DEGREE OF UTILIZATION AND SPECIFIC

EFFECTIVE SURFACE AREA OF ELECTROCATALYSTS

IN POROUS ELECTRODES

K. MLJND and F. v. STURM

Siemens AC, Research Laboratories, Frlangen, Federal Republic of Germany

(Receicrd 8th July 1974)

Abstract-In the development of electrodes, in addition to the space-time yield it IS often us&l
to determine and to establish the degree of utilization of the catalyst.
This is particularly important
in the case of an expensive or scarce material. To evaluate the catalyst, such terms as the “degree
of utilization y” (cd quotient with and without transport limitation) and the “specific ctkctivc
surface area J” (product of q and the specific surface area s of the catalyst) are introduced and
derived for blpor-ous electrodes. The given equations denote lhe influence of the pore dlmenxons
and the reaction parameters. The degree of utilkation can be further affected by the electrolytic
and electronic resmtance in porous electrodes.

INTRODUCTION at a given polarization q and from the specific surface

In heterogeneous catalysis the efficiency of a reactor area s (cm’/g) of the catalyst.
or its catalyst is commonly represented by its space
time yield Cl]. Correspondingly, electrochemical cells (1)
in which mass conversion occurs are characterized
by this expression. It is practical to state the convcr- The degree of utilization q is a quantity without
sion in ampere seconds dimension and can assume a value between c-1. For
a given reaction the degree of utilization y is a mea-
space time yield
sure of the accessible catalyst surface, eg, of the cata-
= conversion per unit volume and time
lyst in a porous electrode.
in heterogeneous catalysis in electrocatalysis
As the structure of the catalyst surface h&s not
cm”/Cm” s As/cm3 s
yet been elucidated, the term f (cm’/g) for specific
The reaction chamber can be related either to the effective surface area is introduced. It is given as a
volume of Ihe cell or to the volume of the working product of the degree of utilization q and the specific
electrode, according to which part is critically exam- surface arca s (cm’/g) of the catalyst:
ined, and should be compared with other reactors.
If the weight of the converter becomes critical, the
conversion can be expressed per unit weight instead
of per unit volume. Thus in electrosynthesisC21 or
(In supported catalysts, i,, and s only refer to the
in power generating cells[3 5,7] a general classifiica-
surface of the active part.)
tion of the cell or electrocatalyst can be made for
a given cell reaction. Types of porous electrodes
In addition it is often desirable to know the degree
Four types of porous electrodes which find appli-
of utilization of the catalyst substance employed in
cation in electrochemical cell design arc schematically
the type of electrode concerned, and still more desir-
represented in Fig. I. There are many attempts to
able to regulate it optimally. This is extremely impor-
comprehend the reaction path quantitatively in
tant if the substance in question is expensive or in
porous systems. Reference is made to some of the
short supply, particularly if economic considerations
work that has been carried out in this direction[4,5].
are involved.
The monoporous type in Fig. 1 corresponds to a
plate-shaped electrode with a roughened surface.
D$nition q/the “deyree of utilization” and the ‘*speciJic The current, its intensity and its distribution have
effectiw surface area”
been calculated considering the IR-drop in the elec-
The less the current is controlled by the transport trolytc of the pore, the Butler-Volmer relation for
of reactants to the catalyst surface and the removal the charge transfer reaction and the concentration
of the products, the better the surface of an electroca- distribution [4]_
talyst can be exploited. We will denote the degree Though a high degree of utilization q can be
of utilization q as a relation between transport-con- obtained, the f values are seldom satisfactory since
trolled cd i, (A/cm’) of a catalyst and the ideal cd the specific area s is too small in these types.
ii, (A/cm’); the latter is limited only by the electrode High s values combined with good accessibility of
reaction at a polarization q but not by transport. the catalyst surface are realized in biporous elec-
The crl i, can be estimated from the current I,, (A/g) trodes.
463
464 K. MUND AND P. v. SI.UKM

Monoporous Biporous

ith 3 phases with 2 phases with 3 mobile phases

? 9

Fig. 1. Types of porous electrodes in electrochemical cells. clcctrolytc tilled diaphragm. 12 electrolyte
filled porous catalyst.

