Int. J. Hydrogen Energy. Vol. 5, pp 401-408. 0360-3199/80/0701-0401 $02.

00/0
Pergamon Press Ltd. 1980 Printed in Great Britain
~) International Association for Hydrogen Energy

ELECTRODES FOR GENERATION OF HYDROGEN A N D

OXYGEN FROM SEAWATER
J. E. BENNETT
Diamond Shamrock Corporation, Painesville, OH 44077, U.S.A.

(Received for publication 16 October 1979)

A~traet---Direct electrolysis of seawater in non-diaphragm cells results in the cathodic evolution of hydrogen
at high current efficiency. Large volumes of chlorine in the form of hypochlorite solution are normally evolved
at the anode, however, and this presents a major environmental problem.
Relative chlorine and oxygen efficiencywas determined in seawater at a variety of temperatures and salinities,
and using a number of typical anode materials. Oxygen is evolved exclusivelybelow the theoretical voltage for
chlorine evolution, but current density is too low (< 1 mA/cm2) at this point to be of practical importance. The
limiting current density for chlorine evolution in seawater is variable depending on salinity, temperature, cell
design, and flow considerations, but for practical cell operation will range from 100 to 1000 mA/cm2. It can be
concluded from these data that the use of conventional electrode materials at any practical conditions of electrolysis
will result in significant evolution of chlorine in the form of sodium hypoehlorite.
Experimentally measured exchange currents and Tafel slopes for both oxygen and chlorine evolution at the
DSA are used to explain the relationship between the two competing reactions under a variety of conditions.
Under normal conditions of seawater electrolysis,mass transfer limitations and reaction kinetics tom brae to make
chlorine evolution the dominant anodic reaction.
Following this basic study, electrodes were prepared to specificallyfavor the evolution of oxygen from brine
solutions. Unique manganese dioxide coatings are capable of evolving oxygen from seawater at 99~ efficiency,
and from saturated sodium chloride brine at 95~ efficiency.A mechanism is proposed in which the surface coating
acts as a diaphragm, causing the chlorine evolution reaction to more rapidly become mass transfer limited. Limiting
current density of chloride oxidation can be lowered 2-3 orders of magnitude in this way, making oxygen the
dominant anodic reaction at all reasonable conditions of electrolysis.

INTRODUCTION
SEVEI~AL proposals have been suggested for sea-based power plants deriving energy from ocean
thermal gradients, wind and wave generators, and from nuclear breeder reactors placed at sea to
minimize thermal pollution. A number of these proposals have suggested the direct electrolysis of
seawater as a convenient source of hydrogen on a large scale. Electrolytic hydrogen could then be
shipped ashore or could be combined with carbon dioxide extracted from seawater to produce
methane, methanol, and other light fuels for transportation to the continents [,1]. As pointed out by
Bockris [2], however, the usual electrode materials and conditions of electrolysis favor the evolution
of chlorine anodically rather than oxygen. Massive quantities of by-product chlorine, such as would
be generated by a major power plant, could not be discharged to the environment and would be
costly to convert back to chloride. It would be an obvious advantage if seawater could be electro-
lyzed directly to produce only hydrogen and oxygen. The purpose of this study was to examine the
variables which affect the relative evolution of chlorine and oxygen from seawater, and to propose
techniques for selectivity evolving oxygen from chloride solution.
The manufacture of commercial seawater electrolyzers which efficiently produce hypochlorite
solution from anodically generated chlorine [-3-5] confirms the predominance of the chlorine reac-
tion. Seawater electrolysis is used today to provide on-site hypochlorite for wastewater treatment
plants, and for coastal power stations and ships where hypochlorite is used to prevent the growth of
marine organisms which tend to foul equipment and make heat transfer difficult. Commercial sea-
water electrolyzers are manufactured today by Diamond Shamrock, Engelhard Minerals & Chemicals,
Pacific Engineering, Daiki Engineering, Mitsubishi, Cumberland Engineering, and Oronzio de Nora.
The SANILEC ® equipment shown in Fig 1 is a portion of the largest seawater electrolysis facility in
the world at Qurayyah, Saudi Arabia. These cells are used to produce 5400 kg/day of available
401
402 J.E. BENNETT

FIG. 1. 5400 kg/day seawater electrolysisplant, Qurayyah, Saudi Arabia.

chlorine for treatment of 7 MM bbl/day of seawater which is then pumped inland for secondary oil
recovery. As with most other seawater electrolysis facilities, by-product hydrogen from this process is
not recovered, but is vented to the atmosphere.

