Prediction of Flatband Potentials at

Semiconductor-Electrolyte Interfaces from

Atomic Electronegativities
M. A. Butler* and D. S. Ginley*
Sandia Laboratories, Albuquerque, New Mexico 87115
ABSTRACT
The electron affinities of several metal oxide semiconductors that have
been used as anodes i n photoelectrochemical cells are calculated using the
atomic electronegativities of the constituent atoms. These electron affinities
are q u a n t i t a t i v e l y related to the measured flatband potentials by considering
the effects of specific adsorption of p o t e n t i a l - d e t e r m i n i n g ions (for metal
oxides used in photoelectrolysis, these are usually O H - and H + ) . Methods
are discussed for d e t e r m i n i n g the pH at which net adsorbed surface charge
and thus potential across the Helmholtz layer is zero (point of zero zeta
potential, pzzp). This pH value is shown to correlate with the electronegativity of the metal oxides. The application of these ideas to other semiconductor-electrolyte systems is discussed.
The use of semiconducting metal oxides to decompose water photoelectrolytically is a process which has
recently attracted considerable interest (1). The ability of the photoelectrolysis cell to operate with little
or no external bias in the system is a function of the
degree to which the flatband potential is more negative
than the hydrogen evolution potential. Thus it is very
useful to be able to predict the fiatband potentials of
possible semiconducting metal oxide electrodes. In a
recent publication (2) we showed that a correlation
existed b e t w e e n the atomic electronegativities of the
constituent atoms in titanates of the l o r m MTiO~ and
the flatband potentials. I n this paper, we extend this
idea to all metal oxides and show it is capable of q u a n titatively predicting the flatband potentials.
In actuality, the q u a n t i t y predicted from the atomic
electronegativities is the electron affinity, EA, of the
semiconductor. However, since the semiconductor's flatband potential, Vfb, a n d its electron affinity, EA, are
essentially measures of the position of the intrinsic
conduction b a n d with respect to different reference%
(standard calomel reference electrode and vacuum, respectively), they can be directly related by

EA -- Eo + Vfb + Arc Jr ApH

will discuss some of the implications of ~hese ideas to

nonoxide electrodes and other t h a n aqueous redox
couples.

Calculation of SemiconductorElectron Affinity

Consiaerale success has been achieved in calculating Fermi energies and photoelectric thresholds for
several classes of compounds (5) using the atomic
electronegativities of the constituent atoms. Mulliken's
definition of the electronegativity of a neutral atom is
the arithmetic mean of the atomic electron affinity and
the first ionization energy
x(M) = 1~ (A~ + I1)

[1]

where Eo is a constant relating the reference electrode

to the v a c u u m level (Eo -- 4.75 eV for SCE) (3), Ale
corrects for the difference between the doped F e r m i
level and the bottom of the conduction b a n d (A~r
0.1 eV for heavily doped metal oxides) ( 2 ) , and ApH
is the potential drop across the Helmh01tz layer due
to specific adsorption of OH = and H + ions. There
exists some u n i q u e point for each semiconductor where
the n u m b e r of positively and negatively charged pot e n t i a l - d e t e r m i n i n g ions at the interface are e q u i v a lent: At this point, the potential drop across the Helmholtz layer due to adsorbed ions is zero and ApH o r its
equivalent for other adsorbed ions is zero. This point,
called the p o i n t of zero zeta potential (pzzp) (4), is
the only point at which t r u l y m e a n i n g f u l fiatbands
can be measured and it is this fiatband t o which the
calculated electron affinities should be compared. We
will discuss the d e t e r m i n a t i o n of the pzzp ior several
metal oxides and show that it correlates to the F e r m i
energy of the undoped metal oxide semiconductor.
With these two correction factors (Arc and ApH) taken
into account, the predicted and measured flatband potentials are in excellent agreement. Additionally, we
* Electrochemical Society Active Member.
/Key words: photoelectrolysis, zeta potential, electron affinity.

