JOUnNALOf

ELSEVIER Journal of ElectrounnlyticalChemistry 437 (1997) 259-262

Short communication

Induced adsoff tion of phosphate (H2PO4) species by Zn adatoms on

platinum
13. Horfinyi a,*, Akiko Aramata h
~' Central Research Institute fi~r Chemistry of the Hungarian Academy t~Seh'nces, Budapest, P.O. Box 17, 1525, Hungmy
b Catalysis Research Center, HokkaMo University, Sapporo 6, Japan
Received 17 June 1997; received in revised form 11 July 1997

Abstract

The specific adsorption of HzPO~- ions accompanying the upd of Zn 2+ ions on platinum electrodes has been studied by a radiotracer
technique using 32p labelled phosphate species in the presence of a great excess of CIO4 ions. It has been found that the specific
adsorption of species induced by Zn adatoms depends on pH and at a given potential on the concentration of Zn 2+ ions. © 1997 Elsevier
Science S.A.

Keywords: Zn; Upd; Induced anion adsorption; Phosphate; Radiotracer technique

1. Introduction 2. Experimental

In a previous communication [I] the specific anion
adsorption accompanying the upd of Zn 2+ ions on
(platinized) platinum electrodes in acidic medium was
studied by a radiotracer technique using aSS labelled sul-
phate species and 360 labelled CI- ions. It was found that
sulphate ions adsorb readily on the top of Zn adatoms
while the adsorption strength of CI- ions on the Zn
adlayer is significantly lower than that of HSO4(SO42-)
ions. The potential dependence of the adsorption of la-
belled species in the presence and absence of Zn 2+ ions
and the competitive adsorption phenomena occurring be-
tween the species present in the system were considered in
detail. Thus competitive adsorption between non-labelled
H2PO 4 and labelled HSO 4 species was canied out and
the high adsorbability of H2PO 4 ions was demonstrated
indirectly. On the basis of the latter preliminary results a
systematic study of the sorption of H2PO 4 species la-
belled by the 32p isotope was suggested as a continuation
of the work. The aim of present communication is to report
the results obtained from the study mentioned above.
" Correspondingauthor. E-mail: hor34@ludens.elte.hu.
The electrochemical cell and the measuring technique
described in previous adsorption studies were used [1-5].
32p labelled phosphoric acid (specific activity 7.4 GBq
mmol- J ) was used in the radiotracer adsorption studies.
Platinized electrodes were prepared by the usual elec-
trodeposition process [2,3] on the gold-plated plastic foil
forming the bottom of the cell. The roughness factor of the
electrodes used (determined by hydrogen adsorption) was
about 100. HCIO4 solutions in various concentrations were
used as supporting electrolytes. Potential values quoted are
given on RHE scale. Zn 2+ ions were added in the form of
salts by dissolving ZnO in the supporting electrolyte used.
3. Results
Fig. 1 shows the potential dependence of the adsorption
of labelled phosphate species in the absence and presence
of Zn 2+ ions (at different concentrations) in the presence
of 0.I mol dm -3 HCIO4 supporting electrolyte at a low
(5 × 10 -5 mol dm -3) H3PO 4 concentration. It may be
seen from this figure (and comparing with the similar
results obtained for labelled HSO4 ions [1]) that there is
no doubt concerning the occurrence of the induced specific
adsorption of phosphate species by Zn adatoms (formed in

0922-0728/97/$17.00 © 1997 Elsevier Science S.A. All rights reserved.

PII $0022-0728(97)00392-6
 260 G, Hordnyl, A, Aramata/ Journal of Elevtrotmalytlval Chemistry437 (1997) 259-262

OmV
700 mV
0,5 i
¢

'o0,25
2

0 . . . . v

0 200 400 600 0 5 l0 15

E/mV
Fig. h Potential dependence of the adsorption of labelled H.,PO4- ions in
0.1 tool dm -3 HCIO4 supporting electrolyte in the absence (curve 1) and
presence of Zn -~+ ions, (curve 2 ) 2 , 5 X 10 -3, (curve 3) 1,5X 10 -2 tool
dm -'~ Zn(CIO4) 2. cH.i,o£ = 5X 10 -'~ tool dm -'~
thnin
Fig, 3. Effect of CI- ions on the adsorption of 1-121'O~ in the presence
of Zn 2+ ions Oil Po- = 5X I0 -'~ tool din-3; Oz,..+ = 2 5 × 10 -3 tool
d i n - 3 in I X l 0 tool d m • HCIO 4. C I - ions were added to the
solution phase at the moment indicated by the arrow (c = 1 X 10-4 tool
din-3),

