Applied CatalysisA: General 114 ( 1994) 295-311

Nickel modified H-ZSM-5 catalysts

D.L. Hoang, H. Berndt, H. Miessner, E. Schreier, J. Vijlter,
H. Lieske”
Institute of Applied Chemistry Berlin-Adler&j Rudower Chausse 5, D-12484 Berlin, Germany

Received29 March 1994

Abstract

Nickel containing H-ZSMJ catalysts were prepared by impregnation with nickel nitrate at pH 1.8
and 4.8. The catalysts were characterized by infrared spectroscopy of adsorbed carbon monoxide and
ammonia, by temperature-programmed reduction as well as by chemisorption of hydrogen andoxygen.
The conversion of n-hexane served as a catalytic test reaction. Impregnation at pH 1.8 leads to nickel
ions exchange of Br@nstedsites in the channel system. These are hardly reducible and are not detectable
by IR spectroscopy of adsorbed carbon monoxide. Aromatization is increased. This is explained by
the presence of ionic nickel Lewis sites, active in dehydrogenation. With impregnation at pH 4.8,
tetrameric nickel ions exist, not able to penetrate into the channels, and nickel is mainly located
outside the channels as metallic nickel. The selectivity to aromatics is still higher. This should be due
to the action of metallic nickel, which promotes the direct dehydrocyclization. The hydrogenolysis
activity of metallic nickel is suppressed.

Keywork Acidity; H-ZSM-5; Hexane conversion; Hid&n position; Hydrogen/oxygen chemisorption; Infrared
spectroscopy; NilH-ZSM-5; Temperature-programmed reduction

1. Introduction

It is well known that H-ZSM-5 zeolite can be modified by incorporation of metals

or metal oxides in order to obtain catalysts for selective hydrocarbon conversions.
For example, the modification of H-ZSM-5 with platinum, gallium oxide or zinc
oxide results in selective catalysts for the aromatization of light alkanes [ l-41. The
catalyst systems prepared in this way operate bifunctionally. The primary role of
the transition metal, or of gallium and zinc species, was suggested to consist in
increasing the rate of alkane dehydrogenation to alkenes as the rate determining

*Corresponding author. Tel. ( + 49-30) 63924372, fax. ( + 49-30) 63924392.

0926-860X/94/$07.00 0 1994 Elsevier Science B.V. All rights reserved

rm,no3K_PLnY IPA \nnn-r? ”
296 D.L. Hoang et al. /Applied Catalysis A: General 114 (1994) 295-311

step [ 561, or in promoting the recombination and desorption of hydrogen, which

was abstracted before from alkane molecules [ 7,8].
Among the Group VIII metals, platinum and palladium supported on H-ZSM-5
have been widely and thoroughly investigated [l-4,9], whereas nickel was only
rarely studied. Nickel on H-ZSM-5 has been found to be active in the aromatization
of higher n-alkanes [ lo], in hydrocracking of n-dodecane [ 111 and in the isom-
erization of Cg aromatics [ 12,131. Nickel exchanged H-ZSM-5 catalysts were
reported to be active in the hydrogenolysis, but not selective in the aromatization
of propane [ 141. A hybrid catalyst composed of H-ZSM-5 and Ni/SiO* has been
shown to exhibit high activity and selectivity for n-butane aromatization [ 71. On
the whole, there is a gap concerning the characterization of nickel in Ni/H-ZSM-
5. The state of nickel, which is strongly dependent on the catalyst preparation and
pretreatment modes [ 15-181, was not sufficiently investigated up to now and the
conclusions about the catalytic role of nickel remained uncertain.
We were especially interested in the investigation of Ni/H-ZSM-5 catalysts,
because it is well documented in the literature that the state of nickel on some
supports, such as alumina or HY zeolite, can be strongly modified, causing sur-
prising changes of the catalytic properties. For example, the well-known hydro-
genolysis activity of nickel could be suppressed, whereas its dehydrogenating
property increased and became predominant in some cases [ 19-2 11.
The aim of this work was to study the interaction of nickel species with H-ZSM-
5. We were interested in the following questions: how, on the one hand, is the state
of nickel influenced by the presence of H-ZSM-5 as a support and how, on the other
hand, can the nickel species influence the properties of H-ZSM-5, especially its
acidity. Finally, we wanted to study the effect of the cooperation of nickel and H-
ZSM-5 on the catalytic properties. The conversion of n-hexane was chosen as a
test reaction. In order to compare the results with a well-known metal promoted
system, we investigated a sample of Pt/H-ZSM-5.
Temperature-programmed reduction (TPR) , oxygen and hydrogen pulse chem-
isorption as well as infrared spectroscopy of adsorbed carbon monoxide (CO-IR)
were used in order to characterize the state of nickel and platinum. The acidic
properties of H-ZSM-5 were investigated by infrared spectroscopy and by temper-
ature-programmed desorption of ammonia (TPDA) .