[2]

where, for clarity's sake, we use Af for the atomic

electron affinity and I1 is the first ionization potential.
Since the ionization potentials (6) and electron affinities (7) for most atoms are tabulated, the Mulliken
electronegativities x(M) form a readily evaluated a b solute elqctronegativity scale based only on m e a s u r able physical parameters. I n a sense, x (M) is the electrochemical potential of the electron in the n e u t r a l
atom. When atoms are brought together to form compounds, charge will flow u n t i l the electrochemical potentials (electronegativities) are equalized. Sanderson
(8) and more recently Nethercot (~), have postulated,
based on bond length arguments, that the resulting
bulk electronegativity of the compound is the geometric m e a n of the electronegativities of the constitu e n t atoms. This assumption appears to be valid for
a large n u m b e r of compounds (5, 9). For a semiconductor the b u l k electronegativity corresponds to the
undoped F e r m i level or halfway b e t w e e n the bottom
of the conduction b a n d and the top of the valence
band. Thus the electron affinity of the compound
will
be given by
EA = X -- I/2 Eg
[3]
where Eg is the bandgap energy. Applying this equation and the postulate of the geometric mean, we find,
for example, that for TiO2, the electron affinity is
EA(TiO2) -~ ~(TiO2)

1/2 E s = [x(Ti) x2(O)] 1/3

-

1/2 Eg ----4.33 eV

[4]

relative to the vacuum level. We have calculated the

e l e c t r o n affinities for a n u m b e r of metal oxides and
they are listed in Table L Even without considering
the correction terms in Eq. [1], there is obviously a
strong correlation b e t w e e n the measured fiatband potentials and calculated electron affinities as is illus-

228
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PREDICTION OF FLATBAND POTENTIALS

V o l . 125, N o . 2
3. O

ZrO2

the solution is close to i d e a l and aA can be r e p l a c e d b y

CA, the concentration of A. In the a d s o r b e d phase at
pzzp the concentration of O H - a n d H + a r e equal; thus
we m a y w r i t e

8aTiO3
9 SrTiO3

4.0

Ta205 9

229

oLdO--

= o;solO

"Jr R T In CoH-~o~ -- R T In CH+sol

9 ZnO
TiO2 9

@ FeTiO3

SnO2

Since (2.303) p H ---- --In CH+sol and the difference in

s t a n d a r d state electrochemical potentials in solution
for O H - and H + is 1.23 eV, this m a y finally be w r i t t e n

CdO

Fe2039

J a d OIl- - - j a d H+ --" 1.23 eV -t- 4.606 R T (PHpzzp -- 7)

5. D

9 WO3
,,

-2

-I

+1

Flatl~nd Potentialvs SCE{V)

Fig, 1. The electron affinity calculated using atomic electronegativities vs. the flatband potentials measured at pH = 13.3
(IM HaOH).

s t r a t e d in Fig. 1. As expected (10), the m o r e negative

flatband potentials come from semiconductors with
s m a l l e r electron affinities. The correction f o r the difference b e t w e e n the d o p e d F e r m i level and the b o t tom of t h e conduction band depends, n a t u r a l l y , on
doping level. However, for h e a v i l y d o p e d m e t a l oxides,
c o m m o n l y e m p l o y e d for photoelectrolysis, this t e r m is
only about 0.1 eV. Such a small correction cannot account for the scatter o b s e r v e d in Fig. 1. This m u s t
come from the specific a d s o r p t i o n of ions.
Point of Z e r o Z e t a Potential ( P Z Z P )

A brief discussion of the n a t u r e of the pzzp and the

techniques e m p l o y e d for its m e a s u r e m e n t a r e in o r d e r
due to the i m p o r t a n c e and m a g n i t u d e of ~pH. T h e r e is
a sizeable l i t e r a t u r e on the pzzp of m e t a l oxides (4,
11-17), which colloidal chemists h a v e t r a d i t i o n a l l y r e f e r r e d to as the point of zero charge (pzc). This t e r m i n o l o g y is c l e a r l y i n a p p r o p r i a t e in the context of
semiconductor e l e c t r o c h e m i s t r y w h e r e pzc refers to the
flatband potential. Thus w e adopt the notation of the
point of zero zeta potential (pzzp) (18). Historically,
the d e t e r m i n a t i o n of the pzzp for m a t e r i a l s has h a d
i m p o r t a n t ramifications in the a r e a of flotation p r o c esses (4). While s e v e r a l ionic species m a y be specifically
adsorbed, for m e t a l oxides, the point of zero zeta p o tential u s u a l l y refers to specific adsorption of OH and
H+ ions. The pzzp is t h e n the p H at which the net s u r face charge is zero or the concentration of a d s o r b e d
O H - and H+ ions is equal. U n d e r these conditions,
t h e r e is no net p o t e n t i a l across the H e l m h o l t z l a y e r
other t h a n the s m a l l dipole contribution of the solvent.
T h e energetics of this condition can be e x a m i n e d b y
considering t h e electrochemical p o t e n t i a l ( ; ) of the
ions in the a d s o r b e d l a y e r and in the' solution.
A n y adsorbed loft in e q u i l i b r i u m w i t h the same ion
in solution will have
~d