the potential range 0-300 mV). In comparison with HSO4-

species (see Ref. [1]), the increase in the H2PO4 adsorp-
tion at E < 300 mV is not too high in the strongly acidic
solution. However, at lower H + ion and higher Zn2+
concentrations the extent of induced adsorption is signifi-
cantly higher as will be shown later. The mobility of the
adsorbed H2PO4- species can be clearly demonstrated by
the exchange of adsorbed labelled species by non-labelled
molecules added to the solution phase. This is shown in
Fig. 2.
On the other hand, the adsorption of H2PO4 species
induced by Zn adatoms cannot be influenced by CI- ions
at least at low CI- concentrations while, as is well known
[6,7], CI- ions displace H2PO~- species adsorbed on
platinum surfaces in the absence of adatoms. This is
demonstrated by Fig. 3.
Fig. 3 clearly shows that the addition of CI- ions does
not result in significant change in the extent of the ad-
sorbed labelled H2PO~- at 0 mV (formation ofZn adatoms)
as only a slight decrease in the count-rate can be observed.
(Compare with the phenomenon occurring after the addi-
tion of non-labelled H2PO4- species to the solution phase
as shown in Fig. 2.) A switch to 700 mV leads to a
complete elimination of the labelled species from the
surface. The maximum appearing after the potential switch
indicates that at the beginning there is an increase in the
HzPO4 adsorption on the free Pt sites in accordance with
the expectations based on the potential dependence of the
adsorption (see Fig. I) and this initial section is followed
by the displacement of adsorbed H2PO4 species by CI-
ions. (These phenomena for HSO[ and CI- competition

,L
t~
60
15
fJ

~10 I~ 40 2
,./
'T

20
1

0 I0 20 30
Vmin
Fig. 2. Exchange of labelled phosphate species adsorbed at 0 mV in the
presence of Zn 2 + ions with non-labelled ones added to the solution phase
in a great excess at the moment indicated by the arrow. Supporting
electrolyte: 0.I mol dm -3 HCIO4. Initial H3PO 4 concentration: 5X 10 -5
tool dn1-3. Final: 1 × 10 -2 mol dm-3.Czn..,- = 1,5X 10 -z tool dm -'~
0 200 400 600
E/mY
Fig. 4. The eftk:ct of HSO4 ions on the potential dependence of ~he
adsorption of labelled H2PO4- species in the presence of Zn 2+ ions
Cl.I po- = 5 X 1 0 -5 mol din-3; C z n 2 + = 5 X l 0 -3 tool dm -3 in 0.l tool
dm:-34HCIO4, cri,po~-:(I)0, (2) 5"x 10-4; (3) 5 X 10-3 mol dm -3.
 G, Horfmyi,A, Aramata/ Journal of Electroana/ytlcalChemistry437 (1997)259-262 261

1,2

q~ 0.4
5 o.s

0,4 0.2

...... 13•. o ~ . °.l-

0 ~,
0 100 200 300 0 . , , ",
"" ..i,:.. ,. q~ :
E/mY 200
100 300
Fig, 5, Potential dependence of the adsorption (F, full line) H2PO~" of E/mV
ions (induced by Zn adatoms) in the presence of CI- ions• c~l po- "= 1 X Fig. 7. Potential dependence of the induced adsorption of H2PO~"
" ~4
10-'1 tool dm-'~; CZnv.=l.5Xl0-2 mol din-'; ccl-=lX10 tool species in the presence of CI- ions at two different H+ concentrations
dm -3 in 0.1 tool dm -3 HCIO4. TIDecorresponding AF/AE vs. E cH21'O;"= I X 10-4 tool dm-'~; Czr,2÷= 2 × If,'- I mol dm -'a; Coo-= 1×
curve (obtained in 25 mV steps) is given by the dotted line. 10-4 tool dm -3. In tide presence of: 0.1 mol dm-3 (dotted line); and
5× I0 -:* mol dm -3 HCIO4 (full line).