2. Experimental

2.1. Catalyst preparation

H-ZSM-5 was prepared by calcination (2 h at 300°C and 2 h at 500°C) of the

NH,+- form of a commercial ZSM-5 zeolite (Si/Al= 19), produced by Bitterfeld
Chemie AG (Germany). The dry H-ZSM-5 was impregnated with a0.05 Msolution
of nickel nitrate at pH 4.8 or at pH 1.8 using vacuum rotary evaporation. The
 D.L. Hoang et al. /Applied Catalysis A: General 114 (1994) 295-31 I 297

Table 1
Catalyst samples

Sample Catalyst symbol Ni or Pt content pH of impregnation

Wt.-% mmol/g

A [ H-ZSM-51
B [0.5Ni1.8] 0.5 0.085 1.8
C r0.5Ni4.81 0.5 0.085 4.8
D [2.ONi4.8] 2.0 0.340 4.8
E [0.3Pt1.8] 0.3 0.015 1.8

samples were dried in air at 120°C for 12 h and stepwise calcined afterwards at
300°C (2 h) and at 500°C (2 h). Pt/H-ZSM-5 was prepared by impregnating H-
ZSM-5 with a H2PtC16solution and treated in the same way. The samples were
stored in dry air. The catalysts prepared are listed in Table 1 and noted A to E.

2.2. Infrared spectroscopy

OH vibration spectra and spectra of adsorbed ammonia

These spectra were recorded with a spectrometer Specord MS5 (Carl Zeiss Jena),
using a heatable cell and self-supporting wafers of ca. 7 mg/cm2. The samples were
heated under vacuum at 400°C for 18 h in order to remove adsorbed water. 20 Torr
( 1 Tot-r = 133.3 Pa) ammonia were adsorbed at room temperature for 30 min and
subsequently desorbed at 100°C in order to remove physisorbed ammonia. The IR
spectra were recorded in the ranges 3800-3200 cm- ’ and 1800-1300 cm- ’ at
room temperature.

Spectra of adsorbed carbon monoxide

Transmission spectra of adsorbed carbon monoxide were obtained using a con-
ventional glass cell with KBr windows, connected to a vacuum line and gas dosing
system for in-situ pretreatment. The samples were pressed into self-supporting
wafers with ca. 10 mg/cm2. The pretreatment consisted in an evacuation ( 10T4
Torr) of the calcined sample at room temperature ( 1 h) and at 300°C ( 1 h) as well
as in a subsequent reduction in hydrogen (ca. 50 Torr, 5OO”C,1 h) followed by
evacuation at 500°C for at least 30 min. After exposing the pretreated samples to
5-10 Torr CO at room temperature, spectra were recorded by means of a PI-IR
spectrometer (BIORAD; FTS6OA) at a resolution of 2 cm- ‘. In order to obtain a
sufficiently high signal to noise ratio, 256 scans were accumulated. The spectra
shown in this paper are corrected for the background and the contribution of the
windows.

