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THE INFLUENCE OF NITROIvfETHANE AIMORFTION ON

THE OXIDATION OF FORMIC ACID AT PLATINUM


ELECTRODES*
A. M. BARUZZI, V. Sotis and M. C. GIORDANO
Pepertamnto de F~uimii, Fact&ad de Cicncias uunuas, Universidad National de Chdoba, So00
c!&dotq AZ&La
(Rec.&& 3 March 1981)
Aktrrt43a-dsorption of nit- at Pt clectr~ and its iIlauencc on HCOOH elatrocatalytk
oxidation were iuvestigated by eyelie veltammetry and pettntiDstatie quasi-steady state polarizatioa ewves.
Potearti&namic I/E culycs in the pmaana of nitromethane show a co&deraMecurmnt -in tbalow
pattntial re&ul (ct.245 v). This &act is, trtaiatainrd uttdar QWJ i-steady atate ccltitious. Electroaotption
studicspcrC~~Nithnitro~iadrcucdthatpartiollyisducedspecicsareadsorbsdwtheekaradt
surfaenThercsPesiescouldbe mspensibtc for the observed promotinE ef%4Z.
The ~WU&S o&aincd with nitrometbane additian are compued with *cctonitrik and dimcthylaulfoixide.
C~mpetitiun for adsorption sitea and mod&cations of au&cc adsorption energy produced by additive
adsorption, account for their specific intlucnce on the HCOOH oxidation rate.
INTRODUCllON
Cogdsarption of several substances on Pt electrodes
have b&n repoti to produce different e&&s on
electrocatalytic processes. An increase in current for
the first oxidation peak on the electr~talytic oxid-
ation of HCOOH is produced by acetonitrile
(M-1, 23, I-[3], suifur[4] and foreign metals
such as Hg, I%, Bi, Cd, Tl, Ag and Cu[l, 5-J. The
prnsencc of these substances influences the HCOOH
eltztrn-oxidation either preventing the formation of
the st r ongl y ,bound intermediate[l, 2, 51 or through
some ape&R type of interaction between the adsorbed
species and Pt su&tcc[24]. In tbis context it would be
interesting to investigate the intluence of other organic
molecules which strongly interact with the Pt sur-
face[6, 9) on the kinetics of the HCOOH electro-
oxidation.
In this work the Wluence of nitromethane co-
adsorption on Pt in HCOOH electro-oxidation is
studied as a function of its bulk concentration, adsorp-
tion time and adsorption potential. Nitromethane
exhibits physicochemical properties between that of a
substance having a high dipolar moment, nucleophyhc
and H-bond acceptor properties as dimethylsulfoxide
(DMSO) and acetonitrile (MeCN) with a lower dipolar
moment. Both substances, DMSO[9] and MeCN[ lo]
strongly interact with Pt in aqueous acidic solutions
but their intluence on HCOOH oxidation seems to be
different[ 1 l]_
This work attempts to correlate some specitic pro-
* This work wm presmted at the International Society of
Bkcnochemistry 31 st meeting, Venice, Italy. 22-26 Septem-
her 1980.
+ prsscmt address Department of Chemistry, SoutlIam-
ptou University, Southampton, U.K. British Couocil post-
doctral fellowship.
perties of the foreign organic molecule and their
in&ence on the formic acid oxidation rate.
EXPERIMENTAL
Nitromethane (Fischer certitied) was pnriSed as
previously described[ 121. Its quality was veriBed by ir
spectrometry, mass spectrometry and gas chmmato-
graphy. Dimethylamine (CH&NH was prepared by
dneomposing its chtorohydrate by adding N&RI The
gas evolved was condensed at low temperature and
later purified by several distillations.
Formic acid (Mallinckrodt) was used without
further purification. The concentration of CHaN02
was changed from lo- to 1 M and the concentrations
of the formic acid solutions were lo- .0.25 and 1 hi.
The supporting electrolyte, 0.5 M H&C?+ was pre-
pared from or grade chemical (AnalaR) and triply
distilled water. Solutions were deoxygenated by bub-
bling purified nitrogen through them
Small sealed 99.999 % Pt wire .working electrodes, a
Ptpt foil counterelectrode and a hydrogen reference
electrode in the same solution were employed. The
geometrical area of the Pt wires ranged from 0.1 to
0.2 cm. Pt foils of 2 and 9 cm were used as workioa
electrodes in some experiments. The real electrode a&
was determined by standard procedu~133. The sur-
face coverage degree by the adaorbed species (Borg)
was determined either from the decrease of the anodic
charge related to the oxidation of adsorbed hydrogen
(Q; - Q~*/Qd, mG&l fmm th
infxaseofcharge
in the O-electrosorpnon region due to the anodic
oxidation of the adaorbed species, (Qz- QuQz
- QE).