~ol

[8]

[9]

It is possible to d e t e r m i n e the s t a n d a r d - s t a t e e l e c t r o chemical potentials for the a d s o r b e d species if the a p p r o p r i a t e h y d r o x y l a t e d and p r o t o n a t e d species and
t h e i r s t a n d a r d free energies of f o r m a t i o n are known.
In this case, the pzzp m a y be c a l c u l a t e d d i r e c t l y using
Eq. :[9]. In general, this i n f o r m a t i o n is not k n o w n a n d
the pzzp m u s t be m e a s u r e d e x p e r i m e n t a l l y or estim a t e d f r o m k n o w i n g the semiconductor e l e c t r o n e g a tivities. We show in Fig. 2 the pzzp for several m e t a l
oxides vs. the e l e c t r o n e g a t i v i t y of those oxides. The
d a t a suggest that t h e r e is a strong correlation. T h e o b served slope h a s the same pHpzzp d e p e n d e n c e as i n Eq.
[9]. However, the q u a n t i t a t i v e relationship b e t w e e n
Eq. [9] and Fig. 2 is not clear. The scatter in the d a t a
u n d o u b t e d l y arises f r o m t h e difficulty in m e a s u r i n g
pzzp's. M e a s u r e d pzzp's seem to d e p e n d s o m e w h a t on
the method of p r e p a r a t i o n of the oxide (4).
S e v e r a l techniques h a v e b e e n used to d e t e r m i n e
pzzp's (4). The simplest is j u s t addition of the m e t a l
oxide p o w d e r to an aqueous solution o f a k n o w n p H
with no o t h e r a d s o r b a b l e species present. The p H of
the solution will shift on a d d i t i o n of the p o w d e r
t o w a r d the pzzp. A t the pzzp the p H of the solution is
i n d e p e n d e n t of the a m o u n t of m e t a l oxide added. A
m o r e q u a n t i t a t i v e m e a s u r e of specific ion adsorption is
obtained f r o m the p o t e n t i o m e t r i c t i t r a t i o n of a m e t a l
oxide suspension with either acid or base for solutions
of specific ionic strength. Since the ions a d d e d m u s t
either go to changing the p H of the solution or be a d sorbed on the m e t a l o x i d e surface, it is possible to d e t e r m i n e the surface charge d e n s i t y as a function of
p H for several concentrations of supporting electroi

6.5
@<a205
--@

6. O

SnO 2

Zr02

Fe203
TiO2oHg01,. @ oCuO
FeTi03g Fe304~Z'~o@Ni0
T \
Cr203 ~
9 Cd0
N
9

%
5.5

[5]

and u n d e r e q u i l i b r i u m situations this should a p p l y to

all a d s o r b e d ions. Thus at the pzzp w e can w r i t e
/~adOH- ~/~ad H ~ ~solOH- -- $~olH+

[6]

gario3
84

The chemical potential of a n y component, A , i n solution can be w r i t t e n as

~ol A

"

o~oI A 4- R T In (aA)

[7]

w h e r e o;~o~A is the electrochemical p o t e n t i a l in t h e

s t a n d a r d state, aA is the a c t i v i t y of A in the solution
phase, R is the ideal gas constant, and T is the absolute
t e m p e r a t u r e . N o r m a l l y the assumption is m a d e that

..,

\
14

PZZP(I~)

Fig. 2. Plot of the pH where the zeta potential is zero (pzzp) vs.
calculated electronegativity for the bulk semiconductor in electron
volts. The line is drawn through:the data and has a slope of 0.12
eV/pH,