2.3. Temperature-programmed desorption of ammonia

In order to obtain information about the Bronsted acidity of the initial zeolite H-
ZSM5, quantitative TPDA measurements of this material were carried out. Appa-
298 D.L. Hoang et al. /Applied Catalysis A: General 114 (1994) 295-311

ratus and procedure for separating the low- and the high-temperature peaks by an
isothermal treatment in helium at 250°C are described elsewhere [ 221. The result
was taken as a basis value for estimating the Bdnsted acidity of the modified
samples, vide infra.

2.4. Temperature-programmed reduction and hydrogen/oxygen pulse

chemisorption

TRR and chemisorption measurements were performed with a dynamic AMI-

characterization system (Altamira Instr., Inc.). The catalyst samples (500 mg)
were heated up to 550°C in a helium flow containing 5% oxygen in order to remove
water and organic contaminations.
TRR was carried out in a argon flow containing 5.34% hydrogen at a gas flow-
rate of 70 ml/min and a heating rate of 20 K/min. The TPR was stopped at 500°C
for samples used for pulse chemisorption, but extended to 1000°C otherwise, in
order to get information on the reduction behaviour of nickel ions at higher tem-
peratures. The TRR was always finished by an isothermal 1 h period at the final
temperature. With nickel containing samples, the reduction degree was corrected
for argon desorption at low temperatures and for the hydrogen consumption of the
zeolite.
The pulse chemisorption of hydrogen or oxygen was carried out at 0°C using a
helium or argon flow of 50 ml/min and 55 ,~l pulses of pure hydrogen or of 20%
oxygen in helium, respectively. For calculating the metal dispersion, adsorption
stoichiometries of Ni/O = 1 and A/H = 1 were assumed.

2.5. n-Hexune conversion

The conversion of n-hexane was carried out under normal pressure at 500°C in
a fixed-bed glass reactor, continuously fed either with a hydrogen or a nitrogen
flow, in each case saturated with n-hexane at 15°C (pn_hexane= 98 Torr) . The catalyst
samples were pretreated in air at 300°C for 1 h in situ, followed by a hydrogen
treatment at 500°C for 1 h. The reaction products, mainly consisting of lower alkanes
C1-C4, alkenes C,-C, and aromatics C&a, were analyzed using gas chromatog-
raphy. The dependence of the n-hexane conversion on the contact time W/F was
investigated. An influence of slow diffusion was excluded. In this paper, the cata-
lytic properties of the catalysts are compared at a contact time Wl F = 4.7 gcatalYSl
h / moLhexane.The conversions were in the 12-20% range in nitrogen atmosphere,
and in the 15-60% range in hydrogen atmosphere. The deactivation of the catalysts
during the 5 h experiments was negligible.
 D.L. Hoang et al. /Applied Catalysis A: General 114 (1994) 295-311 299

3. Results

3.1. TPR, chemisorption and CO-IR: state of nickel and platinum

TPR and chemisorption

Fig. 1 shows the TPR profiles of the samples noted A to E. The peak at room
temperature is not due to hydrogen consumption but to the argon desorption from
the zeolite channels. The peak above 800°C could be assigned to an impurity in
this industrially produced zeolite, perhaps iron species. The small peak at 340°C
with [ 0.5Nil.81 indicates the reduction of a small portion of the total nickel content,
whereas further reduction follows only above 1000°C. With samples [0.5Ni4.8]
and [2.ONi4.8] a considerable amount of Ni” is reduced, at temperatures corre-
sponding to nickel oxide. Finally, [0.3Pt1.8] only gives a relatively small TPR
peak, suggesting an essential thermal decomposition of the impregnated Pt’” com-
pound already during the calcination at 500°C.
In Table 2, quantitative results of TPR and pulse chemisotption are summarized.
As will be shown later on by the results of IR spectroscopy, besides Ni2+ also Ni+
cations could be observed in the reduced samples. However, it cannot be decided
on the basis of the present results, whether these Ni+ ions were already formed
during the reduction of the samples with hydrogen or only during the IR experiments