For the conversion of gaseous reactants. electrodes A diminution of the reactant concentration In the
with two mutually interlinked porous systems have coarse pore system can be kept small by streaming
proved to be reliable in fuel cell tcchnology[5]. The a mixture of electrolyte and reactant. In the case
transport of reactants such as HZ, CH,, CIH, and of a dissolved reactant like methanol, the con-
0, takes place in larger gas-tilled pores. and the clec- centration of the reactant in the active pores can
trode reaction proceeds at the walls of the finer elec- be higher by several orders of magnitude. But in
trolyte-filled pores. comparison the exchange current density i0 can be
Technically used electrode types, as shown by the distinctly below that of the gas converting ones.
micrograph of a supported electrode with silver- In the case of non-mixability of the electrolyte and
tungsten carbide cdtalyst[6] in Fig. 2, arc very close reactant, the reactant can fill the coarse pore system
to this model. The silver-tungsten carbide catalyst as a third phase. This is conceivable for instance
is active for electrochemical hydrogen conversion in for the reaction of benzene in sulphuric acid.
fuel cells with an acid electrolyte. The small active If the fine porous system is connected to the elec-
tungsten carbide particles are bound by silver to trolyte chambers on both sides, it can be equally
larger grains. The gas penetrates into the pores Rushed to minimize the concentration gradient[Q.
between the catalyst particles and dissolves in the
electrolyte at the pore mouths of the grains. Then
the gas diffuses into the narrow pores and reacts In earlier work[9] the current yield of an electro-
at the pore walls. lyte filled single pore wus derived by considering both
For the conversion of reactants such as methanol the diffusion of the reactants through the electrolyte
and formiate dissolved in the electrolyte, the three- to the pore walls and the charge transfer reaction.
phase electrode can be easily moditied so that the Saturation concentration c,, of the reactant is main-
coarse pores are used for the transport of the dis- tained at the pore mouth even under charge. Calcula-
solved reactants, see Fig. 1. tion showed that the IR-drop in acidic or alkaline

Fig. 2. Cross-section of silver-tungsten carbide particles; diameter of the grains ca 40 pm

 Utilization and specific effective surface area of electrocatalysts 465

I
0 Wl I
3 4
1 I
5 0
I
/ 2
I
3
/
4
1 I
5
Pore lenqth. I , lo-4 cm
Pore length. I. ICY4cm
Fly. 3. Degree of utilization y of the pore of a catalyst Fig. 5. Degree of utilktion q of the pore of a catalyst
as u function of pore length i and pare radius qF/R’l’ = 1. as a function of pore length ! and polarization q.

electrolyte of the pore is negligible compared with The following quantities, unless stated otherwise, are
the total polarlation. kept constant:
The formula (3) indicates the nature of the depen- r = 6 x 10m7 cm, cg = 2 x IO-‘mol cmm3; D =
dency of the current yield IporC on pore size (length 10~5cm’s~ I; T= 298K. i0 = 10-hA.cm~‘; c( =
1, radius 1.). the parameters of the reaction (con- 0.5. They represent roughly the conditions for a hy-
centration c(,, diffusion coefficient D, temperature 7: drogcn-converting electrode with a Raney-nickel
polarization q) and the kinetic data (exchange cd iO, catalyst.
charge transfer coefficient 2):
The pore radius is chosen as parameter in Figs. 3
(I - a)Frl and 4. Polarization has been fixed at RT/F and at
IF”” = Z?rri, . i. exp ‘g - exp - 7 4 RT/F in the former and latter figures respectively.
( i In both cases the diminution of q values with declin-
ing r is perceptible. Fig. 5 illustrates the influence
tanh k (3)
of the parameter TV,and Fig. 6 that of iO,
These diagrams denote clearly how the degree of
and
utilization q can be adjusted by a proper choice of
nF,r.D,r, I.” W port dimensions.
j.= (4)
2io 2RT’ Some examples showing the influence on q values
C ! .exp--~
of the reaction parameter s are given m Table 1.
I indicates the pen&ration depth of the current. The anodic oxidation of gaseous hydrogen is com-
Without transport limitation (D c,,- m) one gets pared with the conversion of dissolved reactants. The
the ideal current I, pore dimensions have been kept constant corrcspond-
ing to those of a Raney-nickel catalyst particle.
Ii, = Iim Ipure Owing to the high c0 and low in values, the degree