CycBc vos were obtained at room tem-
perature using a conventionai set up. I/E profiles were
recorded eitber with a X-Y recorder photographed
274
A. M. BARUZZI , V. SO& AND h4. c. GIORD~
from an oscilllecope screen. Also current-time trans- nitromethane is enhaacsd, WhCItthCpOtBIitiBliShCid
ients were recorded after addition of nitromcthane at within the H-adatom potential region. This &cct is
different potentials. An anodic or catholic potentio- shown in Fig. 2 where the positive going potential
dynamic I/E profile was rtazorded immediately folfow- sweep is kcp? at 0.1 V/s (02) and the negative potential
ing the tepnsicnt to determine e&her oxidation charge
sweep is w from u2 to oI = a01 V/s at two
of elcctrosorbed species or change of coverage of diff~t potastinls within the H-&atom potential
electrosorbed H. Potentiost&c polariiW.ion curves for region. Qualitatively the same IL&& is observed when
the HCOOH oxidation both in the presence and the the slow o is employed on the positive going potential
absence of CH,N02 were also made.
sweep
The above observations are opposite to those shown
in the ehztrocatalvtic oxidation of HCOOH at
Pt[l, 141 in the abskcc of the added suhatanas. RESULTS
General features observed on formic acid oxidation in
the presence of nitromethane
The cyclic voltammetric I/E profile For HCOOH
oxidation (Fig. 1) in the absence of CH,NO, exhibits
three &e&y known oxidation currentpeaksPaf.Pa2,
and Pa3during the positive going potential sweep. The
main at-on will be paid on peaks Pal and Pa2 and
how their relative heights change with the CHsNOt
concentration in the bulk of the solution through the
application of different potential time perturbation
programs.
The addition of nitromethane causes the most
sign&ant increase of current in the potential range of
current peak Pal. It also influeRces the current in the
potential range of Pa2 and Pa3 by producing a
decrease in current amxiated with these oxidation
proceSseS.
The maximum current increase OfPalisrcachedat
[CHSNOJ z 1 x lo- M, butevenat 1 M theanodic
current in the low potential region related to Pal is
greater than in the absence of nitromethane. The
promoting influence of CH,N02 on the HCOOH
electro-oxidation rate is maintained at poteatial sweep
rates as low as 0.001 V/s. However, as the potential
sweep rate exceeds 0.S V/s, the predominant effect is
the dcc*casc of the anodic current in the potential
range of Pa2
The increase in current on Pal by addition of
The enhancement of the promotiiry e&ct on F% I by
increstsing the time spent in the H-a&tom region in
the presence of CHSNOl is also shown when the
current for the first anodic peak (Fig. 3) is r ec or ded at
different v both in the presence and in the absence of
CH,NOI after scanning the 0.05-0.4 V range at
0.01 v/s.
Potentiostatic stepwise quasi-steady state Z/E curves
are shown in Fig. 4. Each current value was taken after
an anodicckaning procedure was employed and the
current/time decay at each potential W a very
Sdl BDd BhOSt Cof l Bt ant Sl OpE2. Tht t .i MC da@ WYBS
about 3 min.
In the presence of CHXNOt there is an increase in
current between w 0.1 and 0.4 V. As the oxidation
process associated with Pa2 is inhibited in the presence
of CHSNOI, the current obtained over 0.4 V is lower
than in its absence.
Eiectrosorption of nitromethane and r el aed species
It has been previously shown[6] that CHsN02 is
electroactive at Pt electrodes in acidic aqueous
solutions undergoing a partial ek c t r or c dc t i on to
nitrosomethane,-CH,NOi and methylhydroxylaminc
CH,NHOH. The total reduction to m&Mamine.
CHBNHl is only accomplished either at high tempera:
tures or by increasing the pH[lS].
The possibilities for nitroalkane electroreduction
can be SUmmariXA as follows[16]:
E/V, VI RHE
Fig. 1. Cyclic wltamm~,gxaxmfor HCOQH oxidation in m
and AXeWe of CW,NOA . - c-
0.25 M without additive. --- CHcoon 0.25 M + CcH,N9
1.6x tW2 M. Bme ekctroty&e H,SO, 0.5 M.
sweep rmtc 0.1 v/s.