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J. Electrochem. Soc.: E L E C T R O C H E M I C A L S C I E N C E A N D T E C H N O L O G Y

230

lyte. The point at which these curves intersect is the

pzzp.
We have found that a simple differential potentiometric titration of an aqueous suspension of the semiconductor of interest in a solution of k n o w n ionic
strength gives good peaks for the pzzp on plots of
n p H / A m l vs. pH.
I n general this technique is similar to that employed
for obtaining the fast adsorption isotherms but is
somewhat less complex as only one titration is required. A procedural outline is included so as to clarify
the e x p e r i m e n t a l parameters. All glassware was
cleaned b y boiling i n distilled water, from a n all-glass
Autostill, after a n Alconox wash a n d distilled w a t e r
rinse, then s u b s e q u e n t l y rinsed five times with distilled
water. Reagents used were of the highest available
p u r i t y a n d all of the oxide powders were four nines or
better purity. The pH was m e a s u r e d with a Markson
Electromark pH analyzer equipped with an Orion combination pH electrode and a digital readout. All t i t r a tions were performed i n argon purged, stirred solutions. Typically, 1-10g of the oxide of interest were
added to 600 m l of deionized, distilled water t y p i c a l l y
0.001M i n KNO3, which is a n o n a d s o r b i n g species. The
KNOB was found to be unnecessary, b u t some ionic
strength in the solution helped stabilize pH readings
near the equivalence point. The pH of the solution was
t h e n adjusted to near 10-11 with 1M KOH. The solution was back titrated with HNOa first with 1M and
t h e n with 0.1M as was indicated b y the rate of change
of pH with additional i n c r e m e n t s of titrant. All additions were carried out with microburettcs and typical
accuracies were
ml and +--0.005 pH units. The
reproducibility of the peaks corresponding to the pzzp
was excellent.
On the addition of titrant, conservation of charge
requires that
A(I'H+ -- FOH-) : xCl

V[(CH+

---

--

COIl-)

(CH+ -- CoH-)initial]

[10]

where A is the surface area of the suspended metal

oxide, r is the surface density of the appropriate ion,
x is the volume of t i t r a n t added, C1 is the concentration
of titrant, V is the volume of the suspension, and C is
the appropriate concentration of ions in solution. This
equation assumes that total added volume due to titration is negligible compared to the total suspension volume. if we differentiate this equation with respect ~o
x, we find
A 0(FH+

--

Ox

roll-)

C1

-- "V

8CH+
[1
(gx

kw/C~+ 2]

[li]
where kw is the ionization constant for water. By exp a n d i n g the partial of the surface charge density, we
obtain

OCH+
OX

(CI/V)

A 0r
kw ] - i
i + V OCH+ t- CH+~ l

[12]

where r -- (FH+ - - t o n - - ) . NOW CH+ =- exp (--2.303

pH). This equation and its derivative with respect to
x allows us to convert Eq. [12] to a pH dependence.
F i n a l l y we find

OpIt
Ox

i03

The behavior of this equation is displayed i n Fig. 3 for

p u r e w a t e r and for 10-~M KNO~ solution with two
different a m o u n t s of TiO2 powder added. The solid
curve for pure water is just Eq. [13] with A the surface area of suspended metal oxide set equal to zero.
I n general, the data agree excellently with the theory

Water
io2

/ ~
0 9

]0I

./..

0\
2 gms TiO

..

%/.

6m,T,o2

-o.

i00

10

Fi9. 3. Differential potentiometrir titrations plotted as apH/aX

(ApH/Aml) VS. pH far 3 solutions: O O O 600 ml distilled-deianized water, initial pH adjusted with 0.1M KOH, e S O 600
ml distilled-deionized water 0.001M in KNO3 with 2g of suspended
TiO2 (99.995%) initial pH adjusted with 0.1M KOH, , k A & 600
ml distilled-deianized water 0.001M in KNO3 with 6g of suspended
TiO2 (99.995%). The solid lines represent theoretical fits of the
data from Eq. [13] in the text. All solutions were stirred under a
constant purge af argon and all titrations were performed with 0.1M
HNO~.