1.(5)
D. ‘,,- Z of utilization y of the reactant A is not subject to
any IimitatIon, even at high polarization. The implica-
EFPf
Ii, = 2nr I i, exp - - cxp - (JZ$! tion of these results is that narrow and long pores
c RT (coarse particles) can be tolerated. This knowledge
is significant for the technical design of electrodes.
When the ratio of lrorC and Ild 1s formed, one obtains The decrease of q values becomes noticeable only
the utilization coefficient y of a single pore: when the concentration reduces and the exchange
cd increases by an order of magnitude. This is indi-
&#,,, 2” cated in case 0.
tanh i_ (6)
y=I,m= 1
Using this equation, the decrease in the degree of
utilization can be expressed for given reaction condi- A practical electrode consists of catalyst parlicles
tions. This is described in Figs 3-6 with examples. with a large number of single pores. The degree of

\ &A, cm-”

1 1 1 I I I
1 I I I / 0 1 2 3 4 5
0 I 2 3 4 5
Porelength. L . 10-4C~
Porelength. 1. lo-4cm
Fig. 6. Degree of utilization 4 of the pore of a catalyst
Fig. 4. Degree of utilization 4 of the pore of a catalyst as a function of pore length I and exchange current density
as a function of pore length I and pore radius qF/RT = 4 i,,, qF/RT = 4.
466 K. MUND AND F. v. STLJRM

Table 1.

gaseous reactant dissolved reactant

HZ (A) (J3

c0 (mol .aC3) 2-10~’ 10-3 10-4

D (cm’ s- ‘) IUS IO_” 10 h
i, (A cWL) IO h IO_” 10-E
II 2 \ 4 4
9 (my) 25 100 25 , 100 400 25 100 400
A (cm) 2.7. IO-‘+ 1.3. 10-h 0.27 0 I 25 6~23 lo- -’ 0.027 0~0125 6.23.10-3
I /p,r<(A) 1.1 lo-‘5 3.5. lW1’ 2.,“_‘8 l-4. IO- ” 5.6. IO- ” 2.10- ‘7 1.4. 10-lh 4.6. IO-l4
I,, (A) 2.10- 15 1.4. lo- I4 210~‘” 1.4. IO-” 56.10-” 2,10-” 1.4. 10-lh 5.6. lOm’4
‘/ 0.51 0.25 1 1 w997 1 1 0,829

utilization 4 is not altered by the addition of pores The physical dimensions are thus associated in the
of equal dimensions. factor B. The effective surface area f is dependent on
The specific cffcctivc surface arca will bc cstimatcd the pore radius r. We may discriminate three cases with
with the aid of a simple model. The catalyst particles respect to the L/I ratio :
in Fig. 7 arc dcscribcd as boards having the dimen-
sions h, 2 I and d. The particles are separated from (11)
one another by a distance y. The electrode has the
length a. The quantity y characterizes the macropore
system and is determined by the technical demands
of the transport of the reactants. In a gas diffusion
electrode the distance y is roughly given by the toler-
able gas pressure. If the electrolyte containing a dis-
solved reactant is flushed through the macropores.
J is determined by the available pump capacity. It follows from these equations that the specific
The catalyst particles are traced with pores having a effective surface area j” attains a high value if the
radius I’ and a length 1. They are accessible from two pore radius Y of the catalyst particles is small, and
sides. The number N of pores of a board is given that the quantity f is proportional to r * in the
by the porosity p: range /1</.
2h . d p In practical cases the pore dimensions are limited
N= mipm (7) only by the size of the diffusing molecules and ions.
7cr It is important to realize the influence of electro-
If1 porp is the current of one pore, the specific current lytic diaphragm resistance and electronic resistance
i in A/cm3 of the electrode is obtained by: in the catalyst and the electrode support. Therefore
the degree of utilization can be additively restricted
2&e P
by term q,,,.
i = (21 + y) 7-d
(8)
The polarization resistance w, of an electrode hav-
The quantities Ipore and i. arc known from the equa- ing a thickness d can he described by
tions (3) and (4).
Since s is the surface arca of the pore walls and
considering the degree of utilization q for single pores,
the specific ePfective surface area f can be expressed in which p is the resistivity of electrolyte volume
as: inside the working layer ie the diaphragm resistivity.
‘The meaning of k becomes clear from the limiting
value of the polarization resistance for negligible dia-
with