The inauemr of nitromcthane adsorption
RCHNO,H++ [RCH~NO)] H+ ~[RcH(~H+)=[RC(:NH:)]
I
CRC
RCE
(1) WI
+H,O
NOHJW+ RCHNHOH
(Iv) (W
4e-
4H+
w
$
rJH:) -
2H+ + 2e-
(W
275
--I
The direct clectroreduction of species (H) to (III) is
very difficult in acidic media Moreover, the yield on
As hydrogen ions are depleted from the interface the
spanics (1II) at low pH is hindered by the catalytic
RNHl formation at low potentials becomes more
hydrogen evtilution reaction through an ion radical
likely.
mf4mnism~l5J
The potentiodynamic I/B behavior of CHjNOz at
various concentrations in comparison to the base
RNHOH + H+ -+ RNH,+OH 5 RfiHIOH
,z RNH, + OH-
I
Fig. 2. Effect of lime spent on W regiou ou Pal and Pal in prince of CHJNQ1 I CHCooH 1 x IO- M,
CCH,NO, 1 x 10-s M. sweep rate u* 0.1 v/s; vs 0.01 v/s.
Is?!?-
>
_ m
L I lovil
0 * --.-
-1
0
f
4
_,,--4
k
_---
_u---
C--
4
E
.
B -,/
,I--
.
,a-0
o+
*__*________-
__D-----
Fk. 3. DcpGndcnaofi,,onswap~~v,,~sof
H region at 0.1 V/s. 0 C,,
+ CC,NO,
0.25 M, l cz,,, a25 M,
10-Z M.
electrolyte is shown in Fig. 5. In the presence of
C&NO2 an oxidation peak (1) arises in the d.1. redon
and simultaneously H adwcpticm is gmdaally
hindered. The initiation of O-electrosolorption on Pt is
displaced towards more positive potentials and two
oxidation peaks (II) and (IIr) arc seen before the O3
evolution potential is reached. The total charge for tbc
surface oxide electroredudion does not change
appreciably, but the process appears to be more
irreversible, and an increase of cathodic current in the
o.cbo.3 v range is observed.
This behavior depends on whether the potential
sweep has covered totally or parGaIly tbc O-elec-
trosorption potential range (Fig. 6). The extended I/E
profile obtained after cycling in the H-&atom and
61. potential range (Fig. 7) shows that H
adsorption-desorption is almost CompIeteEy inhibited.
On the folIowiug positive going potential sweep* only
oxidation peak (III) is o&ii&. As the H elec-
trosorption potential region iai excl& the I/E profile
276
A, M. BARUZZI , V. Soris~~D ht. c. ~IORDAIWJ
04
t
Y
LT
2 0.3-
<
l u
02-
log i/PA Cm-
Fi g. 4. Potentiostatic polarization curves for HCOOH oxid-
ation in absence and presnce of CH,NO,. o C,- 625 M,
,c,,, 0.25 M, + CC&N& lo- = M.
of 0.5 M HISO at Pt in the 0ekctrosorption poten-
tial rage is recovered after a few cycks. Zn this case, only
peak (I) in the d.1. region becomes evident. A reversible
component for this peak is found under triangular
modulated linear potential sweep conditions.
A small cathodic current transient is obtaipsd after
CH3N0> has been injected at 0.4V, indicating ,that
adsorption at this potential is fotlowed by the eke-
troreduction of the molecule. This redox process is
almost complete in the d.1. region since the O-
electrosorption potential region remains almost
unaffected. On the other hand, after an appreciable
cathodic transient at 0.2 V, a considerable incrmse in
oxidation charge was found and oxidation peaks II
and III are evident.
Fig. 5. Modifications of cyclic vol tammograms of 0.5 M
H2S04 by CH,NOZ addition. 0 C,, ,.+ O.OM; 1,1
x 1O-4 M; 2.4 Y lo-* M; 3.2.5 x lo- ti; 4,l x IO- M.
Fig 6. Modikation of I/E petentiodynamic proziht as the
negative going potential sweep is sterted at less pcsitive
potentiab. Cm,NO, 0.1 M.
Formally, the kinetics of the adsorption process of
chemisorbed particles in nltromethane solutions was
determined through tkbz oxidation charge ofthe adsor-
bed particles as a function of the adsorption time f, at
diifermt adsorptions Eud. TIE dependenct of B_ on
log t follows a linear dependence, which corresponds
to the kinetic behavior of the majority of organic
substances on Pt electrodeCl7-j and reproduces pre-
vious results[6].
Fii 7. Voltannnolpam obtakd after step (c) in Fig. 6 - - -
-.secondq&.
Tbc itdim of nitromethme iadsorption
271
Also,auappsuentdepeudenceof surfaacoverage by
adsorbed particles in nitromethane solutions, e,, on
Sod was found for low CH.NOa concentration. The
0 Us Ead plot shows a maximum around Ct20-0.25 V.
The 0xidaGon &urge for particles adsorbed at $2 V
atWt~urs~s~on value at [CH,NO,] ca 1Q- _M.
duxease m the H &ctro-oxldatlon
charge at a2V is proportional to the logarithm of the
nitrometbane concentration (Fig. 8) in the 0 range
betweeu 0.2 and 0.6. A Limiting surtke coverage of
about 0.6 is found for CH3NOr concentration be-
tween 10s2 and lo- 1 M.