L
45’C

410°C [0.3Pt1.8]
x10
_______________---- ---_-

._Zg______!t::::
j
.m
_--._LL”s”““___
s;\zyItill
[H-ZSMd]
890°C 1020°C
-------~----_____x_1_0

---iI I

25 25 200 400 600 600 1000 1000 TI’C

Fig. 1. TPR profiles of the samples A-E; dashed lines recorded during isothermal periods; note the.different
amplification and the virtual TPR peak at about 40°C caused by Ar desorption out of the zeolite pores.
300 D.L. Hoang et al. /Applied Catalysis A: General 114 (1994) 295-311

Table 2
Metal state in the reduced catalysts

( 1) Sample (2) Ni or Pt (3) Degree (4)Chemisotption (5) Metal (6) Dispersion (7) Average
content of reduction” (mollg cat.) surface of Ni’ or Pt& metal Patti-
(gmol/g cat.) (%) area= (%) cle sized
(m’/g cat.) (nm)
Oxygen Hydrogen

B; [OSNi1.8] 85 3
C; L0.5Ni4.81 85 75 1.9 0.15 6.2 14
D; [ 2.ONi4.81 340 75 6.1 0.48 4.8 17
E; L0.3Pt1.81 15 IOOb 1.2 0.11 15.7 6

’ From TPR, assuming Pt4’ --t Pt” and Ni’+ + Ni”, respectively.
h Weak TPR signal because of partial thermal &composition Pt4+ + Pt’ during calcination.c Assuming the chemisorption stoichi-
omebies OlNi = 1 and H/Pt = I ,dAssuming cubic particles.

by the interaction with carbon monoxide, like e.g. the formation of Rh(C0)2+
from zeolite supported Rh3 + [23]. Therefore, for determining the degrees of
reduction by TPR, only the reduction of Ni’+ to Ni” could be taken into account.
Nickel in the reduced catalyst [ 0.5Nil.81 almost exclusively exists in the oxi-
dized state. As known, bulk NiO is reduced at about 300°C [ 241. The observed
stabilization of oxidized nickel should be due to an interaction with H-ZSM-5. This
must be an exchange of nickel ions, probably Ni( OH) +, with the protons of the
Br@nsted sites in the pore system. The low reducibility means a remarkable differ-
ence to exchanged nickel in Y zeolites. Depending on the conditions, more or less
high proportions of nickel ions in Y zeolites could be reduced to the metallic state
[ 15-l 81. This will be discussed later on, on the basis of a model assuming ‘hidden
positions’, which are hardly accessible for nickel ions, and assuming a stabilizing
role of these positions.
Unlike [0.5Ni1.8], the two catalysts impregnated at pH 4.8 ( [0.5Ni4.81 and
[ 2.ONi4.81) contained 75% of their total nickel content as metallic Ni” after reduc-
tion. Only 25% remained in the ionic state and were able to exchange Bransted
protons. The results of oxygen pulse sorption indicate a low dispersion of the
metallic nickel. The average nickel particle size was estimated to be 14 and 17 nm,
respectively. Such large particles should be localized exclusively on the outer
surface of the zeolite crystallites.
The reduced sample [0.3Ptl.8] contained only metallic platinum, the main part
of which had been formed already during the calcination step. Hydrogen chemi-
sorption revealed a low dispersion of the metal, with the metallic surface area (0.11
m2/g cat.) being still lower than for the nickel samples impregnated at pH 4.8
(0.15 and 0.48 m2/gotalyst, respectively).
It is known that a calcination at higher temperatures produces large platinum
crystallites, which are located on the external surface of the zeolite, e.g. [ 251. This
is, surely, the case with the sample [0.3Pt1.8], too. The relatively low external
surface area of the zeolite crystallites and the weak interaction of platinum species
 D. L.. Hoang et al. /Applied Catalysis A: General 114 (I 994) 295-31 I 301

with the silicon rich zeolite surface should have avoided a higher dispersion of the
metal.