O2/C12 EVOLUTION RATES IN CONVENTIONAL SEAWATER ELECTROLYSIS

Separate efficiencies for oxygen and chlorine evolution from low chloride solution is difficult to
determine using conventional instrumental techniques. Although individual voltammetry peaks for
chloride oxidation can be obtained under certain conditions, the two reactions usually occur simul-
taneously with no clear definition between them. For this reason, a batch electrolysis is useful where
available chlorine concentration is plotted against ~o efficiency for "available chlorine" production.
The term "available chlorine" includes all free chlorine, hypochlorite, and chlorite, and is easily
determined by iodimetric titration. Once Faradaic efficiency for chlorine is established in raw sea-
water, oxygen evolution can be assumed to consume the balance of the anodic current. A more de-
tailed description of the analytical procedure and other possible chemical and electrochemical
reactions at higher hypochlorite strength is included in an earlier publication I-4].
 ELECTRODES FOR GENERATION OF HYDROGEN AND OXYGEN FROM SEAWATER 403

Figures 2, 3, and 4 show how certain variables effect the Faradaic efficiency for chlorine evolution
in conventional seawater electrolyzers. A typical current efficiency plot for available chlorine produc-
tion in a laboratory cell is shown by Figure 2. This data was taken at slow electrolyte velocity in a
simple beaker cell as described in an earlier publication [4]. An extrapolation of these curves back to
zero concentration of chlorine can then be used to determine the relative efficiency for chlorine and
oxygen evolution in seawater. The decrease in chlorine efficiency with increasing hypochlorite con-
centration is due to both the electrochemical oxidation and reduction of the hypochlorite itself.
An extrapolation of the curves on Fig. 2 shows that chlorine current efficiency can vary appreciably
for different anode materials with the DSA ® and platinized titanium both at 92 ~o, lead dioxide at
76 %, and graphite at 66 ~o. A DSA electrode was used for the detailed parametric study because of
its demonstrated long-term stability and nearly reversible chlorine overvoltage for seawater electro-
lysis. The type of DSA used was the T i O J R u O / coating normally used for commercial chlorine
production and described in patent literature [6].

Electrode materials
155mA/cm 2, 25"C.
I00

8O
- [3 ~ ~ DSA and

c 60
.~_

~ 40

o o ~
20

o I L L I L I L
0 I 2 3 4 5 6 7
Available chlorine, gpl

FIG. 2. Current efficiency vs chlorine concentration in seawater.

Comparison of the four lines in Fig. 3 demonstrates the effect of seawater salinity on current
efficiency in commercial cells. This data was taken on 1250 ampere cells using DSA anodes and
sheet nickel alloy cathodes approximately 1 m high and 25 cm wide. The more rapid drop in effici-
ency than shown in Fig. 2 is due to a higher degree of turbulence than in the laboratory cell. Seawater
velocity of 60 cm/s was maintained to minimize deposit formation on the cathode surface. Salinity
is an important consideration since seawater in coastal areas is often brackish, having a lower salinity
due to the influx of fresh water from continental runoff, while seawater in hot, arid climates may have a
salinity much higher than normal. Solution referred to as ""100 ~o seawater salinity" contains 18,980
mg/l chloride ion [7], an average value for the oceans of the world. The decrease in chlorine efficiency
at low salinity is evidence that the current density is approaching the diffusion limiting current for
chloride oxidation.
The effect of temperature on the relative oxygen/chlorine efficiency is shown by laboratory cell
data in Fig. 4. The decrease in chlorine efficiency at high concentrations of available chlorine is due to
an increase in the rate of reactions of hypochlorite, particularly the cathodic reduction. The variation
of extrapolated current efficiency with temperature at zero concentration of available chlorine is a
direct result of lower limiting current for chloride oxidation, increasing oxygen evolution under these
conditions.

@Registered trademark, Diamond Shamrock Corporation.

404 J. E. BENNETT
25"C
I00

801

60

7'5*/. of s e a w a t e r - ~ x\× :'~.

20
- \\
0 I I I I I I
0 I 2 3 4 5 6
Available chlorine, gpl

FIG. 3. Efficiencyvs chlorine concentration. Effect of salinity.

