Trickle Bed Electrochemical Reactors

Colin Oloman*
Department oi Chemical Engineering, University of British Columbia, Vancouver, B.C., Canada V6T 1W5

ABSTRACT
Electrochemical processes involving gaseous reactants can be carried
out in fixed bed electrodes with co-current d o w n w a r d flow of gas and electro-
lyte solution. Bench scale experiments with the electroreduction of oxygen, the
electroreduction of sulfur dioxide, and the electrowinning of copper in such
"trickle bed" electrodes show that the electrochemical power efficiency can
be increased by co-current gas loads up to 0.5 k g / m 2 see. Preliminary tests on
a scaled up trickle bed electrode of dimensions 2 m high X 0.25m wide X 3 nlm
thick outline potential problems with electrolyte dispersion and current dis-
tribution in such a device.

It is well k n o w n that gas sparging can e n h a n c e interactions b e t w e e n liquid load, gas load, a n d the
efficiency i n parallel plate electrochemical reactors size of the electrode particles. A rough q u a n t i t a t i v e
(1-3), b u t the effect of gas flow through t h r e e - d i m e n - guide to the effects of these variables is presented
sional electrodes has had little attention. I n this con- i n Table I. The n u m b e r s i n Table I were calculated
n e c t i o n there are a few published accounts of three- from the equations set out i n the Appendix, based
phase fluid bed electrodes (4-6) and of the effect of on a hypothetical mass transfer controlled electro-
gas flow i n fixed bed electrodes (7-9). A p a r t from chemical process i n aqueous solution with c o - c u r r e n t
the operation of gas diffusion electrodes, the presence fiow of a n i n e r t or a reactive gas.
of gas i n t h r e e - d i m e n s i o n a l electrodes is u s u a l l y re- E x p e r i m e n t a l observations of trickle bed electrodes,
garded as a nuisance which increases cell resistance together with calculations of the type s u m m a r i z e d
a n d interferes w i t h the electrode function. i n Table I, show that for effective e n h a n c e m e n t of
The use of c o - c u r r e n t r e a c t a n t gas a n d liquid flow- electrode surface area i n the useful electrode thick-
t h r o u g h fixed beds of catalyst particles is an estab- ness, and to avoid excessive pressure drops, the p a r -
lished method of conducting thermochemical reactions ticle size i n the trickle bed electrode should be b e -
(10). Various studies of these "trickle bed" reactors t w e e n about O.1 a n d 2.0 mm. This is somewhat lower
(11, 12) have shown that increased mass transfer rates t h a n sizes from 1 to 10 m m generally employed i n
result from the i n t r o d u c t i o n of gas with the liquid trickle bed thermochemical reactors. The i n t e r n a l
flowing t h r o u g h a fixed bed of catalyst particles. surface area of highly porous particles m a y be of
For electrochemical processes i n v o l v i n g gaseous little value i n electrocatalysts due to the high voltage
reactants the use of c o - c u r r e n t flow of gas and electro- drop through the electrolyte in the tortuous pores.
lyte solution i n fixed bed electrodes has interesting Gas and liquid loadings i n the trickle bed electrode
possibilities. E v e n w h e n gaseous reactants are not can be i n the range of about 0.Ol-l.0 kg m -2 sec - I
concerned it m a y be instructive to see the effect of a and 0.1-10 kg m -2 sec -1 respectively, which corre-
c o - c u r r e n t flow of i n e r t gas on electrode performance. spond to superficial velocities a b o u t 1-100 c m sec - I
This paper describes some investigations of such for air at S T P and 0.01 to 1.0 cm sec -1 for water.
trickle bed electrochemical reactors. These values are i n the region characterized as "gas
continuous flow" i n work on trickle bed reactors (10)
Characteristics of Trickle Bed Electrodes and illustrate the r e l a t i v e l y high ratio of gas to
By analogy with the trickle bed thermochemical liquid flow which can be used i n trickle bed elec-
reactor the trickle bed electrode consists of a fixed bed trodes. Such gas loadings do not make the electrode
of electroactive particles t h r o u g h which a gas a n d a n inoperative b u t m a y increase c u r r e n t efficiency b y
electrolyte solution are passed i n c o - c u r r e n t d o w n -
w a r d flow. A m a j o r difference b e t w e e n a t h e r m o -
chemical a n d a n electrochemical trickle bed reactor is
that i n the latter the decreasing potential difference
b e t w e e n the electrode and the solution limits the
effective electrode thickness to about 1 cm, i n the direc- GAB + ~- ~ GAS +
tion of the c u r r e n t flow (13). This constraint, together ELECTROLYTE !: :l ELECTROLYTE
:51
with a r e q u i r e m e n t for useful chemical conversion 9:.~d
:'.::(I
at high space-velocity and low voltage drop dictates /I COUNTER '" COUNTER
the practical form of the trickle bed electrode for ELECTRODE ELECTRODE
most purposes to be a long sandwich of electrocatalyst
particles b e t w e e n a counterelectrode a n d a feeder !:i.l
:.~'.1. J
MEMBRANE . ..,,
electrode as indicated in Fig. 1. Cylindrical electrodes .,.11
can be constructed this w a y b u t a plane configuration FEEDER FEEDER
has several advantages. ELECTRODE :)::I ELECTRODE

Depending on the electrochemical process to be " POROUS

"2 INSULATION
carried out the reactor m a y be divided into separate ELECTROCATALYST
cathode and anode chambers by a n ion-specific m e m - B E O ~
:4
b r a n e (Fig. 1A) or the electrode bed m a y be com-
:".:1
pressed against the counterelectrode, b u t p r e v e n t e d GAS + - ! GAS +
ELECTROLYTE~!"I ELECTROLYTE
from touching it by a porous i n s u l a t o r (Fig. 1B). m

A B
The operating characteristics of a trickle bed elec-
trochemical reactor depend i n a complex w a y on
* Electrochemical Society Active Member.
Key words: three-dimensional, flow-through, g a s , electrode, oxy-
gen reduction, sulfur dioxide reduction, copper electrowinntng,
scale-up. Fig. 1. Configurationof trickle bed electrochemicalreactors

1885
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 1886 J. E~ectrochem. 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 N o v e m b e r 1979

Table I. Predicted effects of liquid load, gas load, and particle size on active bed thickness and
superficial current density under mass transfer control in fixed-bed electrodes

Conditions: Fluid properties as f o r w a t e r and air at 20~

Kb > > KL, KL = 25 mho m-z, eb = 0.4, C = 0.01M, DL = 10-9 m~ sec -1, h = w = 10 nun, AV = 0.6V

L, kg m~ sec-1 0.1 10
G, k g m -2 sec-z 0 0.01 1.0 0 0.01 1.0
d, m m 0.1 10 0.1 10 0.1 I0 0.I 10 0.I 10 0.1 10

