React. Kinet. Catal. Lett., Vol. 37, No.

2, 301-305 (1888)

ESR INVESTIGATIONS ON

ZnO

7-A1203 CATALYTIC

SYSTEM

I,V.

Nicolescu a, M. Chipar~ b, C. Pascu a, D. Barb~

I. Untea a, M. Floarea a and E. Chiril~ c

apolytechnic

Institute of Bucharest,
Faculty,

bInstitute

Chemical Technology

Polizu - 1,

for Physics and Technology of Materials,

CInstitute of Chemical and Biochemical

Bucharest,

Energetics,

Romania

Received April 4, 1987

Accepted November 16, 1882

ESR investigations on ZnO doped with various amounts

of y-AI203 thermally treated,are reported.
tal data are related to t h e electronic
ZnO-y-AI203 and to desulfurization

Experimen-

structure of

specific activity

for natural gas.

HpHBO~HTC~ Hccne~OBaHHe MeTO~OM 9HP ZnO, HaHeceHHoPo
Ha pasnHqHble Ko~nqeCTBa TepMHqeCKH
AI203 . ~KcHepHMeHTa~bH~e

o6pa6OTaHHOFO

~aHHble O 6 ~ C H ~ D T C H

pOHHb~ CTpOeHHeM ZnO/y-AI203 H cpaSHHSamTCH

y-

9neKTCO cne-

HH~HqeCKO~ aKTHBHOCTbm K HpoHeccy ~eCynb~ypHpOB~HHS

HpHpO~HOFO

Fa3a.

The Zn0 as well as the ZnO-T-AI203

system exhibit semicon-

ducting features, which may be related to catalytic

under various reaction conditions

[1-3].

ESR spectroscopy may

be used to investigate the presence of active centers

in the ZnO-y-AI203

activity
(a.c.)

system.

EXPERIMENTAL
ESR spectra of the Zn0-y-Al203

system as well as of the

Akad~miai Kiadd, Budapest

NICOLESCU et al. : ESR INVESTIGATIONS

pure ZnO and pure y-AI203

a JES-ME-3X

components,

spectrometer,

Measurements

have been recorded using

operating

have been p e r f o r m e d

in X band

(about 9 GHz).

in air, at roan temperature.

samples have been m e a s u r e d

in the temperature

using a J E S - V T - 3 X v a r i a b l e

t e m p e r a t u r e accessory.

estimate a c c u r a t e l y
has b e e n

300-500 K,

In order to

freshly r e c r y s t a l l i z e d

DPPH

used as field marker.

The catalysts
phase,

the g value,

range

The

have been p r e p a r e d bv the reaction

among ZnO, h e x a h y d r a t e d

m o n i u m carbfmahe. The products

a l u m i n i u m nitrate

have been thermally

in a wet

and acid amtreated at 773-

-1073 K. Samples have been s p e c i f i e d by various molar ratios

between X-AI203

and ZnO,

denoted by r

(r=0.05-0.5).

The activity

test has been p e r f o r m e d w i t h carbon

sulfide at 673 K, in a re-

circulating

The specific

(SA wt.%)

system during

10 hours.

activity

is e x p r e s s e d by the amount of sulfur retained on

ZnO-~-AI203 9
RESULTS AND D I S C U S S I O N
Pure ZnO thermally

trea~ed at 773 K, unlike 7-A1203,

a narrow asymmetrical

resonance

value close to g= 2.0

(Fig.

peak to peak resonance

shape

line,

characterized

i). Resonance

line parameters

line width Hpp in Tesla,

factor K), are given in Table

i. Shape

been e s t i m a t e d using the slope m e t h o d

gives

by a g
(the

g value and

factor K, has

[4] and a.c.

concentra-

tion C has been d e r i v e d using the formula

where

I is the resonance

As may be noticed
for r=0.1.
r

y-Al203
nance

line w i d t h

increase

302

introduced

K I H2
PP

line intensity.

from Fig.

The resonance

(Table i) supports

2, curve

line w i d t h

this result.

i, C reaches

dependence

Increasing

on mole ratio

the amount of

in the system from r=0 to r=0.1,

is n a r r o w e d due to the a.c.

(which enhances

exchange

a maxim~n

the reso-

concentration

interactions,

responsible

NICOLESCU et al. : ESR INVESTIGATIONS

ZnO

b
------

r -0.05
TA-?'t3

r -0.10

- - - - . . . . TAo 773
d

r - 0.25

--'--

TA- 3

r-0.50

TA" 7 n
f

r-0.10

TA" 973
,
Fig.