DIStXJSSION
The experimental data would indicate that different
efectrosorbed species exist on Pt in nitromethaae
solutions. These species would arise from the gradual
electroreduction stage of the chemisorbed CHoN02
molecule.
From the reduction charge of the transient obtained
at 0.2 V and the related hydrogen coverage recovered
after the transient a number of 2 ap.s. was o&&cd.
T&i&g into account the possibility of two adsorption
sites on the pt surface for each CH,N02 molecule, the
exchange of four electrons on the electroreduction
process would account for the possibility of the NH-
intermediate on tbe electrode surface. Species such as
Fii 8. Dcpcod- of steady slate covetage on nitrometbane
bulk conantration at gad 0.2 V.
(V)and (Vi) in reaction scheme (l), should he stabilized
by adsorption on the electrode surf.. preventing its
further hydrolysis. Theii interaction with Pt should
account for the promoting influence of CH3N02 on
HCOOH electro-oxidation. Further experiments
made with a substance containing -NH group give
support to this interpretation. Figure 9(a) shows the
potentiodynamic I/E profile of a Pt electrode in the
278 A M. BMUZZL V. Sods AND M. C. G~ORDANO
E/V, v WE
Fig. 10. Voltammogram of HCOOH oxidation in pnscncc of (C&),NH. Crmooir 0.25 M. activated
ekctrodc in base elec~oiyte --- After dipping in @ZEI,),NH.
base electrolyte immediately after it has been dipped
into liquid (CH,),NH, for few seconds. The chemi-
sorptz~n of (CH&NH on Pt influences both the
strongly adsorbed intermediate oxidation [Fig. 9(b)]
and the potentiodynamic i /E profile of HCOOH
oxidation (Fig. JO).
These effects are qualitatively very similar to that
due to the adsorbed particles electroformed in the
CHJNOs containing solutions. The enhancement of
the promoting effect after holding the potential in the
H adatom potential region is in agreement with the
above mentioned results. Therefore, the intluence of
CHBNOl in the HCOOH electraoxidation on Pt is
qualitatively similar to that produced through com-
petitive adsorption by other substances such as
CH,CN[l, 23 and (CH,),SO[lO]. The relative ef-
ficiency of the i&uence of the diRerent substances can
be evaluated in terms of the current density read at the
potential of current peak Pal with respect to that
found for the electrolyte in the absence of foreign
substances. For the three substances aiready men-
tioned the following order results
(iCH3CN/iH10) > (iCZ&N$,/iH,O) > i(CH&SO/
2 .
The slope of the linear dependence 0 vs log
[CH3N0,] at the maximum adsorption potential
under stationary state conditions, yields an apparent
surface heterogeneity parameter ari&ng from ad-
sorbed spe&s in CHJNOs containing solutions of
cu 5.4 kcal/mol. Under practically the same experi-
mental conditions the corresponding apparent he.tero-
gene&y faders in DMSO containing solutions[9]
and in MeCN containing solutions[iO] are 2 and
9 kcai/mol, respectively.
The differences in surf= h&erogen&y pammeter
byadsorptionofpartickscomingfromdi@etent added
substances should selectively I-&e& through th#0 ad-
sorption energy of hydrogen atoms[ 181 and, con-
sequently on the electro-oxidation rate of HCOOH
q CH,CN
z
y CH,NO,
.
\
,/.e
& y
\
,
Fig. Il. Dcpendrpce of relative current values for Pal on
additive molar mthalpy ef vaporization.
through the weakely adsorbed -COOH inter-
mcdiate[l4]. The strongly adsorbed intermediate for-
mation, which inhibits HCOOH electro-oxidation in
the low potential region, must also be modified. In
addition, considering the molar cnthalpy of vapor-
ization (AH,,) of each added substance as an ap-
proximate measurement of the interaction energy with
the surface, a good correlation is found (Fig. 11)
between AH, and the oxidation rate of HCOOH at low
potentials in the presence of co-adsorbed organic
spaGs. Thus, it appears that molecuks strongly
iotera&ng with platinum surface influence the
HCOOH electro-oxidation through competition for
adsorption sites and modification of surf&x adsorp-
t & n energy for rcadants and products. This leads
either to activation or to inhibition of the clec-
trocatalytic process,
_~&~DwW#~#~JW-T~M work was supp&tal in put with
tM#th~ from the t&tmcjo Naeioaal de In~oncs
- y T- of Arpentine. Oae of WI (A. M. B.)
tbmttks CONKET of Argentina for the fc&wship granted.
The innucnce of Ditrot#mtmnc adsorption
279
l-l30 authors also wish to thmk Professor w. viilstich for his Rocmniki, Chemii, Ann. Sot. Chim Pohmorum X4, 2113
suggcstioos duriog preparation of this paper. (1976).
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