Infrared spectroscopy of adsorbed carbon monoxide

Adsorption of carbon monoxide as a probe molecule was followed by IR spec-
troscopy to characterize the state of nickel. Relevant studies of nickel supported on
other carriers have shown that carbon monoxide is adsorbed on metallic nickel in
a linear form with wavenumbers between 2100 and 2000 cm- ’ and in a bridged
form with wavenumbers from 2000 to 1900 cm-‘, e.g. [ 26-291. With high metal
dispersions and especially on zeolites as supports, also surface carbonyl species of
positively charged nickel have been reported, with wavenumbers higher than that
of the stretching vibration of linearly bound carbon monoxide [ 21,27,3&37] .
As an example, Fig. 2 shows the IR spectrum of carbon monoxide adsorbed on
[ 2.ONi4.81 in the region of the CO stretching vibrations. The band at 2210 cm-’
can be assigned to Ni*+ ions coordinated to cation sites in the zeolite pores [ 31-
371. The carbon monoxide adsorbed on these sites is rather weakly bound and is
desorbed already by decreasing the carbon monoxide pressure. The bands at 2136
and 2092 cm-’ appear in all experiments as a doublet with a constant intensity
ratio (2136:2092) of ca. 0.5. These results indicate a dicarbonyl species with the
symmetric and antisymmetric stretching CO vibration at 2136 and 2092 cm-‘,
respectively. With a centre of gravity at 2114 cm-‘, this species should be assigned
to a cationic Ni(CO)*+ complex, localized at cation positions. This has already
been proposed by other authors [ 34-371. The band at 2158 cm- ’ is assigned to

- ii00 2150 2000 1850 1700

WAVENUMBERS. cm -’
Fig. 2. IR spectra of carbon monoxide adsorbed on nickel containing zeolite [ 2.ONi4.81 (a), [ O.SNii.8] (b, c) ,
.@d [ OSNil.8 ] (d) , reduced and outgassed in situ at 500°C. 10 Torr CO were admitted; subsequent evacuations
io 1 Torr (b) and to 1.5.10-’ TOIT (a, c, d) at room temperature lead to observed spectra. The signal between
1800 and 1950 cm-’ is influenced by weak shifts of strong suppoxt absorbances.
302 D.L.. Hoang et al. /Applied CatalysisA: General 114 (1994) 295-311

carbon monoxide adsorbed on framework atoms of the zeolite support [ 441. The
small broad band centred at ca. 2030 cm- ’ and the band at ca. 1903 cm-’ can be
attributed to carbon monoxide adsorbed on metallic nickel in a linear and a bridged
form, respectively [26-291. All bands could be observed with the sample
[ 2.ONi4.81 (curve a) and with the sample [OSNi4.8] (curves b and c) after
calcination and reduction. However, for the sample [ 0.5Ni1.81 (curve d) , the only
one prepared at lower pH, no bands due to carbon monoxide adsorbed on nickel
species are observed. The intensity of the band assigned to metallic nickel ( 1905
cm- ’ ) decreased. However, this band is significantly disturbed by overlapping
lattice vibrations of the zeolite, preventing an unambiguous decision. The complete
disappearance of all the bands indicating ionic nickel is very surprising. As known
from the TPR results (Table 2), this sample contains 97% ionic nickel, whereas
the sample [ O.SNi4.81 contains only 25% ionic nickel. The only conclusion can be
that after impregnation at pH 1.8 the nickel ions are not accessible for the probe
molecule carbon monoxide. As will be discussed later on, we suggest that these
nickel ions are located in hidden positions of the framework. Such positions were
found for nickel in Y zeolites [ 321 and postulated for copper in H-ZSM-5 [ 381.