A p , b a r m -1 0.025 10 -6 1.11 0.0005 29 0.039 2.5 0.0006 23 0.014 115 0.14

,~ 1 1 0.18 0.032 0.046 0.028 1 1 0.63 0.37 0.32 0.27
KGa, s e c -~ -- -- 8.7 2.0 1300 18 -- -- 53 2.4 3300 38
KLa, s e c -1 -- -- 0.058 0.0012 0.30 0.011 -- -- 2.6 0.066 5.9 0.20
K,a, s e e - 1 2.1 0.0015 3.1 0.012 11.8 0.014 9.8 0.0071 8.6 0.010 17 0.014
Koa, s e c -1 -- -- 0.056 0.0011 0.29 0.006 1.9 0.0008 4.4 0.013
ta, m m (Inert gas) 1.4 50 0.45 3.1 0.12 2.7 ~5 24-- 0.53 12 0.26 8.4
il, kA m -2 5.5 0.15 2.7 0.07 2.6 0.07 12 0.32 8.7 0.23 8.5 0.23
ti, m m ( R e a c t a n t -- -- 3,3 10 0.75 4.0 -- -- 1.1 12 0.51 8.7
gas}
h , k A m-~ -- ~ 0.36 0.021 0.42 0.046 -- -- 4.1 0.21 4.3 0.22

t he i r positive effect on gas to liquid and liquid to bed el ect r o ch em i cal reactors. The reactors used h e r e
solid mass t r a n s f e r and by m a i n t a i n i n g excess r eac- w e r e constructed according to Fig. 1, by compressing
tive gas to sustain the desired electrode reactions. the cell components b e t w e e n fiat m e t a l plates w h i c h
Gas flow also decreases the axial dispersion that acted r e s p e c t i v e l y as the anode and the cathode feeder.
always occurs in this type of "plug-flow" reactor
and this too can i m p r o v e process efficiency (14).
Pressure drop and dispersion.--Typical pressure drop
curves for a 3 m m thick trickle bed el ect r o d e are s how n
The flow of gas in a fixed bed e le c t r o d e decreases
in Yig. 2. The reactor used h e r e was constructed as in
the liquid h o l d - u p and increases pressure drop (15).
Fig. 1B w i t h a synthetic fabric separator compressed
D e p en d i n g on gas loading the liquid h o l d - u p m a y be
f r o m about 10-90% of the bed voidage and this lowers against the counterelectrode.
the effective conductivity of the e le c t r o l y t e in the fixed Results of pulse i n p u t t r a c e r tests for axial liquid
dispersion characteristics of the r eact o r are displayed
bed in about t h e same proportion (16). Table I shows
that for a r e a c t i v e gas an increase in gas load is p r e - in Fig. 3. The decrease in dispersion w i t h increased
dicted to increase the mass t r a n s f e r l im i te d superficial gas flow is obvious in these curves, w h i ch yield P e c l e t
c u r r e n t density as w e l l as to shift the e le c t ro act i v e n u m b er s f r o m 22 to 10. M e a n residence time and liq-
uid hold-up are correspondingly decreased by about
zone n e a r e r the c o u n t e r e l e c t r o d e and raise the c u r r e n t
concentrations wh ic h can be used in the reactor. A n a l -
14% due to the fiow of gas. Though more data is
ogous calculations for an i n e r t gas show a decrease needed to decide the point, this result, together with
in the limiting superficial c u r r e n t density but an in- rough measurements of liquid hold-up, indicates that
crease in c u r r e n t concentration as a result of increased Eq. I-A-5] underestimates the hold-up in beds of small
gas load. This is because the effect of gas load on the (< 1 m m ) irregularly shaped particles.
gas to liquid mass transfer (KL) is of no consequence Reduction of oxygen.--The r e d u c t i o n of o x y g e n in
in a process i n v o l v i n g only transfer f r o m liquid to trickle bed electrodes was i n v e s t i g a t e d in connection
solid, wh i l e the calculated increase in the liquid to w i t h w o r k on the g e n e r a t i o n of alkaline solutions of
solid t r a n s f e r coefficient (Ks) does not balance the h y d r o g e n p e r o x i d e (17). These studies w e r e carried
drop in el ect r o act iv e bed thickness. out using the r eact o r configuration of Fig. 1B w i t h a
In general, the effect of gas to liquid flow ratio on cathode bed of porous g r a p h i t e particles and a s y n -
c u r r e n t efficiency and cell voltage depends upon the thetic fabric d i a p h r a g m compressed b e t w e e n s t a i n l e s s
controlling step in the electrode process. U n d e r p u r e
kinetic control one w o u l d e x p e c t an increase in the
gas load to h a v e no effect on or to decrease the c u r r e n t i i i
efficiency wh i l e increasing the cell resistance due to
t he need fo r h i g h e r overpotentials in a n a r r o w e r elec-
t ro act i v e region of the fixed bed. F o r p u r e mass trans-
fe r control an increase in gas load will l o w e r the con- 4
centration o v e r p o t e n t i a l as w e l l as decrease the elec- T
i:
t ro act i v e bed thickness. The r e l a t i v e m a g n i t u d e s of
these effects depend on other factors, such as the p a r -
ticle size, bed porosity, liquid load, liquid conductivity,
bed conductivity, and w h e t h e r the gas is a r e a c t a n t in
m 3
~ Q

the process, but the net effect can be an increase in

c u r r e n t efficiency and a decrease in cell resistance. "' 2
hr.
A secondary effect of decreased h o l d - u p is a r e d u c -
tion of the influence of homogeneous chemical r e a c -
tions on the process efficiency.
T h e practical range of pressure drop in a trickle b e d o. I
electrode is about 0.1 to 5 bar per m e t e r of bed length.
This can introduce mechanical problems in r e a c to r con-
struction and operation. Such problems are p a r t i c u l a r l y
t r o u b l e s o m e in d i v i d e d cells w h e r e it is necessary to 0 I i i
0 0.1 0.2 0.3 0.4
support the m e m b r a n e or balance the pressure in the
two chambers and h e r e the best solution seems to b e GAS LOAD kgr~ 2 s-I
a c o m p l i m e n t a r y fixed bed in the c o u n t e r e l e c t r o d e Fig. 2. Pressure drop in trickle bed electrode. Conditions: Dia-
chamber. phragm cell (Fig. 1B). Bed dimension, 0.5 X 0.05 X 0.003m.
Experimental Results Graphite particles --0.49 -I-0.20 mm. Temperature, 23~ Outlet
Th e following is a s u m m a r y of results of some e x - pressure 1.1-1.4 bar. No current. Water load kg m - 2 sec -1. 9
p e r i m e n t s in our l a b o r a t o r y w i t h bench scale t r i ck l e 1.1, ~ - - 2 . 2 , I~--3.3.
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 VoL 126, No. 11 ELECTROCHEMICAL RF_~kCTOI%S 1887

