Hydrogen Gas Absorber Made of Manganese Dioxide

Akiya Kozawa*
Union Carbide Corporation, Battery Products Division, Cleveland, Ohio 44101

Manganese dioxide catalyzed with p a l l a d i u m (1) or Results and Discussion

silver was found to be a good hydrogen absorber. M a n -
ganese dioxide alone (without a catalyst) has practi-
cally no ability to absorb h y d r o g e n gas at room t e m -
p e r a t u r e (2). This note describes the p r e p a r a t i o n con-
ditions and the properties of the h y d r o g e n absorber and
also a f e w possible applications.
Experimental
A typical method for p r e p a r i n g the hydrogen gas ab-
sorber is as follows. The components listed i n Table I
are mixed thoroughly. A n appropriate a m o u n t of water
(for example, 300g of w a t e r per 1000g of the dry mix)
is added, and the m i x t u r e is well b l e n d e d to produce
a moldable paste. The paste is e x t r u d e d or molded
into various shapes (rod, pellet, sheet, etc.) depending
on the application. T h e n it is dried at 75~176 over-
night. The shaped body becomes rigid because the
cement sets d u r i n g the d r y i n g process. The stainless
steel wool is not necessary b u t makes the porous body
Absorption capacity.--When 100 mg of the absorber
having the composition shown i n Table I was tested in
the apparatus shown i n Fig. 2, the m a t e r i a l absorbed
about 17.5 cm 8 of H2 gas in 5 days as shown i n Fig. 3.
According to the reaction (MnO2 + H2 --> MnO -t-
H20), t h e MnO2 contained i n the absorber should a b -
sorb about 19 cm 3 of H2 gas. This result (Fig. 3) i n -
dicates that MnO2 is reduced almost to MnO. I n the case
of Ag20 or AgO catalyst, MnO2 was reduced to only
MnOOH or slightly more t h a n MnOOH.
Absorption rate.--The absorption rate is fast ini-
tially and becomes slower and steady after 1 hr. The
steady rate depends on the a m o u n t of the catalyst as
well as b i n d e r as shown in Table II for Pd-catalyzed
absorbers and Fig. 4 for silver-catalyzed absorbers.
The test t e m p e r a t u r e and particle size of m a n g a n e s e

~
strong, p a r t i c u l a r l y i n the case of sheets. The solid
body is porous and most of the water added i n the
b l e n d i n g step is removed in the d r y i n g process.
The rate of h y d r o g e n absorption was tested with the
apparatus shown in Fig. 1 and 2 for fast adsorption and
slow absorption, respectively. The absorption is a H \
chemical reaction b e t w e e n H2 gas and MnO2. The ap-
paratus shown i n Fig. 1 is used to test the initial ab-
sorption rate employing a 1 ~-, 2g sample. The a p p a r a -
tus shown in Fig. 2 is used to m e a s u r e the total ab-
sorption capacity employing a 100-200 mg sample.
To operate the apparatus (Fig. 2) first the air i n the
test tube (B) was replaced b y N2 gas b y p u r g i n g while
the m o u t h of the test tube was m a i n t a i n e d slightly
above the oil level (H). T h e n .the oil level i n the test
tube was raised to a r o u n d (I) by applying a vacuum.
F i n a l l y H2 gas was introduced and the oil level was
b r o u g h t down to (H). All the fine plastic tubes (D)
were t h e n removed. The oil level was read from time
to time to m e a s u r e the h y d r o g e n gas u p t a k e b y the
sample. This was not a v e r y accurate m e a s u r e m e n t
(• cm3), b u t satisfactory for the present purpose.
* E l e c t r o c h e m i c a l S o c i e t y L i f e Member.
Key words: hydrogen, m a n g a n e s e dioxide, palladium, gas ab-
sorber.

c
Table I. Components of the hydrogen gas absorber

Typical
example Range

1. M a n g a n e s e dioxide* 73.7% (by wt) 50-80% (by wt)

2. B i n d e r ( P o r t l a n d c e m e n t ) * * 18.5 10-40
3. Pd-catalyzed carbon* ** 4.6 0.4-20
(or Ag20 or AgO) (3.0) (1-10)
4. C h o p p e d s t e e l w o o l 2.3 0-5
5. A c e t y l e n e black 0.9 0-5
Fig. 1. Apparatus for measuring the hydrogen gas absorption rate.
After evacuation of the sample tube, the sample tube was con-
* E l e c t r o l y t i c m a n g a n e s e dioxide for dry cell such as I.C.
MnO2 No. 1, 2, a n d 3 (6). nected to the main gas burette by opening stopcock A. A: Stopcock,
** E l i m i n a t e P o r t l a n d c e m e n t in t h e case of A g 2 0 o r AgO B: gas burette (100 cm3), C: liquid paraffin bath, D: magnetic
catalyst.
*** O b t a i n e d f r o m E n g e l h a r d Industries, Incorporated. This ma- stirrer and hot plate with temperature control, E: sample tube, F:
terial c o n t a i n e d 5% P d , 45% carbon, and 50% H20. mercury, G: hydrogen gas cylinder, H: vacuum pump.