155mA I c m z
DSA electrode
I00

80

i
6o

2O
45"C 350C

I I I l I I
0 2 4 6 8 fO 12 14
Available chlorine, gpl

FIG. 4. Efficiencyvs chlorine concentration. Effect of temperature.

These data clearly demonstrate that chlorine evolution is the predominant anodic reaction in
seawater when using conventional anodes and usual conditions of electrolysis. This conclusion might
be unexpected since oxygen evolution is actually the thermodynamically favored anodic reaction. The
next figures and the following discussion now show how mass transfer limitation and reaction
kinetics combine to supress oxygen evolution at the anode. An understanding of this theory can then
be used to suggest conditions for seawater electrolysis which will result in the production of only
hydrogen and oxygen.

THEORY OF SEAWATER ELECTROLYSIS

By applying the Nernst equation to standard electrode potentials it can be seen that oxygen
evolution is actually the thermodynamically favored anodic reaction, occurring significantly less
 ELECTRODES FOR GENERATION OF HYDROGEN AND OXYGEN FROM SEAWATER 405

anodic than chlorine in neutral seawater. Such a superficial analysis is highly misleading, however, and
two major factors are responsible for the evolution of chlorine at practical operating conditions.
First, in unbuffered solutions such as seawater, both oxygen and chlorine evolution cause the
solution adjacent to the surface of the anode to become acidic. This is obvious for the case of oxygen
evolution which generates H ÷ as follows:
2H20 -~ 02 -}- 4H + + 4e-.
Any chlorine generated at the anode undergoes immediate hydrolysis which also generates H + as
follows:
2C1- ~ C12 q- 2e-
C12 + H 2 0 ~ H C I O + C 1 - + H+
HC10 ~ C l O - + H +.

As the anode surface becomes more acidic, the thermodynamic voltage for oxygen evolution becomes
more anodic, a trend favoring chlorine evolution which is independent of pH. As power is first applied
to an anode, the theoretical voltage for oxygen evolution will therefore become more anodic accord-
ing to the equation [8]
RT RT
Eo2 = 1.23 + -if-log(a.+)a,ode + ~ - l o g Po2'

The steady-state pH of the solution adjacent to the anode, and hence the voltage at which the anode
operates during continuous electrolysis, is dependent primarily on conditions of flow rate and
current density. As will be shown by measurements described later, the effective anode pH under
practical conditions of electrolysis is about pH 1-2. Even when the effective anode pH becomes very
low, oxygen evolution is thermodynamically preferred to chlorine evolution by about 200 mV. This
analysis is incomplete, however, since thermodynamic voltages are valid only at zero current flow.
The second factor which then inhibits the evolution of oxygen is its well-known high overpotential
at practical current densities. The difficulty of evolving oxygen relative to chlorine is illustrated by a
comparison of their exchange current densities which is an indicator of the ability of an electrode to
catalyze a given electrochemical reaction. The ratio of exchange current densities for chlorine and
oxygen evolution on most anode materials is very high

= 1 × 103 - 1 × 107,
ioo~
which is a measure of the ease of evolving chlorine relative to oxygen.
Figure 6 is a semilogarithmic graphical representation of single electrode potentials vs current [2].
By superimposing data for the oxygen and chlorine evolution reactions at the DSA, the relative kinet-
ics of the two oxidations can be shown. The Tafel slope for chlorine evaluation in 1.0 M HC1 was
determined to be 37 mV, and the exchange current to be 1.3 x 10- 3 A/cm 2. This Tafel slope agrees
with that determined by previous workers [9, 10]. Below the exchange current, the plot for chlorine
evolution essentially becomes a straight vertical line. At high current density chlorine evolution
becomes diffusion limited at about 1000 mA/cm 2 and the plot approaches a horizontal line. This
limiting current was determined in 100 ~o seawater salinity from chlorine efficiency data as described
previously.
The Tafel plot for oxygen evolution is much more difficult to locate because of the uncertainty of
pH of the solution at the anode interface. The data points shown for oxygen evolution were mea-
sured in this laboratory at the DSA in 1.10 M H2SO 4 over three decades of current. The Tafel slope
was determined to be 45 mV, and the exchange current to be 6 x 10-10 A/cm 2.
The effective current-voltage curve for oxygen evolution in seawater is experimentally found to be
not parallel to the Tafel lines, but cuts diagonally across them to intersect the pH 7 Tafel line at the
exchange current. The actual line representing oxygen evolution from seawater on Fig. 6 was calcu-
lated from chlorine efficiency data as described previously over a range of current densities. A compari-
son of this line with the chlorine line can be used to illustrate why chlorine evolution is predominant
between 1 and 1000 mA/cm 2 and between the anode potentials of 1.38 and 1.55 V vs NHE.
406 J. E. BENNETT
DSA electrode
/ / / /
10° / / ~¢
"~"~ ]~Z"
.;L 2,Jrnitirlg