3.2. Catalyst acidity

IR of adsorbed ammonia
The bands at 1616 cm-’ and 1460 cm-‘, not depicted in this paper, were taken
as a measure for coordinatively bound (Lewis sites, ‘L sites’) and protonated
(Bronsted sites, ‘B sites’) ammonia, respectively [ 541. From the area intensities
of the bands, normalized extinctions were calculated. They are listed in Table 3
(columns 1 and 2). On the basis of the values in column 1 and of the B site
concentration of the parent H-ZSM-5, determined by TPDA, B site concentrations

Table 3
Catalyst acidity determined by TPDA and IR; comparison of measured and expected values

Sample IR of adsorbed ammonia normal- (3) B sites, measured” (4) Ni ions, (5) B sites,
ized extinctions of (from TPDA and IR) exchanged expectedd
(mmol/g cat.) (rnmol/g ~at.)~ (mmol/g cat.)
(1) 1460 cm-’ (2) 1610 cm-’
(B sites) (L sites)

A; [H-ZSM-51 2.1 0 0.62b 0.62b

B; [0.5Ni1.8] 1.8 0 0.53 0.082 0.54
C; [0.5Ni4.8] 1.6 0.09 0.47 0.021 0.60
D; [2.ONi4.8] 1.1 0.38 0.33 0.085 0.53
E; [0.3Pt1.8] 1.8 0 0.53 0 0.62

a Calculated using value ‘b’ (0.62 mmol/g) as a basis and the values from column ( 1) .
bResult of TPDA.
c Calculated from columns (2) and (3) in Table 2.
d Calculated as: ‘b’ (0.62 mmol/g) minus tbe values from column (4).
 D. L Hoang et al. /Applied Catalysis A: General I I4 (I 994) 295-31 I 303

of the catalysts were calculated (column 3). Moreover, we estimated ‘expected’ B

site numbers under the assumption of the exchange stoichiometry H-ZSM-
5 + Ni (OH) + + Ni (OH) + ZSM-5 + H+ .These B site numbers are listed in col-
umn 5 and can be compared with the values in column 3, calculated from lR data.
With [ OSNil.81, the measured and the expected B site concentrations are the
same. But with [ 0.5Ni4.81 and even more so with [ 2.ONi4.81, some differences
are observed, the measured values being significantly below the expected ones.
This means that with the samples impregnated at higherpH, lowerBr@nsted acidities
were found than one would have expected according to the original acidity of the
H-ZSMJ and to degree of exchange.
Nickel in these catalysts predominantly exists as large particles on the external
surface of the zeolite (see foregoing chapter), as nickel oxide before reduction and
as metallic nickel after reduction. We assume that aggregates of nickel species
block some zeolite channels and reduce the accessibility of the interior of the zeolite
crystals for ammonia molecules. This results in too low acidity values. This expla-
nation could be connected with the surprisingly low catalytic activity.
Lewis sites could only be found in the samples impregnated at pH 4.8, with their
number being proportional to the nickel content (Table 3, column 2). These samples
predominantly contain reducible nickel species outside the zeolite crystallites, but
additionally some unreduced and perhaps also some reduced nickel species inside
the channel system. Surprisingly, we could not find any coordinatively bound
ammonia in [0.5Ni1.8], although there is no doubt about the presence of nickel
cations in this catalyst. This behaviour emphasizes the qualitative difference
between the samples prepared at different pH values.

OH vibration spectra
The OH vibration spectra of our parent zeolite, not depicted, exhibited the known
sharp bands of the terminal silanol groups (3740 cm- ‘) and of the bridged OH
groups (3612 cm- ’ ) . Moreover, a shoulder at 3660 cm- ’ was observed, which
can be assigned to OH groups on non-framework alumina [ 391. Hence, our catalysts
contain a certain amount of non-framework alumina, which should be able to
interact with the surface of metallic nickel in a specific way.

3.3. n-Hexane conversion

Fig. 3 summarizes results of n-hexane conversion on the catalysts A-E. The bar
graphs symbolize yields of aromatics, alkanes and alkenes, respectively.