m u m air loading h e r e corresponds to a superficial i n l e t

a i r velocity t h r o u g h the bed of 0.10 m sec -1 a n d a ratio
of v o l u m e t r i c gas to liquid flows of a b o u t 40. T h e r e s u l t
of o p e r a t i n g t h e cell w i t h o x y g e n gas at 15 b a r is
shown in Fig. 5. I n Fig. 5 the e x i t p e r o x i d e c o n c e n t r a -
tion corresponding to 1000 A / m 2 a t 79% c u r r e n t effi-
ciency is 0.52M, while t h e s a t u r a t i o n concentration of
o x y g e n in the e l e c t r o l y t e a t 15 b a r is a b o u t 0.01M.
The decrease in a p p l i e d v o l t a g e in the presence of
air or o x y g e n of up to 1.0V is that e x p e c t e d for c a t h -
odic d e p o l a r i z a t i o n b y o x y g e n u n d e r a l k a l i n e condi-
tions. O x y g e n p r e s s u r e is i m p o r t a n t h e r e b u t t h e r e is
also a clear effect of gas load, p a r t i c u l a r l y a t t h e h i g h e r
c u r r e n t densities w h e r e t h e r a t e of o x y g e n r e d u c t i o n
is l a r g e l y d e t e r m i n e d b y t h e r a t e of o x y g e n t r a n s f e r
to the e l e c t r o d e surface. The decreased voltage w i t h
h i g h e r gas flow is p r o b a b l y due to the corresponding
increase in the r a t e of o x y g e n t r a n s f e r to the electrode.
PULSE INPUTi C o m p a r e d to this the l o w e r effective conductivity of
i the electrolyte due to d e c r e a s e d l i q u i d h o l d - u p is of
0 2 4 6 8 16 s e c o n d a r y importance.
TIME MINS
I n Fig. 5 the mass t r a n s f e r l i m i t e d superficial c u r -
r e n t d e n s i t y for o x y g e n r e d u c t i o n at the l o w e r gas
Fig. 3. Liquid dispersion in trickle bed electrode. Conditions: flow (0.06 kg m -~ sec -1) is p r e d i c t e d as about 700
Diaphragm cell (Fig. 1B). Bed dimension, 0.5 X 0.05 X 0.003m. A m -~ b y the m e t h o d given in the A p p e n d i x . I n this
Graphite particles --0.99 +0.30ram. Temperature, 20~C. Pressure, case the h i g h e r efficiency for p e r o x i d e w i t h i n c r e a s e d
in 2.3-3.3 bar, out 1.1 bar. No current. gas load is a reflection of i m p r o v e d o x y g e n transfer.
1 2 3
Reduction o] sulfur dioxide.~The cathodic r e d u c -
Water load kg m - ~ ser - 1 2.2" 2.2 = 2.2 tion of sulfur dioxide in w a t e r was c a r r i e d out in a
Air load kg m - ~ sec - 1 0.0 0.014 0.14 t r i c k l e bed reactor w i t h the object of p r o d u c i n g so-
d i u m dithionite. The r e a c t o r configuration was that of
steel plates. O x y g e n o r a i r a n d a 2M solution of sodium Fig. 1A, in which a cation specific m e m b r a n e s e p a r a t e d
h y d r o x i d e at 20~ w e r e m i x e d in a tee a n d flowed a cathode bed of t u n g s t e n c a r b i d e particles f r o m t h e
c o - c u r r e n t l y t h r o u g h the bed at pressures up to 20 bar. anode chamber.
This was e s s e n t i a l l y an u n d i v i d e d cell in which o x y - A n IM solution of sodium h y d r o x i d e was r e c y c l e d
gen d e p o l a r i z e d the cathode to f o r m p e r o x i d e or h y - t h r o u g h the anode c h a m b e r w h i l e w a t e r and a m i x t u r e
d r o x i d e while o x y g e n was g e n e r a t e d f r o m h y d r o x i d e of n i t r o g e n and sulfur d i o x i d e w e r e passed t h r o u g h
at the anode, to give the n e t cell r e a c t i o n the cathode, the gas a n d liquid being m i x e d at a tee
before e n t e r i n g the reactor.
4e- W i t h the passage of c u r r e n t the d e s i r e d n e t reaction
O2 + 2 O H - > 2HO2- [1] is
F i g u r e 4 shows h o w the i n t r o d u c t i o n of a i r to the 2e-
cathode bed drops the a p p l i e d cell voltage. The m a x i - 2SO2 + 2NaOH > Na2S204 + 89O2 + H20 [2]

' ' ]
I00

/
- /L / 80
hi
(.9
/ /
w
-- ~ O~
0
I---
60 o
>
..J w
,,m 0
l.u >
h
_I LI.
O. (3
o.. uJ I 4O
/
0.
o_ ul
a:

20 u

0 I I I I 0 I r I I 0
0 200 400 600 800 I (300 0 200 400 600 800 1000
SUPERFICIAL CURRENT DENSITY A m- 2 SUPERFiCiAL CURRENT DENSITY Am .?.