(no adjustable parameters) except where the rate of

change of pH becomes quite large (near the equivalence point). Here, adsorption onto the glass surface
and small a m o u n t s of impurities can buffer the solution to significantly lower the rate of change in pH.
The "theoretical" curves for the TiO2 suspensions were
calculated f r o m Eq. [13] with a n assumed constant
value for Or/apH of 4 X 10 -11 m o l e s / c m 2 (13). The
surface area was then adjusted to fit the data at pH ---7. Note that the rate of change i n pH at pH ---- 7 scales
inversely with the a m o u n t of TiO2 added. This i n d i cates that the particle size was the same for two powders. We find from the fit a surface area for the powder of ~ 17.3 mZ/g. This m a y be compared to the r e sults of Berube and D e B r u y n (13) who used TiO2
powder of 43 mZ/g. If we assume spherical particles,

-- ( e l ~ v ) exp (2.303 pH)

[
0r
2.303 1 + kw exp (4.606 p H ) - - (A/2.303V) ~

February 1978

]
exp (2.303 pH)

[13]

o u r surface area corresponds to diameters of --~ 900A.

These n u m b e r s are q u i t e reasonable. At the pzzp it is
evident (4) that or/apH becomes small. From Eq. [13]
we would thus expect a peak i n the derivative curve
at the pzzp. As you can see in Fig. 3, this is indeed the

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PREDICTION OF FLATBAND POTENTIALS

Vol. 125, No. 2

Table I. Calculated electronegativity and electron affinity and

measured flatband potential and point of zero zeta potential for
several metal oxides
Compound*

X
(eV)

EA
(eV)

V~b
(SCE) * 9

WO8
SiOa (a)
Ta~O~
SnO2
ZrO2
FelOn (b)
TiO3

6,53
6.46
6.38
6.24
5.92
5.88

-0.20

(19)

5.83

5.18
-4.08
4.49
3.42
4.71
4.33

-~-A4
-- 0 82
--2,94
-0.32
-0.90

(2"O)
(2 I)
(20)
(9)
(1O)

HgO
CuO
Fe~O~
ZnO
NiO
FeTiOa (c)
Cr~Os
CdO
AhOs
Ag20
MgO
SrTiOa ( d )
BaTiOs (e)

5.81
5.80
5.77
5.75
5.74
5.72
5.66
5.55
5.35
5.29
5,27
5.27
5,19

4.57
--4.15
3.89
4.30
4.80
4.55

----1.09

---(22)
-(2)

--0-.59

4.~9
1.42
3,71
3,60

PZZP
(pH) ~

Ref.

-0.22
~
~

(~)
~

--1.19
--1.22

~)
(2)

0.43
2.0
2.9
4.3
6.7
8.6
5.8
7.3
9,5
6,5
8.8
10.3
6.3
8.1
11.6
9.2
11.2
12.4
8.6
9.9

--

Ref.
(17)
(24)
This w o r k
( 14)
(12)
(10)
(13) and
this work
(24)
( 24 )
(25)
(11)
(24)
This work
(26)
(24)
(24)
(27)

(28)
This work
This work

* T h e s o u r c e s f o r t h e s e m a t e r i a l s w e r e : (a) J o h n s o n M a t t h e y
C h e m i c a l s L i m i t e d , p u r i t y 99.999%. (b) J o h n s o n M a t t h e y Chemic a l s L i m i t e d , 99.999%; F i s h e r , 99.95%; a n d M a t h e s o n C o l e m a n Bell,
99.5%; all g a v e c o m p a r a b l e r e s u l t s . (c) See D. S. G i n l e y a n d R. J.
B a u g h m a n , Mater. Res. Bull., 11, 1539 (1976). (d) N a t i o n a l L e a d
C o m p a n y , R e s e a r c h D e p a r t m e n t , " H i g h p u r i t y r e a g e n t " . (e} N a t i o n a l L e a d C o m p a n y , p u r i t y 99.99%.
** M e a s u r e d or c o r r e c t e d t o p H = 13.3. M e a s u r e m e n t a c c u r a c y
is a b o u t _0.1V.
T h e r e is a g r e a t d e a l os s c a t t e r in t h e m e a s u r e d pzzp's.
T h e s e a r e b e l i e v e d t o be the m o s t reliable v a l u e s .

case for TiO2 whose pzzp is ~ 5.8. A w o r d of caution

is p e r h a p s r e l e v a n t at this point. C o n t a m i n a t i o n of the
suspension b y a buffer or other m e t a l oxides will r e sult in spurious peaks in the curve. The r e a l i t y of the
p e a k can be checked b y using the simple m e t h o d of
direction of p H change with a d d i t i o n of a d d i t i o n a l
m e t a l oxide. The pzzp's for several m e t a l oxides a r e
shown in Table I. In general, we have found t h a t this
simple technique yields results in. good a g r e e m e n t w i t h
p r e v i o u s l y p u b l i s h e d results.