[H-ZTM-51
In nitrogen atmosphere, activity and selectivity of this basis zeolite correspond
to what was found by other authors under the conditions chosen [ 3,4], i.e. com-
parable yields of cracking products and aromatics as well as comparable amounts
of alkanes and alkenes within the cracking products.
304 D.L.. Hoang et al. /Applied Catalysis A: General 114 (1994) 295-311

yield, mol/g*h

lalkanes(Cl-C4)
0.12
FBalkenes(CZC4)
0.10 omatics

0.08

0.08
N2 “2
0.04

0.02

0.00
([t-l-ZSMQ] LO.5Ni 1.81 2.0 Ni 4.81 IO.3 Pt 1.81
Fig. 3. Catalytic results of n-hexane conversion at 500°C in nitrogen and in hydrogen atmosphere, W/F=
4.7 g, hlmol,,,,.

Compared to nitrogen, in hydrogen atmosphere, an essentially higher total activ-

ity and an increased yield of cracking products, but a markedly decreased yield of
aromatics is observed. If assuming exclusively the protolytic carbonium ion mech-
anism and/or the classic carbenium ion mechanism [40,41] as reaction pathways,
this behaviour could not be explained. An action of hydrogenating impurities should
be excluded, because we found no significant differences with H-ZSM-5 samples
of differing purities [ 421. So we assume that with increased hydrogen partial
pressures additional reaction pathways become important, as was proposed recently
[431.

[0.5Nil A]
This catalyst almost exclusively contains nickel as Ni*+ ions. But small amounts
of Ni” could be detected by TPR. Compared to [ H-ZSM-51, its Bronsted acidity is
weakly decreased by the ion exchange.
According to this slight decrease of the acidity, the total activity of the catalyst
is practically equal to that one of H-ZSM-5, but the selectivity towards aromatics
is higher than with the unmodified zeolite. This proves to be true in hydrogen
atmosphere as well as in nitrogen atmosphere.

[0.5Ni4.8] and [2.ONi4.8]

Nickel in these catalysts is mainly localized outside the zeolite crystallites as
metallic nickel. Only a minor part of nickel could exchange Bronsted protons as
nickel cations. The catalytic results are remarkable because of the decreased total
activities and extremely high selectivities towards aromatics. This is best seen with
the catalyst [ OSNi4.81. Another striking catalytic result is the very low cracking
activity of the catalysts, this feature becoming especially obvious by comparison
with [0.3Pt1.8].
 D.L Hoang et al. /Applied Catalysis A: General 114 (1994) 295-311 305

[0.3Pt1.8]
The metal content of this sample is relatively low. The reduced metal has a low
dispersion and should therefore be localized outside the channel system. Hence, a
remarkable change of the acidity of the zeolite by the modification procedure could
not be expected and in fact was not observed.
Consequently, the total activity of [0.3Pt1.8] in nitrogen atmosphere corre-
sponds well to that of the unmodified zeolite, but, as in the case of [ 0.5Ni 1.81, the
selectivity of aromatization is significantly increased at the expense of cracking
products. This can easily be explained by the dehydrogenation activity of platinum.
n-Hexane can undergo a direct dehydrocyclization or primary cracking products
can be dehydrogenated to alkenes, which can be oligomerized, and converted into
aromatics thereupon. Furthermore, we cannot exclude that platinum additionally
acts as a catalyst for the recombination and desorption of H species after a ‘long
distance hydrogen back-spillover’ from the inner to the outer surface of the zeolite
crystals. Such action of metals and semiconductors has been proposed [ 7,8].
In hydrogen atmosphere, the platinum modified catalyst surprises by an
extremely high total activity. The total activity is distinctly the highest of all of the
catalysts investigated and almost reaches a value threefold that of the total activity
in nitrogen atmosphere. This is mainly due to a multifold increase of the cracking
activity. Obviously, the small amount of low dispersed platinum has such a remark-
able hydrogenolysis activity.