were discussed in the previous paper; for the details, see
Ref. [!])
The study of the competitive adsorption of HSO 4 and
H2PO 4 species using labelled H2PO 4- and non-labelled
HSO 4 confirms the results presented in the previous com-
munication [1] (where the opposite labelling was used),
i.e., the adsorption strength of H2PO ~- species is highe r
than that of HSO4- ions. This is demonstrated by Fig. 4. It
may be seen from this figure that a significant displace-
ment of H2PO 4 species can be attained only by the
presence of a great excess o f HSO 4 ions in the solution
phase in comparison to the concentration of phosphate
species.
The result presented in Fig. 3. allows us to determine
adsorption phenomena occurring on free Pt sites (see Ref.
[1]),
Fig. 5 shows the F vs. E and A F / A E vs. E curves
obtained by potentiostatic point by ~oint method (in 25
mV steps) in the simultaneou);'pr'esence of C I - , Zn 2÷ and
labelled H2PO 4 ions in 0.I tool dm -3 HCIO4 supporting
electrolyte. The shape of both curves practically coincides
with those obtained for H S O 4 ions reported in Ref. [1],
i.e., the potential dependence of the anion adsorption is
determined by that of the formation of the upd layer. The
extent of induced adsorption at a fixed potential depends
on the concentration o f Zn 2+ ions. This is shown ill Fig. 6.
On the other hand, a decrease in the hydrogen ion
concentration also leads to a significant increase in the

30]
the potential dependence of the adsorption of H2PO 4 ions extent of the anion adsorption as shown in Fig. 7.
induced by Zn adatoms without the interference o f the

o, 0.2
: JJ o

0.1 i 0 10 20 30
-'1 ,
t/min
0.1 0.2 Fig. 8. The count-rate vs. time curve in the pr.sence of labelled HaPO4
c, zn(clq) 2 (c = 1X 10-4 tool dm -3) in 5:< 10-2 tool dm-3 Zn(CIO4)2 at pH = 3.5
following sprinkling ZnO (full line) and formationofa Zn(OH)z layer on
Fig. 6. The influence of the concentrationof Zn"+ ions on the extent of the surface of the electrode. CDIvo- = I × 10-4 tool dm-3; Czn2*= 1.5
--3 2 4_4
induced adsorption at 50 mV in the presence of IX10 -4 mol dm-3 ×10 -2 tool dm "; Cct-=l×10 mol dm -3 in 0.1 tool dm -3
H3PO4 in 0.1 tool dm-3 HCIO4 supporting electrolyte. HCI04).
 262 G, tlor(myi, A, Ammam ~Journal tf Electmtmalytlcal Chemisto' 437 (1997) 259-262
I 2
400
200
0
0 100 200
t/rain
Fig. 9. Count-rate vs. time curve in the course of the electrodeposltion of
Zn at -720 mV (I); at open-circult conditions ,'tt - 6 8 0 mV (2) in 0.2
tool dm -3 Zn(CIO4)2 solution at pH = 5; and following the addition of
3X 10-" tool dm -3 HCIO4 (3).
As the pH increases the formation of Zn... OH surface
species seems to be a probable process and in the first
approximation a decrease in the adsorption of other anions
would be expected. It can be shown, however, that on ZnO
or Zn(OH)2 surfaces, an accumulation of phosphate species
OCCURS.
Using a cell with a gold-plated bottom (without pla-
tinization) and sprinkling on the bottom, a small amount of
ZnO powder or depositing a thin Zn(OH)2 layer by addi-
tion of small droplets of diluted NaOH solution to the
solution phase, the sorption of H2PO4 species can be
observed.
This is shown in Fig. 8 where the transient increase in
the apparent phosphate sorption is demonstrated, following
tile sprinkling of a small amount of ZnO on the bottom of
the cell (full line) or formation of Z n ( O H 2) at the surface
in the presence of a slightly acidic medium.
Since the medium is slightly acidic, following the forma-
tion of the ZnO or Zn(OH)2 layer, the sorption of the
labelled species and the slow dissolution of the newly
formed layer proceed simultaneously. Thus, the count rate
vs. time curve goes through a maximum.
It follows from these observations that at high pH
values the formation of surface oxide, hydroxide species
could play an important role.
A similar increase ot' the count-rate can be observed in
the course of electrodeposition of Zn at pH = 5 from a
2 × 10-j tool dm -3 Zn(CIO~)2 solutioll at very low po-
tentials ( - 7 0 0 mV).
This is shown in Fig. 9. Interrupting the electrodeposi-
tion process, the sorption can be studied under open circuit
condition. The results presemed in Fig. 9 demonstrate that
phosphate species adsorb on the surface of electrode-
posited Zn. The elimination of tile adsorbed labelled
molecules can be achieved only by the dissolution of the
Zn layer.
4. Conclusions
The experimental results presented above confirm the
assumptions made previously that the specific adsorption
of phosphate species cannot be neglected in the evaluation
of the data obtained from the study of the formation of Zn
adlayers.
Thus data obtained for the upd of Zn in systems con-
taining phosphate species should be reconsidered in the
light of these results.
Acknowledgements
Financial support from Hungarian Science Fund (OTKA
T 023056 and T 014446) is acknowledged.
References
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