1193
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 1194 J. Electrochem. Sot.: ELECTROCHEMICAL SCIENCE AND TECHNOLOGY August 1976

Table II. Effect of the catalyst content on the H2 absorption rate

(data given in this table are the average of two experiments)

Catalyst Actual A m o u n t of Maximum H~ a b s o r b e d H2 a b s o r b e d Absorotion

content* sample MnO~ in the H2 to be ab- in 2 h r at in first 30 rate after 1
(%) t e s t e d (g) sample (g) s o r b e d ( c m ~) 45~ (cm s) min (cm s) h r (cmS/hr)

0.8 1.51 0.97 200 g.o • 0.5 3.0 -- 0.5 4.5 -- 0.5
2.0 1.47 0.95 195 23.0 IO.O 7.0
4.0 1.45 0.90 187 32.0 15.0 11.0
9.2 1,35 0.76 162 48,0 27.0 11.0
16.0 1.38 0.73 151 54.0 32.0 13.5

* T h e basic composition is as follows, the catalyst content being varied: MnO~: 160g, P d - c a r b o n : 0,4-16.8%, acetylene black: 2g, binder
( P o r t l a n d c e m e n t ) : 80g, steel wool: 5g.

dioxide influence the absorption rate as seen in Fig. 5 (polyethylene, polysulfone, etc.) sometimes deactivate
and 6. the catalyst, probably because the polymer covers the
Use of Hz gas permeable #lm.--If the hydrogen gas active centers of the palladium.
to be absorbed coexists with a solution, e.g., in the CO absorption.--It was found in a preliminary test of
alkaline manganese dioxide-zinc cell, this porous hy- this Pd-catalyzed hydrogen absorber for CO absorption
drogen absorber may be wrapped with a thin poly- that this material does have a relatively good capability
ethylene film through which I-I2 gas is permeable at a for CO adsorption.
sufficient rate but which prevents the solution from
going into the porous body. A 1 mil thick polyethylene
20
film (such as Zendel made by Union Carbide Corpora- I I I I
tion) has a sufficient hydrogen gas permeability for
most applications.
Other catalysts.--The catalyst can be platinum black
or other noble metals; palladium dispersed on carbon 15
o
is satisfactory and inexpensive compared to other noble
metal catalysts. The function of the palladium would
be the dissociation of hydrogen molecules to atomic 9
hydrogen. lO
Bonding agent.--Among various bonding agents in-
cluding organic plastics dissolved in organic solvents,
a few inorganic binders, water, glass, and cement
were found to be m o s t convenient. Organic plastics

c 0 I I I I I
0 1 2 3 4 5 6
Time, Days
Fig. 3. Hydrogen gas absorption by a 100 mg crushed sample
I having a formula shown in Table I,
t
I L
.
"////"
Z / I l l ,
I 5O I I I I
I : ;;S;,;,;,
D -
, i z / z z 5.5' ~ 4

40 - 4' --
I i

P~ I/
f7 AgO
Ag20
--

o
(H> _a
~ 20

7 ///
iii1~
..Q

rl//#
~ ....-. --"" ~ . . . . . . - - - 3
L,.. i
////.,
~ / / / / , , 2.2'
i / / /
o I ~ I J I ~'~
Fig. 2. Apparatus for measuring hydrogen gas absorption (see 0 1 2 3 4 5
text for operation). A: 10 cm3 beaker containing sample, B: an Time, hours
inverted test tube (3.5 cm in diameter, 30 cm long), C: hydrogen
gas, D: fine plastic tubes, E: hydrogen cylinder, F: nitrogen cylinder, Fig. 4. Hydrogen gas absorption by lg sample (MnO2 + Ag20 or
G: vaccum, H: oil level, I: top of the plastic rod, J: plastic rod, K: AGO). Ag20 or AgO content was as follows: 1.1':0.1%, 2.2':0.3%,
vacuum pump oil in 250 cm~ beaker. 3.3':1%, 4.4':3%, 5.5':10%.
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 Vol. 123, No. 8 HYDROGEN GAS ABSORBER 1195