Discussion
Since both of the correction t e r m s can now be e v a l u ated, we can c o m p a r e t h e m e a s u r e d flatband potentials
d i r e c t l y to the calculated electron affinities as is shown
in Fig. 4. The solid line is the b e h a v i o r expected from
Eq. [1] w i t h no a d j u s t a b l e p a r a m e t e r s . One expects a
u n i t a r y slope and an i n t e r c e p t at zero flatband p o t e n tial of Eo. The a g r e e m e n t w i t h t h e o r y is excellent and
3.O

Zr02O ~ N x @ BaTi03

<~

FeTiO3
Ti02 I I \

SnO2 "~

,'7;

CdO

Fe203
5.

~ 0 3
I

-2

-I
O
FlaibsndPotentialvsSC[-(V}

+I

Fig. 4. The electron affinity calculated using atomic electronegativities vs. the measured flatband potentials for the labeled
semiconductors corrected to their respective pzzp's. The solid
line is that expected from Eq. [1] if the correction term, Aft, is
ignored. The flatband potentials and pzzp's not measured by us
are those listed in Table I.

231

shows that the flatband potentials for m e t a l oxides

can be calculated w i t h an a c c u r a c y of --~ 0.2V f r o m the
atomic electronegativities of the constituent atoms if
specific a d s o r p t i o n of p o t e n t i a l - d e t e r m i n i n g ions i s
p r o p e r l y t a k e n into account. E v e n w i t h o u t an a c c u r a t e
accounting for the pzzp t h e p r e d i c t e d flatbands a r e
close enough so as to act as a guideline for electrode
selection.
While most of the considerations in this p a p e r h a v e
been concerned specifically w i t h O H - and H + as the
p o t e n t i a l - d e t e r m i n i n g ions, the results c e r t a i n l y a r e
m o r e g e n e r a l l y applicable. It is possible, for instance,
that the flatband could be shifted b y the addition of
other ions which a r e specifically a b s o r b e d while not
changing t h e p H and c o n s e q u e n t l y the H2 and 02 evolution reaction potentials. The effect of specific ion
adsorption on the cathode should also be e v a l u a t e d
since this m a y result in an a d d i t i o n a l p o t e n t i a l drop
in the circuit.
These ideas a r e of considerable i m p o r t a n c e w i t h
respect to w e t photovoltaic cells and o t h e r systems
e m p l o y i n g nonoxide electrodes w i t h nonaqueous r e d o x
couples (29-31). M a n y of these systems show no p H
d e p e n d e n c e of the flatband p o t e n t i a l but do show a
Nernstian t y p e d e p e n d e n c e on the concentration of
potential d e t e r m i n i n g ion. F o r e x a m p l e , in t h e cadm i u m sulfide, sulfur, sulfide ion cell ( C d S / S - S - 2 O H - / P t ) , the flatband p o t e n t i a l of the CdS depends
on the S -2 concentration. Thus, t h e r e will b e a Aps correction t e r m in Eq. [1] and a pzzp for sulfide ion,
since the p o t e n t i a l across the H e l m h o l t z l a y e r will d e p e n d on ( S - 2 ) . Therefore, in general, one must correct
the m e a s u r e d flatband potentials to the respective
pzzp of the p o t e n t i a l - d e t e r m i n i n g ions to obtain a
m e a s u r e of the intrinsic flatband potential. We are c u r r e n t l y in the process of e v a l u a t i n g some of these n u m bers for nonoxide systems.