Fig 4. Effect of air load on cell voltage in a trickle bed cathode. Fig. 5. Effect of oxygen load on cell voltage and current effici-
Conditions: Diaphragm cell (Fig. 1B). Cathode dimensions 0.78 X ency for peroxide generation in a trickle bed cathode. Conditions:
0.0S X 0.003m. Graphite particles --0.99 +0.30 ram. Electrolyte Diaphragm cell (Fig. 1B). Bed dimensions, 0.78 • 0.05 X 0.003m.
2M NaOH at 2.6 kg m-2 sec-1. Temperature 20~176 Exit pres- Graphite particles --0.99 + 0.30 mm. Electrolyte 2M NaOH at 2.1
sure 1 bar, Air load, kg m - 2 sec -1. A--0.0, O--0.13, I--I--0.63. kg m - ~ sec -1. Temperature 20~176 Pressure, in 15.5-16.7 bar,
Inlet pressure, bar 2 3 4 out 14.6 bar. Oxygen load kg m - 2 sec -1. A A - - 0 . 0 6 , O O--O.24.
Stoichiometric air at 1000 Am - 2 - - 0.17 kg m - 2 sec -1. Stoichiometric oxygen at 1000 Am - 2 - - 0.034 kg m - ~ sec-%
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 1888 J. EIectrochem. Sac.: 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 November 19~9
The cation m e m b r a n e was used here to p r e v e n t 50% SO2 i n the gas. A similar result is seen with 5%
oxidation of dithionite on the anode a n d / o r its reac- SO2 i n the gas b u t here there is a peak i n the c u r r e n t
tion with oxygen generated at the anode. efficiency curve which corresponds to the stoichiometric
The purpose of c o - c u r r e n t n i t r o g e n and sulfur di- equivalence b e t w e e n the SO2 feed a n d the applied cur-
oxide flow was to provide a source of reactant sulfur di- rent. At superficial c u r r e n t densities below about 200
oxide while limiting its concentration i n the liquid A m -~ the low c u r r e n t efficiency is p r o b a b l y due to an
phase to suppress the homogeneous decomposition of u n f a v o r a b l e balance b e t w e e n c u r r e n t concentration a n d
dithionite. the rate of dithionite decomposition.
Resutts of experiments w i t h feed gas c o n c e n t r a - The m e a s u r e d cell voltages reflect the effect of SO2
tions of 5, 20, a n d 50 v o l u m e p e r c e n t ( v / o ) sulfur di- concentration on electrode potential a n d electrolyte
oxide (corresponding respectively to e q u i l i b r i u m liquid conductivity.
phase SO2 contents of 0.16, 0.53, a n d 1.30M) are shown Eiectrowinning of copper.--The recovery of c o p p e r
i n Fig. 6. I n these experiments the ratio of gas to cath-
from an acid solution of cupric sulfate was carried out
olyte flow b y volume e n t e r i n g the reactor was about i n a reactor constructed as i n Fig. lB. This reactor u s e d
20.
a lead anode, graphite cathode bed, stainless s t e e l
The mass transfer limited superficial c u r r e n t density cathode feeder, and synthetic fabric diaphragm.
calculated for the case of 20% SO2 in the gas is about
Three runs were made to m e a s u r e the c u r r e n t effi-
3000 A m -2 a n d it is evident from the linear relation
ciency for copper deposition, (a) with electrolyte so-
b e t w e e n dithionite concentration a n d c u r r e n t density
l u t i o n alone passing d o w n w a r d t h r o u g h the reactor,
i n Fig. 6 that the rate of dithionite production is not
(b) with c o - c u r r e n t d o w n w a r d flow of n i t r o g e n gas
controlled by mass transfer. Under the p r e v a i l i n g
a n d electrolyte, and (c) with c o - c u r r e n t d o w n w a r d
catholyte pH of b e t w e e n about 1 and 3 homogeneous
flow of air a n d electrolyte. The results are g i v e n in
decomposition of dithionite is very fast and dithionite Table II.
yield is d e t e r m i n e d by the relative rates of its f o r m a -
The n u m b e r s i n T a b l e II show the c u r r e n t efficiency
tion, electroreduction, and homogeneous decomposition
for copper deposition rising w i t h increasing superficial
(18). The increased rate of dithionite formation antici-
c u r r e n t density. This has been previously observed for
pated from raising the SO2 concentration is a p p a r e n t l y
copper w i n n i n g i n p a r t i c u l a t e electrodes (20) and is
countered by a corresponding increase i n the rate of
due to the electrode potential g r a d i e n t i n the bed
homogeneous decomposition. As a result the c u r r e n t
which leaves copper more v u l n e r a b l e to attack b y oxy-
efficiency for dithionlte is higher for 20% t h a n f o r
gen at the lower c u r r e n t densities.
I n case (a) the transfer limiting superficial c u r r e n t
Ol.01 I [
/o/ I t/'r
"-,
density is calculated at about 2800 A m-~, c o r r e s p o n d -
i n g to a m a x i m u m electroactive bed thickness of 0.3
m m at ~V = 0.hV. Since the m a x i m u m c u r r e n t d e n -
sity from Table I is 500 A m -2 it is u n l i k e l y that m a s s
8 transfer was a controlling factor i n this situation. T h e
positive effect of c o - c u r r e n t n i t r o g e n flow on the cur-
W
F- r e n t efficiency was p r o b a b l y the result of p u r g i n g oxy-
~.6
0 gen (produced at the anode) from the bed. This effect
"r" was p a r t i c u l a r l y noticeable at low superficial c u r r e n t
density. At the highest c u r r e n t the oxygen content of

/,
Q .4
the gas leaving the reactor was about (a) 100%, (b)
i.-
ro
/r" 10% and (c) 30%, that is, increasing O2 content cor-
responded to decreasing c u r r e n t efficiency for copper
0n.,. .2 deposition. Oxygen dissolved in the electrolyte e n t e r -
ing the reactor was negligible h e r e , being e q u i v a l e n t
to less t h a n 2% of the m i n i m u m current.
0 I J I I I The gas to liquid volumetric ratio i n runs (b) a n d
(c) was close to 10 a n d the calculated h o l d - u p about
0.5. This resulted in a small increase in cell resistance
b u t the negative effect of gas flow on power efficiency
80 was mostly balanced b y increased c u r r e n t efficiency.
I 9 f' _ >- S u b s e q u e n t e x a m i n a t i o n of the cathode bed showed
t)
Z copper deposition up to about 2 m m into t h e b e d
60 ~ from the p l a n e of contact w i t h the diaphragn~
_o
U-
U-
> \ /
Table II. Effect of ca-current gas flow in copper electrawinning
40 ~

/!i _o,/" o.,I {2." Conditions

20 ~
Cathode bed d i m e n s i o n 0.4m x 0.05m x 3 m m
Graphite particle size --0.99 + 0.3 m m
Electrolyte feed 9.03 1 m i n -1 of 0.1m CuSO, in H~SO4 (3.3
Ol,, I I I J I 0 kg m --~ sec -1)
0 400 800 1200 PH = 1.0
SUPERFICIAL CURRENT DENSITY A m-2 Gas flow 0.3 1 min-z STP (0.043 k g m-~ sec-~). In.
let p r e s s u r e 0.2 b a r
Fig. 6. Effect of sulfur dioxide load on cell voltage and current
Current A
efficiency for dithionite generation in trickle-bed cathode. Condi-
tions: Cation membrane cell (Fig. 1A). Bed dimension 0.5 • 0.05 T e m p e r a t u r e , 22~ 2 4 6 8 10
• 0.003m. Tungsten carbide particles --0.43 + 0 . 3 0 mm. Catho-
lyte, water at 3.6 kg m - 2 sec -1. Temperature, 10~ Pressure, E l e c t r o l y t e alone 35"1.80 49"1.95 66*2.05 73"2.15 77*2.25
in 1.5 bar, out 1.0 bar. Gas load kg m - 2 sec -1. A A - - N 2 = E l e c t r o l y t e + N~ 66"1.85 72'1.95 76*2.05 81"2.20 87*2.35
0.130, SO2 = 0.016, Q e - - N 2 = 0.110, SO2 = 0.063, V T - - E l e c t r o l y t e + air 9'1.90 50"2.00 66"2.10 75*2.30 81"2.35
N2 = 0.069, SO2 = 0.158. Stoichiometric S02 at 1000 A m - 2 =
0.048 kg m - 2 sec -1. * F i g u r e s indicate, c u r r e n t eIBciency (%) * r e a c t o r voltage.