Stability in air.--A h y d r o g e n a b s o r b e r was p r e p a r e d

u lO0 | I I I I I
w i t h 0.4% p a l l a d i u m - c a r b o n catalyst, stored in air for
5 years and tested. A l t h o u g h the a b s o r b e r contained
only 0.4% of the catalyst, it was possible to m a i n t a i n
80
65~
almost the same a b s o r p t i o n r a t e as the f r e s h sample.
The total a b s o r p t i o n capacity, however, decreased to
70% of the initial capacity d u r i n g t h e 5 y e a r storage
~ 60 -- - in air at 23~ T h e r e d u c e d MnO2 in the h y d r o g e n a b -
s o r b e r b y the reaction w i t h h y d r o g e n gas is reoxidized
g up to about 30-60% b y o x y g e n in air. The r e g e n e r a t i o n
f e a t u r e of this m a t e r i a l is i m p o r t a n t for certain a p -
~,. 4o plications.
212
/ ~ 23~ _ Applications
One application of the h y d r o g e n a b s o r b e r is the r e -
m o v a l of h y d r o g e n gas in sealed cells (1). In sealed
cells such as a l k a l i n e MnO2-Zn cells, H2 gas evolved
f r o m t h e zinc anode b y corrosion accumulates, and this
o I I I I I h y d r o g e n m u s t be r e m o v e d before the i n t e r n a l p r e s -
20 40 60 80 100 i20 sure becomes too high. A rod or p e l l e t form of this h y -
Time, Min. d r o g e n absorber, w h i c h is w r a p p e d w i t h a thin p o l y -
e t h y l e n e film, can be used for this purpose.
Fig. 5. Effect of temperature of the hydrogen gas absorption rate. A n o t h e r application is the r e m o v a l of accumulated
The composition of the absorber was as follows: MnO2: 160g, h y d r o g e n gas in confined areas or compartments, since
Pal-catalyzed carbon: 25g, cement: 80 g, acetylene black: 2g, a n y possible explosion h a z a r d m u s t be e l i m i n a t e d for
steel wool: 5g. The sample of each test had about 1.5g in a crushed safety. Such confined areas i n c l u d e u n d e r w a t e r vessels
powder form.
or closed rooms in which h y d r o g e n gas m a y be l e a k e d
from a pipeline or g e n e r a t e d b y various chemical or
6O I radiochemical reactions or f r o m l e a d - a c i d batteries.
A n o t h e r application is the r e m o v a l of h y d r o g e n gas
g e n e r a t e d from a b a t t e r y p o w e r p a c k w h i c h operates
a d j a c e n t to electronic equipment. H y d r o g e n gas is often
g e n e r a t e d from d r y b a t t e r i e s and r e c h a r g e a b l e b a t -
teries and alters the characteristics of the capacitors
and resistors in the electronic circuit. This t y p e of
u 4O p r o b l e m can be easily e l i m i n a t e d b y using the p r e s e n t
h y d r o g e n a b s o r b e r at the top of the b a t t e r y pack.

~' 20
o I I I I I
0 20 40 60 80
Time, Min.
Fig. 6. Effect of particle size of manganese dioxide used in the
adsorber having a formula as follows: MnO2: 160g, Pd-catalyzed
carbon: 10g, acetylene black: 2g, cement: 40g, steel wool: 5g.
Particle size of MnO2: A: less than 40/~, B: 50-100#, C: 150-300~.
Mechanism of MnOz reduction.--The r e d u c t i o n of
MnO2 in d r y cells has been e x t e n s i v e l y studied (3-5).
A c c o r d i n g to the studies, the electrochemical r e d u c t i o n
process is a p r o t o n injection into t h e MnO2 lattice at
least up to MnOl.~, as shown b e l o w
MnO2 4- H20 -k e - --> MnOOH -p O H -
The reduction of MnO2 b y H2 gas w o u l d involve the
same mechanism, a l t h o u g h t h e source of protons is
H2 ( : 2H) i n s t e a d of H20 ( : H + -~- O H - ) .
Acknowledgments
The a u t h o r wishes to t h a n k Mrs. H. M. J o s e p h for
h e r assistance in p r e p a r a t i o n of the manuscript.
Manuscript s u b m i t t e d Jan. 29, 1976; revised m a n u -
script received March 10, 1976. This was P a p e r 2.19
p r e s e n t e d at the Chicago, Illinois, Meeting of t h e So-
ciety, May 13-18, 1973.
A n y discussion of this p a p e r will a p p e a r in a Discus-
sion Section to be p u b l i s h e d in the J u n e 1977 JOURNAL.
A l l discussions for the J u n e 1977 Discussion Section
should be s u b m i t t e d b y Feb. 1, 1977.
100 120
Publication costs of this article were assisted by
Union Carbide Corporation.
REFERENCES
1. A. Kozawa, U. S. Pat. 3,893,870 (19'75) and 3,939,006
(1976); Brit. Pat. 1,321,853 (1975); A u s t r i a n Pat.
302,436 (1972); Belgian Pat. 755,337 (1971); G e r -
m a n Pat. DT 2,042,266 (1971).
2. C. S. Brooks, J. Catalysis, 4, 535 (1965).
3. A. K o z a w a and J. F. Yeager, This Journal, 112, 959
(1965).
4. A. K o z a w a and R. A. Powers, ibid., 113, 870 (1966).
5. A. K o z a w a and R. A. Powers, J. Chem. Education,
49, 587 (1972).
6. I n t e r n a t i o n a l common s a m p l e of m a n g a n e s e dioxide,
This Journal, 119, 152C (1972). The MnO2 samples
a r e a v a i l a b l e from the I. C. S a m p l e Office, spon-
sored by the Cleveland Section of The Electro-
chemical Society, P. O. Box 6116, Cleveland, Ohio
44101.

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