I I I I I I I
0 O-02 0.04 006 008 040

Thickness of working layer. d

Fig. 8. Degree of utilization q, of a porous electrode as

a function of thickness d of the working layer and polariza-
____ a tion resistance k ol the catalyst, the electronic resistlvity
Fig. 7. Model of catalyst particles in a porous layer has been neglected.
 Utilization and specific effective surface area of electrocatalysts 467

trodes. The clcctronic r&stance of the working layer

has not been considered in Fig. 8.
The influence of the electronic resistivity on the
q,--d relation is described in Fig. 9. Only when the
electronic resistivity exceeds 1 R.cm and approaches
the value of the diaphragm resistivity does it notice-
ably reduce qw, even at a thickness larger than
0.02 cm. Once again k is taken as a measure for
the catalytic activity and its value has been fixed
at lo-’ R.cm’.
Thickness of working layer. d AcknowlPdg~menr-This work has been supported by the
technical programme of the Federal Department of
Fig. 9. Degree yw of utilization of a porous electrode as Research and Technology of the FRG. The authors alone
a function of thickness d of the working layer and the are responsible for the contents.
electronic rcsistivity p. Diaphragm resistivity and polariza-
tion resistance k of the catalyst powder are constant.
REFERENCES
I. F. G. Schlosser, H~fwogw~~~ Kutolysa. Verlag Chemie,
Weinheim (1972). Ch.W. Satterfield, Mass Transfer ill
phragm resistivity p: Hrterogrneous Catalysis. M.I.T. Press, Cambridge,
Massachusetts, (1970).
2. L Ebersen and H. Schgfer, Forlschrillc, rl~r chemrschetl
Forschurlg 2!, (1971).
3. F. von Sturm. Elektrochemische Stromerseugung Ver-
The factor k represents the polarization resistance lag Chemie, Wemhelm (1969).
for an electrode when it has a negligible diaphragm 4. J. O’M. Bockris and S. Srinivasan, Fuel Ccl/s,
resistivity and a catalyst volume of 1 cm3. McGraw-Hill. New York (1969).
The condition for equation (14) is that the polariza- 5. E. Justi and A. Winsel, lCalte Vrrbrenmq-Furl Cells,
tion resistance is independent of the local polarization Franz Steiner Verlag. Wiesbaden (1962).
.in the working layer. The degree of utilization qw 6. K. Mund, G. Richter and F. von Sturm: Aktlvitats-
vergleich an Katalysatoren ftir same Rrennstoffzellen
is obtained by und Entwicklung einer Ag-WC-Elektrode fir die HZ-
Oxidation. Colln Czech. them. Commun. 36, 439
q,,.=i.$. tanh(8.d). (16) (1971).
7. W. Vielstich, Rro~nsrq~,lrmcntc, Verlag Chemie, Wein-
heim (1965).
q, declines with increasing layer thickness. The slope
8. E. Wendtland and A. Winsel, Elektrochemische
of the curve increases with the activity of the electro- Gas Diffusionselektroden,
Elgenschuften gespiilter
catalyst. This activity is illustrated in Fig. 8 by the Ch~~mir-I,2g~rripur_Tc~rhnik 39, 756 (I 967).
polarization resistance obtained by linearization of 9. K. Mund, Uber die Struktur von Katalysatoren und
the characteristic curve at low polarization. In the Elektroden fiir die elektrochemische Umsetzung von
curves in Fig. 8 the diaphragm resistivity p is given Gasen. Sivmens Forschungs- und Entwicklungsherichte,
at 10 R.cm. This is a current value in practical elec- 4, I (1975).