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 VoL 126, No. 11 ELECTROCHEMICAL REACTORS 1889

Scale-Up
Commercial operations with a trickle bed electro-
chemical reactor would r e q u i r e electrodes of the o r d e r
of one square m e t e r i n area i n stacks c o n t a i n i n g u p
to about 100 i n d i v i d u a l cells. Scale-up to a reactor o f
this size presents several problems.
A p a r t from the usual aimcu• of selecting satis-
factory electrode a n d d i a p h r a g m materials there is
the p r o b l e m of constructing such a reactor to ac-
c o m m o d a m pressure drops up to 5 bar a n d possibly (as
i n the case of o x y g e n reduction) to operate with i n -
t e r n a l pressures up to 20 bar. A n o t h e r difficulty lies
i n feeding reactants to the electrodes a n d m a i n t a i n i n g
a u n i f o r m gas and liquid d i s t r i b u t i o n both w i t h i n a n d
b e t w e e n the cells. Combined with this is the p r o b l e m
of controlling the c u r r e n t d i s t r i b u t i o n i n the three-
dimensional, plug-flow electrodes. Joule heating of
the reactor m a y compound these difficulties a n d the
possible p l u g g i n g of the fixed bed electrode i n ex-
tended operation would be fatal to its practical ap-
plication.
Some of these problems h a v e b e e n examined, i n a
p r e l i m i n a r y way, in our l a b o r a t o r y b y the operation
of a small bipolar cell stack a n d a large single trickle
b e d electrode ~or the r e d u c t i o n of oxygen to peroxide
i n sodium hydroxide solutions.
The bipolar cell stack contained five parallel trickle
bed electrodes, each the same size as that described
i n Fig. 5. This reactor (19) was constructed with 3 m m
thick beds of graphite particle contained i n gaskets
s a n d w i c h e d b e t w e e n 6 parallel stainless steel electrode
plates, with porous diaphragms as i n Fig. lB. Manifolds
for r e a c t a n t feed and product r e m o v a l from the stack
were formed by 10 m m diam holes which were p u n c h e d Fig. 7. Bipolar cell stack with trickle bed electrodes
into both ends of each electrode plate a n d covered with
plastic screen to p r e v e n t contact of the graphite p a r - .8 I l I J
ticles i n adjacent cells. The whole stack was com-
pressed b e t w e e n bolted steel channels a n d the pro-
t r u d i n g lugs of the outside electrodes connected to
the d-c source. Liquid a n d gas were delivered to the
stack t h r o u g h couplings w e m e d into the outside elec- =E.6
trodes. A d i a g r a m of this reactor is shown i n Fig. 7 a n d 6
z
the conditions of a typical r u n are given in Table II. o
Table II shows results similar to those expected from / ~ f REACTOR
/ / y OUTLET _
a single ce• unae~" e q u i v a m n t conditions and the volt- W .4
age drop across each cell indicates a r e l a t i v e l y u n i -
form d i s t r i b u t i o n os liquid a n d gas b e t w e e n the cells. 0e~
The s t u d y of larger electrodes was carried out i n
a reactor 2m high, able to hold cathode beds up to 0.
0.25m wide a n d capable of operation at i n t e r n a l pres- .2
sures up to 20 bar. The v a r i a t i o n of peroxide concen-
t r a t i o n with reactor l e n g t h was observed i n this a p -
p a r a t u s using two cells, one 0.05m wide, the other
0.25m wide w i t h sample points n e a r the cell centerlines
0 I 2
at 0.5m intervals. Typical results are i n Fig. 8.
Values of peroxide c o n c e n t r a t i o n predicted from a REACTOR LENGTH m
theoretical model of the process, using rate constants Fig. 8. Operation of scaled-up trickle bed electrodes. Conditions:
d e r i v e d from e x p e r i m e n t s o n a n 0.5m Iong reactor Diaphragm cell (Fig. |B). Graphite particle size, --0.99 +0.30ram.
with the assumptions of u n i f o r m superficial c u r r e n t Electrolyte, 2M NoaH at 2.2 kg m - 2 sec - I . Temperature, 20 ~
d e n s i t y a n d plug flow of the electrolyte, are also dis- 30~ Pressure, in 10 bar, out 7.6 bar. Oxygen load 0.12 kg m - 2
played i n Fig. 8. Details of the model are i n the A p - sec -1. Superficial current density, 500 Am -2. Reactor dimension
pendix. 9 • 0.05 X 0.003m, A - - 2 • 0.25 • 0.003m. - - - Pre-
The data for the 0.05m wide cell fall below the p r e - dicted value.
dicted line, but the diilerence m a y be accounted for
b y the dispersion described i n Fig. 3. For the 0.25m
wide bed the results i m p l y that a disproportionatel7
large fraction of the electrolyte flowed n e a r the e d g e s
Table III. Operation of bipolar cell stack of the bed. This p h e n o m e n o n caused the i n f e r i o r p e r -
formance of the wide bed a n d presents a n obstacle t o
Electrolyte 2M NaOH at 55 x 10-em~ min-z the successful scale up of trickle bed electrodes.
Gas Oxygenat 2.5 • 10-3 ma rain-z STP
Pressure Inlet 11 bar, outlet 7 bar Conclusions
Temperature Inlet 20~ outlet 46~ Fixed bed, plug-flow electrochemical reactors can
Current 30A (770 A m-~) be operated as trickle beds with c o - c u r r e n t gas loads
Product peroxide conc. 0,68M into the gas continuous regime.
Current efficiency 78% C o - c u r r e n t gas flow results i n a n increase i n p r e s -
Voltage Cell 1 2 3 4 5 sure drop, a decrease i n liquid hold-up, a n d a d e c r e a s e
1.61 1.59 1.52
1.57 1.64
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 1890 J. EZectrochem. 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 N o v e m b e r 1979