,o-' ,~.W/Ii1~.~.~
,,~11~/ curren,

t6 3

/
~ ~65

io -7 ,, I I I
I2 13 14 15 16 17
Voltage vs NHE

FIG. 5. Log current vs voltage for chlorine and oxygen in seawater.

Conditions of seawater electrolysis can now be proposed to favor oxygen rather than chlorine
evolution. It can be concluded from Fig. 5 that electrolysis at very low current density, < 1 mA/cm 2,
will result in exclusive evolution of oxygen. This is not considered to be practical, however, due to the
very large electrode area required. It can also be shown that operation far in excess of the limiting
current for chloride oxidation will favor oxygen evolution. Limiting current in practical cells ranges
from 100-1000 mA/cm 2, however, and operation at several thousand mA/cm 2 would be necessary to
achieve high coulombic oxygen efficiency. This is also considered impractical since I.R. heating and
power consumption would become unreasonably high at such current densities.
It might also be suggested to develop anodes which are more active kinetically for oxygen evolu-
tion. An anode with an exchange current of oxygen comparable to that for chlorine would preferenti-
ally evolve oxyen, but this is contrary to common behavior, and development of such anode materials
seems unlikely in view of past experience.
The only major cathodic reaction in seawater is hydrogen evolution. Although hydrogen evolution
occurs at high coulombic efficiency, it also causes a localized pH change, resulting in a higher cell
voltage and causing deposit formation. As the cathode surface becomes more basic during electro-
lysis, the thermodynamic voltage for hydrogen evolution becomes more cathodic according to the
equation [8]

RT RT
EH2 = ~ log(aH*)~.h. ~ - 1og PH2"

As with the anode reaction, the actual pH of the solution adjacent to the cathode, and hence the
voltage at which the electrode operates during electrolysis, is dependent on conditions of flow rate,
current density, and temperature. Effective cathode pH will usually range from pH 11-14.
The basic nature of the solution at the cathode surface results in a surface deposit which is the
most troublesome operational problem encountered with the electrolysis of seawater. A chemical
precipitation of magnesium hydroxide occurs at a pH of 10.7-11.0. This deposit tends to adhere to
the cathode surface and later to grow onto neutral surfaces. If such a deposit is allowed to continue
building, it causes even higher pH at the cathode interface and will eventually clog the electrode gap.
Such deposits cannot be eliminated entirely, but they can be effectively minimized by high seawater
turbulence and proper choice of current density and cathode surface.
 ELECTRODES FOR GENERATION OF HYDROGEN AND OXYGEN FROM SEAWATER 407

