
uJ
l a ,
not possible.
. _J
I
r n ~ r n 2
(b)
6 0 0
>
E
3 0 0 -
uJ
o t
ia, mA / ~ m z
t ~
i
0 2 0 I
io, ~ n A / ~ r n 2 io, m a i m 2
, J
o 2 o !
FIG. 8. i(E) curves on bright Pt / 2 N HsSO4, l M CHsOH, N2, ro = 100 mV/sec.
Effect of temperatur on "regenerat i on pot ent i al " (a), (b) 25C; (c), (d) 50C;
(e), (f) 95C.
To explain the activation, Gi l man and Breiter a suggest t hat met hanol is oxidized
to a larger extent on a surface which is free of met hanol adsorption. They base this
supposition on adsorpt i on measurements made at different potentials duri ng a slow
potential sweep (30 mV/sec). 1 These measurements demonst rat e t hat , at the
potentials at which the anodi c sweep shows less current t han the cathodic, more
adsorpt i on is present duri ng the anodi c sweep.
Fr om our experiments with platinized pl at i num, which show the format i on and
poisoning effect of "reduced COl ' (CO, COOH), we suggest t hat duri ng the anodi c
Anodic oxidation of CH~OH and reductiv adsorption of COt 75
sweep, poisoning "reduced CO2" is oxidized, while duri ng the cat hodi c sweep this
poisoning product is formed at lower potentials. This woul d explain the activation
observed in the cat hodi c sweep. The pre-wave observed by Gi l man and Breiter
could be due t o the oxi dat i on of this "reduced CO~".
The adsorpt i on measurements of Breiter and Gi l man 1 can be interpreted at le~/st
partially as measurement s of chemisorbed "reduced COs" and not CH3OH as sug-
gested by these authors. This would explain the higher adsorpt i on f ound at a given
potential duri ng the anodi c sweep compared with the cat hodi c sweep.
Formic acid
The curves of Fig. 9 and 10 were obt ai ned under very similar condi t i ons as those of
Fig. 7 and 8 and the same comment s as for those figures apply here.
2(2,00 (o) 2000- (b) 2000 (c'~
>
=
tO
I000.
bJ
5
u O 0 0 >
. . = i O 0 0 "
7
0 8 0 0 2 0 0
i o , m A / c m 2 i a , m A / c m 2 i = , r n A / ~ m z
FIG. 9. i(E)-sweep curves on bright Pt/2 N HtSO4, 1 M HCOOH, N= ro = 300 mV/sec;
(a) 25C; (b) 50C; (c) 95C.
It is interesting t o not e t hat in the anodi c sweep (Fig. 9) a small wave at E h = 500
mV is found, especially at low t emperat ure (curve a). I t could be assumed t hat duri ng
this prewave an addi t i onal amount of chemisorbed poison is formed which coul d not
have been formed t ot al l y duri ng the cat hodi c sweep. This i nt erpret at i on agrees with
the difference observed on format i on of the chemisorbed poi son on platinized plati-
num between met hanol and formi c acid (Table 2 and 3), i.e. it confirms t hat the
met hanol oxi dat i on poisons the electrode wi t h "reduced CO2'" faster t han the formi c
acid oxidation.
CONCLUSIONS
Met hanol and formi c acid in acid solution when anodically oxidized on platinized
pl at i num electrodes f or m a chemisorbed poisoning intermediate.
Fr om t he compari son of potential-sweep curves and especially of the shape of the
adsorpt i on peak, and the sweep-rate dependence and t emperat ure dependence, it
is concluded t hat this pr oduct is the same as t hat obt ai ned by CO S reduct i on on Pt
electrodes, x This pr oduct is called here "reduced CO9." because its composi t i on is
not yet known; i t can be, for t he time being, visualized as CO or COOH.
This product is also formed at open circuit, especially in the case of formi c acid at
high t emperat ure. Thermodynami cal l y it is plausible t hat a currentless dispropor-
t i onat i on of the reactants occurs at open circuit.
76 J. GINER
The f or mat i on of this poi soni ng i nt ermedi at e explains t he rapi d current decay
duri ng t he anodi c oxi dat i on of met hanol and f or mi c acid at l ow pol ari zat i on. The
cur r ent decay is accompani ed by t he progressi ng coverage of t he electrode. As soon as
t he el ect rode is br ought t o pot ent i al s at which t he "r educed COs " can be readi l y
oxidized, gas evol ut i on is ot)served and t he activity of t he el ect rode is regained.
( o)
0 I
t o , m A ~ C m 2
9oo (b)
>
E~600
300
I c , m ~/ / C rD ~
~ o o ~ ,~ ~ .,//~ ~oo ~ ~
,O O T i , ~ ~ ,o o
0 4 0 ' ~
Lo, mA/cm z ~, ~n/cm~
It,~ (e)
d 3 0 0 [
0 I O0
i o, mA/ / Cm 2
(f)
~ o o
3 0 O
L.U
o
t
I G , r'n A / C r n 2
FIG. 10. i(E)-sweep curves on bright Pt/2 N H2SO4, 1 M HCOOH,
N~, r0 ~= 100 mV/sec. Effect of temperature on "regeneration
potential" (a), (b) 25C; (c), (d) 50C; (e), (f) 95C.
Fr om t he earlier results, x which show the reducibility of CO2, and f r om t he results
obt ai ned here with platinized pl at i num and with bright pl at i num, it is suggested t hat
t he adsor pt i on measurement s existing in t he l i t erat ure t are at least part i al l y measure-
ment s of adsorbed "r educed COs", and not measurement s of adsor bed methanol
Fi nal l y t he oft en discussed di spl acement of the first wave in the fast linear pot ent i al
sweeps t o negative values duri ng the cat hodi c sweep is equal l y i nt erpret ed as caused
by f or mat i on of t he poi soni ng "r educed CO2" duri ng the cat hodi c sweep and oxi dat i on
dur i ng t he anodi c sweep.
Acknowledgment--The author wishes to thank Dr. J. G. Tschinkel for his helpful discussions and
to B. Tyez for the conscientious performance of the. experiments.
Anodi c oxidation of CHsOH and reductive adsorption of CO, 77
R E F E R E NC E S
1. J. GINER, Electrochim. Acta, 8, 857 (1963).
2. W. VIELSTICH, Extended Abstracts of Indianapolis Meeting of the Electrochemical Society,
Abst ract 113, pp. 149-151. W. VIELSlICH, Chem. h~. Teeh. 35, 362 (1963).
3. R. P. BUCK and L. R. GRIFFITH, J. Electroehem. Soc. 109, 1005 (1962).
4. S. GILMAN and M. BREITER, J. Eleetrochem. Soc. 109, 1099 (1962).
5. F. WILL and C. A. KNORR, 2. Elektrochem. 62, 378 (1960).
6. J. GINER, J. Electrochem. Soe., in press.
7. B. ER.SHLER, Acta Physicochim. URSS 19, 139 (1944).
8. J. GINER, Electrochim. Acta 4, 42 (1961).
9. W. BOLD and M. BREITER, Electrochim. Aeta 7, 25 (1962).
10. M. BREITER and S. GILMAN, J. Eleetrochem. Soc. 109, 622 (1962).