i n liquid dispersion while it enhances mass transfer / ad' ~0.6~

i n the reactor a n d raises the c u r r e n t concentration p = 3.86ReLO.~-SGa*L-O.'=~---~-
b ) [A-5]
i n the active zone of the electrode bed.
W~th sparingly soluble reactive gases, i n the regime where Ga*L is the modified Galileo n u m b e r
of mass t r a n s f e r control of the electrode reaction, cell
resistance can be decreased a n d c u r r e n t efficiency d'3pL(PLg Jr APLG)
Ga*L : [A-6]
raised with increasing gas to liquid volumetric ratios ~L ~
up to at least 50. Gas flow also m a i n t a i n s a supply of
reactant whose concentration i n the liquid can be ad- Mass transfer coe~cient.--The gas and liquid phase
capacity coemcients come from Reiss (24)
justed t h r o u g h the composition of the gas. I n t r o d u c t i o n
of a c o - c u r r e n t flow of i n e r t gas to a fixed bed elec- KLa = 0.0173 (APLGUL) 0.5 [A-7]
trochemical reactor causes a n increase i n cell resist-
ance which m a y not be compensated b y increased cur- KGa -- 2.0 Jr 0.69 (APLGUG)0.67 [A-3]
r e n t efficiency unless the i n e r t gas performs another while the liquid to solid t r a n s f e r coefficient i n a
f u n c t i o n such as p u r g i n g oxygen from the reactor. trickle bed is obtained Zrom the correlation of Sato
Trickle bed electrodes have b e e n operated on the e~ a~. (10)
b e n c h scale at pressures uP to 20 b a r a n d allow s u p e r - 0.429
Ksa = Re~o-sScLO.~3aSD~, [A-9]
ficial c u r r e n t densities of the order of 1 k A m -~, at P
useful c u r r e n t efficiency, i n electrochemical reactions
involving gaseous reactants such as oxygen a n d sul- The o v e r - a l l capacity coefficient for mass t r a n s f e r is
f u r dioxide. A c u r r e n t concentration of 200 k A m -3 calculated from
was achieved for the electroreduction of oxygen to
Koa =
( i
+
i
+
I )-I
[A-IO]
peroxide i n a bipolar stack of trickle bed cells.
P r e l i m i n a r y tests with a large trickle bed electrode
indicate n o n u n i f o r m d i s t r i b u t i o n of liquid across the on the assumption that the specific gas/liquid and
bed, with a consequent loss of electrochemical effective- liquid/solid interracial areas are equal to the specific
surface area of solid particles i n the bed.
ness. I n the absence of gas flow the liquid to solid t r a n s -
Acknowledgment fer coefficient m a y be estimated from the correlation
This work was supported b y grants from the Na- of Wilson and Geankopolis (25).
L,b
tional Research Council of Canada. Most of the experi- Ks = 1,09 Re-0.67Sc-0.6~ [A-11]
m e n t a l work was carried out b y Ms. Riva K a p l a n PL
(n6 Gillilova).
Electrode e~ectiveness.--For p u r e mass t r a n s f e r con-
M a n u s c r i p t submitted J u l y 31, 1978; revised m a n u - trol of the reaction rate i n a t h r e e - d i m e n s i o n a l elec-
script received A p r i l 9, 1979. This was P a p e r 469 p r e - trode in which ~b > > KL the m a x i m u m eIectroactive
sented at the Seattle, Washington, Meeting of the So- bed thickness for a given difference i n electrode
ciety, May 21-26, 1978. potential across the bed AV, can be calculated as (13)
A n y discussion of this paper will appear i n a Dis- ( 2~'AV ) ~
cussion Section to be published i n the J u n e 1980 ta = il*a [A-12]
JOtmNAL. All discussions for the J u n e 1980 Discussion
Section should be submitted by Feb. 1, 1980.
where K', the effective electrolyte conductivity, is
Publication costs of this article were assisted by the estimated by the relation of Neale and Nader (16)
Nationat Research Council o] Canada.
2 ~Lg
~' = - - [A-131
APPENDIX 3 we ~
in which
Prediction of Active-Bed Thickness and Superficial Current 9' -- ebb [A-14]
Density in Trickle-Bed Electrodes Under Mass Transfer Control and
For a n electrochemical process governed by m a s s il*a : n F K o a C [A-15]
transfer i n a trickle bed electrode the electroactive
bed thickness a n d m a x i m u m superficial c u r r e n t density The mass transfer limited superficial c u r r e n t density
can be estimated from the following relations found is t h e n obtained from
in the l i t e r a t u r e on tnermochemical trickle Ded reac- ii = taiffa [A-16]
tors:
Finally, the c u r r e n t concentration i n the active elec-
Pressure d r o p . ~ S i n g l e phase pressure drops are ob- trode is given b y
t a i n e a J~rom the E r g u n e q u a t i o n (21) i,
(150 Jr 1.70ReL)#LUL(I -- L%)2 j -- i**a - - [A-17]
APE : [A-l] t.
d'Seb3
The above relations are approximate, i n that t h e
(150 + 1.75 ReG)~GU6(1 -- ~b)2 h o l d - u p a n d mass transfer correlations were developed
APG = [A-2] from data on cylindrical beds with particle diameters
d'2eb~ greater t h a n 1 mm. E v e n for the larger particle
diameters there is u n c e r t a i n t y about the validity of
d the correlations i n the various flow regimes of a
d' = [A-3] trickle bed. However, the equations do give a q u a n -
(t + w ) d titative guide to the effects of liquid flow, gas flow,
1+
3tw (1 -- ,) and particle size in operation of a trickle bed electrode.
Where d' is the (spherical) particle diameter modified Model of Peroxide Generation in Trickle Bed Electrochemical
to account for the high ratio of particle size to bed Reactor
thickness i n a bed of r e c t a n g u l a r cross-section (22, Peroxide is generated b y electroreduction of oxygen
23). The two phase pressure loss is calculated from i n aqueous sodium hydroxide solution i n a trickle
the correlation of Sato et al. (22) bed reactor of the type shown i n Fig. lB. The net
(APL '~-0.4251s rate of p e r h y d r o x y l a c c u m u l a t i o n in a differential
APLG -- APL [1.30 Jr 1.85 "~G'G / J [A-4] length i n c r e m e n t of the reactor is d e t e r m i n e d b y
competition b e t w e e n three separate reactions.
On the cathode,
Liquid hold-up.~Hold-up is d e t e r m i n e d from the r
correlation of Specchia a n d Baldi (15) O~ + H s O + 2e ~ c O H - + HO~ [A-e]
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 V o l I ~ , No. 11 ELECTROCHEMICAL REACTORS 1891

r LIST O F S Y M B O L S
HO2- + H20 + 2e --> d 3 O H - [A-d] A superficialelectrode area, m 2
{Z specific surface of bed, m -1
a n d o n the anode C b u l k r e a c t a n t concentration, kg mole m - s
r D diffusivity, m 2 s e c - 1
HOz- + O H - ~ e O= + H~O + 2e [A-el d particle diameter, m
W~th the simplifying assumptions of a u n i f o r m po- d' efl'ective particle diameter, m
t e n t i a l d i s t r i b u t i o n i n the cathode bed a n d pure F Faraday's number, C equiv -I
kinetic control of the (first order) cathode reactions g gravitational constant, m sec -2
G gas load, kg m - " sec -1
Ga* modified Galileo n u m b e r , --
re-- kcS HP exp ( , -~RT ) [A-18] H H e n r y ' s constant, kg mole k g - 1 m - 2 sec+2
h d i a p h r a g m thickness, m
and [HO~-] p e r h y d r o x y l ion concentration, kg mole m - s
superficial c u r r e n t density, A m -~
ra = kaS[H02-] exp RT [A-19] i, mass transfer limited superficial c u r r e n t d e n s -
ity, A m - ~
The rate of destruction of p e r h y d r o x y l at the anode real c u r r e n t density, A m -2
is t a k e n as its rate of transport, b y diffusion a n d mass transfer limited real c u r r e n t density,
migration, t h r o u g h the diaphragm. By adopting the A m -~
a p p r o x i m a t i o n D o l l - --~ 2D~o2- the t r a n s p o r t rate J c u r r e n t concentration, A m - a
can be deduced as K mass transfer coefficient, m sec-~