D E V E L O P M E N T O F THE OXYGEN-SELECTIVE ELECTRODE

Recently, an anode coating which selectively evolves oxygen from chloride solutions has been
identified. The oxygen-selective coating can be applied to a DSA substrate during the electrolysis of
seawater or dilute sodium chloride solution at 150 mA/cm 2. The electrolyte is first doped with
150 rag/1 manganous ion and is then acidified below pH 1 with HC1. The acid electrolyte will first
cause chlorine to evolve as a gas, but the chlorine is quickly replaced by oxygen as electrolysis pro-
ceeds. Continued electrolysis for 15-20 min is sufficient to complete application of the coating. An
anode prepared in this manner is stable for long-term electrolysis of seawater solution. This is not
true of conventional thermally desposited or electrochemically deposited manganese dioxide which
degrades anodically in the presence of significant amounts of chloride ion.
The coating is apparently a porous deposit containing about 100 mg/m 2 manganese. Attempts to
characterize the coating with X-ray diffraction show no crystalline pattern, but only a broad amor-
phous ring, leading to the conclusion that it is essentially a poorly crystallized or amorphous form
of MnO 2. Voltammetry of anode surfaces confirms the slow buildup of an electrochemically reducible
layer ofMnO 2 with time. The mechanism of formation is probably both electrochemical and chemical.
The anode voltage is high enough to permit the anodic deposition of MnO 2 according to the reaction
Mn2++ 2H20 ~ MnO 2 + 4H ÷ + 2e-, E ° = 1.23 V,
and the chlorine evolving from the surface of the anode is simultaneously capable of oxidizing
manganous ion as follows:
Mn 2÷ + CI 2 + 2H20 ~ MnO 2 + 2C1- + 4H +.
An anode prepared in this manner will evolve oxygen from seawater at 99 + ~o efficiency with no
significant production of chlorine. In order to further test its efficiency for evolving oxygen, a series of
efficiency tests were conducted in saturated (310 g/l) sodium chloride brine. Remarkably, the anode
still evolved oxygen at 95 ~ efficiency.
Voltage and efficiency tests were then conducted in an effort to determine the mechanism for this
unusual behavior. It was first suggested that the evolution of oxygen from chloride solution was a
kinetic phenomenon caused by either an increase in the exchange current for the oxygen evolution
reaction or a decrease in the exchange current for the chlorine evolution reaction. Examination of
Fig. 5 shows that if the anode could be catalyzed for oxygen evolution such that ioo ~ io , oxygen
would become the preferred anodic product. This cannot be directly confirmed since It is not c,2 possible
to evolve chlorine in sufficient quantity to accurately determine the chlorine Tafel slope and exchange
current when using the oxygen selective electrode in aqueous media. Single electrode potential
measurements can be determined for oxygen evolution, however, and measurements taken in 1.0 M
H2SO 4 indicate almost no change in oxygen single electrode potential before and after addition
of the MnO 2 to a DSA surface. The measurements were made using a fast relay switch ( < 2 x 10- 6 S)
to interrupt current, eliminating the I.R. component in the system. A saturated calomel electrode was
used as a reference and a Nicolet 1090 AR oscilloscope was used to record electrode voltages.
Chlorine efficiency measurements in saturated NaCI brine were then used in order to indirectly
establish the position of the current-voltage curve for chlorine relative to oxygen evolution. Electro-
lysis at several different current densities failed to alter the rate of chlorine production, resulting in
the location of a horizontal line independent of anode voltage at about 10 mA/cm 2. It is not likely that
this limiting current is a kinetic phenomenon since it varies directly with chloride concentration in the
electrolyte. This apparently represents a true diffusion limiting current which is about three orders of
magnitude lower than expected in 310 g/1 NAC1 brine. The reason for this apparent lowering of limit-
ing current density is not clear. It appears that the MnO 2 coating acts as a diffusional barrier to
chloride ions causing a high degree of concentration polarization. There is no corresponding problem
with oxygen, however, since water is always available for oxidation. This relationship is graphically
illustrated for seawater solution by Fig. 6, which shows that oxygen evolution is now the preferred
anodic reaction over chlorine at any current density. The limiting current density of 1 mA/cm 2 for
seawater solution can be calculated from that measured in saturated brine by assuming that the
limiting current is proportional to chloride concentration.
It is, therefore, possible by proper choice of electrode materials to electrolyze seawater directly to
produce only hydrogen and oxygen. Cell voltages will be somewhat higher than those of conventional
408 J. E. BENNETT

,oO

~ 16z
J
,/
<

i(~3
#Y'#/ CL z limiting
current

L)

i(~ ~

~L 2

id ]
L I I I
12 15 14 15 16 17
Voltage vs NHE
FIG. 6. Log current vs voltage. Oxygen-selectiveelectrode.

water electrolyzers because the resistivity of seawater ( ~ 25 D-cm) is much higher than that of strong
KOH electrolyte, and also because of the pH drift at the electrode surfaces leading to higher thermo-
dynamic decomposition potentials. These two factors combine to raise seawater cell voltage in con-
ventional electrolyzers to about 3.0 V at 100 mA/cm 2. This voltage is, however, a result of conditions
maintained to optimize the production of hypoehlorite. Recirculation of electrolyte could be used to
raise operating temperature and concentration of salts, reducing cell voltage considerably in cells
designed for the direct production of hydrogen.
This study has established the technical feasibility of direct electrolysis of seawater to produce
hydrogen and oxygen. The advantages of this route can now be compared to alternate routes of
hydrogen production for shipment ashore.

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