,4xlO'4T

I. ESR spectra of the ZnO-y-AI203

system

Table 1
Resonance

line parameters

for samples thermally

treated at 773 K

Sample

Hpp (10- 4T)

ZnO

6.8

1.09

2.0054

ZnO-y-Al203

(r=0.05)

7.0

1.16

2.0047

ZnO-y-Al203

(r=0.10)

3.8

1.44

2.0043

ZnO-y-Al203

(r=0.25)

5.0

1.37

2.0044

ZnO-y-AI203

(r=0.50)

7.2

i.ii

2.0045

y-AI203

for resonance

line narrowing and reduce the relative weight of

dipolar interactions leading to a Lorentzian line

the mole

ratio r is further increased,

[i,4]). As

C decreases and the

303

NICOLESCU et al. : ESR INVESTIGATIONS

25
1.00

20

=1
'~

0.75
10

,5
0

o.so

\,,

(.)

0.25

0.1

~2

0.3

0.4

0.5

~6

Fig.

2. The dependence

of relative

a.c.

concentration

(i) and of the specific

activity

desulfurization

of natural

mole

process

SA

(2) on the
gas on the

ratio r for the sample thermally

treated

at 773 K

resonance

line w i d t h increases,

dominant.

These

shape

features

(K) dependence

The d e p e n d e n c e
ature

(a.c.)

the a.c.

773

(K)

Hpp(10-4T)
3.8

line

temper-

for the sample

spinel phase develops,

are located.

line parameters
at various

treatment

is m a x i m u m

973 a defected

Table

TA

become

on r.

(Table 2) shows that C

Resonance

interactions

of C for r=0.1 on thermal

calcined at 773 K. Above

in which probably

as dipolar

are supported by the resonance

for samples

temperatures

K
1.44

TA

thermally treated
(r=0.1O)

g
2.0043

(r.u.)

1.00

873

4.0

1.14

2.0044

0.9~

973

3.4

1.09

2.0052

0.88

1073

1.6

1.30

2.0063

1.71

304

NICOLESCU et al. : ESR INVESTIGATIONS

The g factor deviation

from the free e l e c t r o n

pends on the amount of 7-A1203

as on the thermal
of the g value
ZnO-T-AI203

treatment

(from g=2.0023)

system,

conductor

between the e l e c t r o n i c

[2,5],

from Fig.

the dependence

of a.c.

(2) on mole

gas,

2, there

as well

for the sample

(Tables

structure

to d e s c r i p t i o n

the specific

process of natural

may be noticed

tivity

has been o b s e r v e d

ESR data and a c c o r d i n g

reactivity

furization

in the system,

The m i n i m u m d e v i a t i o n

specified by r=0.1 and calcined at 773 K

1 and 2). A connection

-7-A1203

introduced

temperature.

g value de-

activity

of ZnOof semi-

in the desul-

has been investigated.

is a good a g r e e m e n t

concentration

As"

between

(I) and of specific

ac-

ratio r.

CONCLUSIONS
ESR data on the ZnO-y-AI203
concentration
T-A1203

ratio r between

as well as on the thermal

maximum concentration
r=0.05-0.25
The result
shape

system are reported.

depends on the mole

of a.c.

and at a c a l c i n a t i o n

respectively.

the electronic

temperature

on mole

of about 773 K.

line w i d t h H

and

between r e s o n a n c e

process

tem-

data,

of the system and the specific

in the natural gas d e s u l f u r i z a t i o n

in the range

PP
ratio and c a l c i n a t i o n

A connection

structure

temperature.

has been o b s e r v e d

is supported by the resonance

factor K dependence

perature,

treatment

The a.c.

ZnO and

activity

is derived.

REFERENCES
i. G. Lancaster:

Electron

Hilgar and Watts,

2. F. Volkenstein:
conductors.
3. J.C.

Ltd.

London

Electronic

Moscow

Slater:

Spin Resonance

in Semiconductors.

1966.

Theory of C a t a l y s i s

on Semi-

1963.

Q u a n t u m Theory of M o l e c u l e s

and Atoms,

Vol.

II.

M c G r a w Hill Book Co., New York 1965.

4. B. Roanby,

F. Rabek:

Springer-Verlag~
5. Y.A. Gerasimov:
1974.

ESR S p e c t r o s c o p y

Berlin
Physical

in Polymer

Research.

1977.
Chemistry,

Vol.

II. Mir,

Moscow

305