Acknowledgments
The authors a r e i n d e b t e d to W. H. S m y r l for h e l p ful discussions. The w o r k r e p o r t e d in this p a p e r was
done for the U.S. E n e r g y Research a n d D e v e l o p m e n t
A d m i n i s t r a t i o n u n d e r Contract AT(29-1)-789.
Manuscript s u b m i t t e d J u n e 20, 1977; revised m a n u script r e c e i v e d Sept. 17, 1977.
A n y discussion o f this p a p e r will a p p e a r in a Discussion Section to be p u b l i s h e d in the D e c e m b e r 1978
JOURNAL. All discussions for the D e c e m b e r 1978 Discussion Section should be s u b m i t t e d b y Aug. 1, 1978.

Publication costs o] this article were assisted by

Sandia Laboratories.
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Behavior of Polymeric Sulfur Nitride, (SN) ,

Electrodes in Aqueous Media
Robert J. Nowak,* Wlodzimierz Kutner,I and Harry B. Mark, Jr.**
Department 05 Chemistry, University 05 Cincinnati, Cincinnati, Ohio 45221

and Alan G. MacDiarmid

Department o5 Chemistry, University o] Pennsylvania, Philadelphia, Pennsylvania I9174
ABSTRACT
Polymeric sulfur nitride, (SN)x, has been characterized as an electrode
material in aqueous solution by cyclic v o l t a m m e t r y and cyclic chronoamperometry. Background currents, resulting from oxidation and reduction of
electrode surface functional groups, were studied in different supporting electrolytes and pH values. A large influence of the n a t u r e of the alkali metal
cations and Ca 2+ of supporting electrolytes on the m a g n i t u d e of background
currents and cathodic b r e a k d o w n potentials was found. This was interpreted
in terms of differences in the interaction strength b e t w e e n these cations and
electrode surface functional groups. The f e r r o - f e r r i c y a n i d e couple was used
to d e t e r m i n e r e l e v a n t electrochemical p a r a m e t e r s as well as electrode s u r face areas. Other redox couples which are active at (SN)x electrodes are discussed, e.g., p b 2 + / p b o, Ru(NH3)63+/Ru(NH3)62+, q u i n o n e / h y d r o q u i n o n e . It
was not possible to reduce Cr 3+ at (SN)x electrodes. F u r t h e r m o r e , a dramatic
decrease i n background currents was observed for Cr ~ + electrolyte solutions.
The (SN)z was found to be r e m a r k a b l y stable i n aqueous solutions u n d e r
a wide variety of conditions and a suitable electrode material for chemical
modification.
Polymeric sulfur nitride, (SN)x, has been reported
recentlY (1) as a n e w electrode material. This substance has been classified as a metal even though there
are no metal atoms present in its structure (2). The
(SN)x exhibits electrical and chemical anisotropy and
its surfaces make available n u m e r o u s types of f u n c tional groups and surface types for possible chemical
modification (3). In order to use (SN)x in this capacity, iX is of P r i m a r y importance to characterize its
general electrochemical behavior before a n y modification experiments are performed. Therefore, we report
here systematic f u n d a m e n t a l studies using (SN)x as a
working electrode i n order to evaluate ~it with respect
to the criteria suggested by MueUer and Adams (4).
* Electrochemical Society Student Member.
** Electrochemical Society Active Member.
1Permanent address: Institute of Fundamental Problems of
Chemistry, Warsaw University, Warsaw, Poland:
Key words: polythiazyl, polymeric electrodes, chemically modified electrodes, lead deposition, ferri-ferrocyanide.

Experimental
Reagents.--All chemicals were of reagent grade and
were used without f u r t h e r purification. C h r o m i u m ( I I I )
perchlorate was obtained from V e n t r o n Corporation.
Solutions were prepared with distilled water which
was passed through ion exchanger and, finally, activated carbon columns. Solutions were deoxygenated
with argon or high p u r i t y nitrogen.

Instrumentation.--Cyclic voltammetric and chronoa m p e r o m e t r i c experiments were carried out with the
use of PAR T M Model 173 potentiostat/galvanostat
equipped with a PAR T M Model 176 c u r r e n t to voltage
converter, a PAR T M Model 175 universal programmer,
and a Hewlett P a c k a r d Model 2D-2M X - Y recorder or
alternatively, a PAR T M Model 170 electrochemistry
system. Micrographs were obtained with a Coates and
Welter Cwikscan 100-4 or I n t e r n a t i o n a l Scientific I n s t r u m e n t s Model 7 scanning electron microscope.

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