re = DHO2-[HO2-] \ h + 2F[Na+]DoH -
) k
kl
L
electrochemical reaction rate constant, m sec-1
ratio of electrochemical rate constants, --
liquid load, kg m -2 sec-~
[A-20] 9% n u m b e r of electrons, --
[Na + ] sodium ion concentration, kg mole m - s
Further, i n the absence of h y d r o g e n g e n e r a t i o n [ O H - ] h y d r o x y l ion concentration, kg mole m -3
(confirmed b y gas analyses) the superficial c u r r e n t P pressure, kg m -1 sec -2
density is given by aP pressure drop per u n i t length, kg m -2 sec -2
Q liquid flow, m 3 sec-1
R u n i v e r s a l gas constant, j ~ -1 m o l e - 1
2--f = exp k + k SEHO -]e p r electrochemical reaction rate, kg mole m -~
see-1
[A-211 Re Reynold's n u m b e r for particle 9= d'pU/~
A s s u m i n g c~l = oc2 -- r S real electrode surface area per u n i t of super-
ficial electrode area, m 2 m -2
Sc Schmidt n u m b e r = ~/pD
exp ~ -- 2 F S ( k l H P + k2[HO2-]) T temperature, ~
[A-22] ta electroactive bed thickness i n the direction
of current, m
a n d the n e t rate of peroxide a c c u m u l a t i o n i n a dif- t bed thickness, m
ferential l e n g t h e l e m e n t of the reactor is U fluid velocity, m sec -1
V electrode potential, V
r = rc -- (rd + re) [A-23] ~V difference in electrode potential across a
t h r e e - d i m e n s i o n a l electrode, V
--" ( r c -~- r d ) - - (2ra -t- re) [A-24] w bed width, m
[ kli cr electrochemical charge t r a n s f e r coefficient, --
=-- [HO2-] liquid hold-up, --
2F F (HP + k 1[HO2- ] ) ~b bed porosity
ed diaphragm porosity

+ DHo2- \ h -~ 2F[Na+]DoH -
)] ,'
Kb
~L
effective bed porosity
bed conductivity, mho m -
liquid conductivity, mho m -1
k2 2ed ~' effective liquid conductivity, mho m -1
where kI-~ and ,'d = - - (16) [A-26] viscosity, kg m -1 sec -1
kl 3 -- ,d p density, kg m -~
A mass balance for peroxide over the differential Subscript8
i n c r e m e n t of reactor length gives G gas phase
rdA
Q d [ H G , - ] ----- [A-27] L liquid phase
O over-all
A t 20~ H = 0.7 • 10-8 m o l e / l i t e r atm and if P _~ 10 S solid phase
atm, [HO~-] < 1M, k~ ~ 10 - s
REFERENCES
H P + k~[HO~ - ] _~ H P 1. N. Ibl, Chem. Ind. London, 326-328, April 19, 1975.
2. V. A. Ettel, A. S. Gendron, and B. C. Tilak, P a p e r
T h e n for a constant oxygen pressure and no peroxide presented at the 102nd A n n u a l Meeting of AIME,
i n the feed Eq. [A-271 can be i n t e g r a t e d along the Chicago, lllinois, Feb. 1973.
reactor to o b t a i n 3. D. Jennings, A. T. Kuhn, J. B. Stepanek, and R.
[HO2-]z--~ l--exp -- b [A-28] Whitehead, Electrochim. Acta., 20, 903 (1975).
4. T. Berent, R. Mason, and L Fells, J. Appl. Chem.
where Biotechnol., 21, 71 (1971).
k~i 5. N. R. Barucha and P. L. Claessens, C a n a d i a n P a t -
ent 1001986 (1973).
b=D~o~-\ h + 2F[Na+]DoH - + FH-----~ 6. C. Oloman and A. P. Watkinson, Can. J. Chem.
[A-29] Eng., 53, 268 (1975).
7. G. H. Sedahmed and L. W. Shemilt, P a p e r 254
The value of k 1 is obtained b y fitting Eq. [A-28] presented at the Electrochemical Society Meet-
for a specific set of operating conditions. ing, Washington, D.C., May 2-7, 1976.
U n d e r the constraints specified above a n d with a 8. C. O l o m a n and A. P. Watkinson, Can. J. Chem.
fixed liquid and gas load, Eq. [A-28] predicts p e r f o r m - Eng., 54, 312 (1976).
ance of the peroxide reactor to w i t h i n about _+20% 9. G. H. Sedahmed, J. Appl. Electrochem., 8, 399
for superficial c u r r e n t densities up to about 800 A m-~. (1978).
However, the assumptions made in its derivation 10. C. N. Satterfield, AIChE J., 21, 209 (1975).
m a k e this type of model of limited value i n the gen- 11. J. C. Charpentier, Chem. Eng. J., 11, 161 (1976).
eral analysis of trickle bed electrochemical reactors. 12. C. N. Satterfield, M. W. Van Elk, and G. S. Bliss,
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 1892 Y. E[ectrochem. 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 November I979

AIChE J., 24, 709 (1978). 19. C. Oloman and A. P. Watkinson, U.S. P a t e n t 4,118,-
13. R. D. Armstrong, O. R. Brown, R. D. Giles, and 305 (1978).
J. A. Harrison, Nature (London), 219, 94 (1968). 20. S. G e r m a i n and F. Goodridge, Electrochim. Acta.,
14. O. Levenspiel, "Chemical Reaction Engineering," 21, 545 (1976).
J o h n Wiley, New Y o r k (1962). 21. S. Ergun, Chem. Eng. Prog., 48, 89 (1952).
15. V. Specchia and G. Baldi, Chem. Eng. Sci., 32, 22. Y. Sato, T. Hirose, F. Takahashi, a n d M. Toda, J.
515 (1977). Chem. Eng. Jpn., 6, 147 (1973).
16. G. H. Neale a n d W. K. Nader, AIChE J., 19, 112 23. M. L. Batia, M.A.Sc. Thesis, U n i v e r s i t y of British
(1973). Columbia (1976).
24. L. P. Reiss, Ind. Eng. Chem. Process Des. Dev., 6,
17. C. O l o m a n a n d A. P. Watkinson, J. Appl. Electro- 486 (1967).
chem., 9, 117 (1979). 25. E. J. Wilson and C. J. Geankopolis, Ind. Eng. Chem.
18. C. Oloman, This Journal, 117, 1604 (1970). Fundam., 5, 9 (1966).

Semiconductor Electrodes
XXI. The Characterization and Behavior of n-Type Fe203 Electrodes in
Acetonitrile Solutions
Ronald A. Fredlein *.I and Allen J. Bard*
Department o~ Chemistry, The University o:f Texas at Austin, Austin, Texas 78712

ABSTRACT
T h e electrochemical b e h a v i o r of P b - d o p e d single crystal, T i - d o p e d p o l y -
c r y s t a l l i n e compacts, and chemical v a p o r deposited films of Fe2Os was i n -
v e s t i g a t e d in acetonitrile solutions. Details of the surface electronic b a n d
s t r u c t u r e w e r e o b t a i n e d f r o m capacitance a n d p h o t o - e x c i t a t i o n techniques
a n d by c o m p a r i n g the cyclic v o l t a m m o g r a m s of various electroactive species
of k n o w n s t a n d a r d potential to the N e r n s t i a n response at a P t disk electrode.
T h e r e is evidence t h a t surface electronic states capable of m e d i a t i n g e l e c t r o n
t r a n s f e r exist at ~0.9 eV and ,-.1.8 eV negative of conduction bandedge.
Results a r e i n t e r p r e t e d in' terms of a n a r r o w conduction b a n d of w i d t h d e -
p e n d e n t on the d o p a n t level.

Recent i n t e r e s t in the semiconductor e l e c t r o c h e m - Experimental

i s t r y of Fe20~ stems from the small b a n d g a p (2.2 eV),
S i n t e r e d p o l y c r y s t a l l i n e compacts of ~-Fe20s w e r e
n - t y p e conduction, and s t a b i l i t y in aqueous a l k a l i t h a t
p r e p a r e d doped w i t h t i t a n i u m in the range 0.05-1.0
Fe.~O3 possesses. This m a k e s it an a p p a r e n t a t t r a c t i v e
atomic p e r c e n t ( a / o ) Ti. Fe2Os ( F i s h e r Certified)
possible s u b s t r a t e for the photo-assisted decomposition
was s t i r r e d o v e r n i g h t w i t h TiO2 (MBC r e a g e n t g r a d e )
of w a t e r (1-5) but q u a n t u m effieiencies a r e low (2-4).
in acetone, the solvent e v a p o r a t e d and the p o w d e r
Less w o r k has been done on its f u n d a m e n t a l electro-
pressed into disks at 7000 psi before firing in air
c h e m i s t r y as dictated b y its electronic b a n d s t r u c t u r e
at ll00~ for 16 hr (3, 10). Single crystals of ~-Fe20~,
(6, 7). Intrinsic Fe2Os is an excitation semiconductor
grown from a PbO melt, were generously d o n a t e d b y
of high r e s i s t i v i t y (8) b u t w h e n s u b s t i t u t i o n a l l y doped
S a n d i a Laboratories. The black, lustrous crystals w e r e
b y d i v a l e n t ( p - t y p e ) or t e t r a v a l e n t ( n - t y p e ) cations,
h i g h l y conductive and on i l l u m i n a t i o n gave rise to
becomes conductive w i t h charge t r a n s f e r occurring
only negligibly small anodic p h o t o c u r r e n t s in 0.1M
by a t h e r m a l l y a c t i v a t e d hopping m e c h a n i s m (9-12).
aqueous acetate buffer ( p H 7.0) (1). However, h e a t -
F o r example, a Ti 4+ on a Fe S* site is a c c o m m o d a t e d
ing t h e crystals in a i r at 540~ for 120 h r resulted in
b y the presence of a Fe 2+ and conduction results from
g r e a t e n h a n c e m e n t of the photocurrents. T h e P b con-
electron hopping b e t w e e n a d j a c e n t Fe 2+ and Fe s+
tent of the crystals was e s t i m a t e d to be in the 1-10 a / o
ions. In this respect n - t y p e Fe203 does not possess the
r a n g e b y x - r a y fluorescence. The surfaces of the h e a t -
usual wide conduction band composed of a c o n t i n u u m
t r e a t e d and u n t r e a t e d crystals were e x a m i n e d b y
of delocalized electronic states. The electronic struc-
E S C A and A u g e r spectroscopy. Each c r y s t a l h a d one o r
t u r e of ~-Fe2Os has been r e v i e w e d (13-15).
two w e l l - d e v e l o p e d faces which were d e t e r m i n e d to
One of the m o r e successful techniques for p r o b i n g
be (012) ( h e x a g o n a l indices) and the p r e p a r e d elec-
the surface electronic structure of semiconductor elec-
trodes exposed this face. Films of Fe2Os on P t foil
trodes exploits the isoenergetic charge t r a n s f e r b e -
were p r e p a r e d b y chemical v a p o r deposition (CVD) as
t w e e n the semiconductor and d o n o r / a c c e p t o r states
p r e v i o u s l y described (1) and a n n e a l e d for a few m i n -
in solution (16-18). The solution electronic states a r e
utes in the oxidizing flame of a F i s h e r burner. A Cu
p r o v i d e d b y r e d o x couples of k n o w n s t a n d a r d p o t e n -
wire contact was m a d e to each electrode with conduc-
tial. Acetonitrile (ACN) is a p r e f e r r e d solvent for
tive silver acrylic cement (Allied P r o d u c t s C o r p o r a -
such studies because of its e x t e n d e d potential range of
tion) the contacted surface of the sintered compacts
s t a b i l i t y (,~SV) and o t h e r p r e v i o u s l y d o c u m e n t e d
and single crystals being first s m e a r e d w i t h I n / G a
reasons (18, 19). This p a p e r reports studies of single
alloy. The electrodes w e r e m o u n t e d in glass tubes w i t h
crystal and p o l y c r y s t a l l i n e compacts of a-Fe2Os and
silicone r u b b e r s e a l a n t (Dow Corning) and s t u d i e d
chemical v a p o r deposited (CVD) films of a p p r o x i m a t e w i t h o u t p r i o r etching.
composition a (70%), ~ (20%), a n d 7 (10%)-Fe2Os
(4). The p r e p a r a t i o n o r purification of the a n h y d r o u s
acetonitrile solvent, the t e t r a - n - b u t y l a m m o n i u m p e r -
" Electrochemical Society Active Member. c h l o r a t e ( T B A P ) e l e c t r o l y t e and the various e l e c t r o -
Permanent address: Chemistry Department, University of active reagents h a v e been p r e v i o u s l y d e s c r i b e d (18,
Newcastle, N.S.W. 2308 Australia.
Key words: semiconductor, capacitance, voltammetry. 20). F o r some reagents, controlled potential coulome-
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