4. Discussion

4.1. Role of ‘hidden positions ’

Among the characterization results of our catalysts, three findings with the sample
[ 0.5Ni 1.8 ] are remarkable and need interpretations:
(i) Nickel in this catalyst, which was impregnated at pH 1.8, is practically unred-
ucible below 8OO”C,unlike nickel e.g. in Y zeolites [ 341.
(ii) With ammonia as a probe molecule, unexpectedly no Lewis sites, i.e. no
coordination of ammonia molecules to nickel ions, has been found.
(iii) With carbon monoxide as a probe molecule, unexpectedly no coordination of
carbon monoxide molecules to nickel ions has been found.

Each of these ‘negative’ findings can be assumed to be caused by a special

localization of the nickel cations, leading to low reactivity and/or low accessibility
for probe molecules. Hence, it seems reasonable to look for a more comprehensive
explanation for the three results in this direction.
Recently, reduced reactivity of transition metal cations towards carbon monoxide
as a probe molecule has been observed in Y zeolites [33] as well as in ZSM-5
[ 441. ‘Hidden positions’ were proposed to be responsible for the low reactivity of
306 D.L. Hoang et al. /Applied Catalysis A: General 114 (1994) 295-311

nickel and copper ions, respectively. As hidden positions, e.g. sodalite cages or
hexagonal prisms in the case of Y zeolites and positions in five-membered units,
aside the main channel system, in the case of ZSM-5 zeolite have been proposed.
In the following we shall try to explain the differences in the nickel state and in
the nickel localization in our catalysts in terms of a model involving the assumption
of nickel cations in hidden positions and involving the well-known dependence of
the aggregation state of transition metal ions in aqueous solutions on pH.

[O.SNi1.8]
At the low pH 1.8, relatively small monomeric nickel ions exist in nickel nitrate
solutions in a hydrated state [ 45 ] . Presuming the existence of hidden positions for
nickel ions in H-ZSMJ as mentioned above, these relatively small monomeric ions
could enter the channel system and could preferentially occupy these hidden posi-
tions, because they could reach highly coordinated and especially stable states
there.
It can be imagined that nickel ions in such stable positions are hardly reducible
and give TPR signals only at very high temperatures, possibly after the thermal
decomposition of the zeolite structure. Moreover, they are protected there against
the attack of probe molecules like ammonia or carbon monoxide. Hence, it is
understandable that with the catalyst [0.5Ni1.8] no IR peaks of ammonia and
carbon monoxide, coordinated to nickel ions, could be observed.

[0.5Ni4.8] and L2.ONi4.81

In contrast to the sample [0.5Ni1.8], the major part of the nickel in these two
catalysts, impregnated at the higher pH 4.8, is reducible and is surely located outside
the channel system after reduction. Obviously, most of the nickel cations were not
able to reach and to occupy the stabilizing hidden positions.
It is well known that the tendency of transition metal cations to form dimeric or
polymeric ‘polyoxo cations’ increases with increasing PH. At pH values higher
than 3.5, nickel salt solutions predominantly contain tetrameric nickel ions [ 451.
The accessibility of the main channel system for such large ions should be heavily
reduced, perhaps be impossible. Hidden positions surely are inaccessible for such
ions. Hence, as has been found, the major part of the nickel ions remains outside
the main channel system. Only a minor part, perhaps nickel ions of a lower degree
of aggregation, can enter the main channels, but cannot occupy hidden positions.
During the calcination, nickel oxide crystallites are formed on the outer zeolite
surface from the tetrameric nickel ions outside the channels and perhaps also from
some nickel species, which migrated from the main channels to the outer surface.
These nickel oxide crystallites are reducible and therefore detectable by TPR. The
TPR of the minor part of the nickel, which remained inside the main channels, but
outside the hidden positions, results in different oxidation states between Ni*+ and
Ni’. All these species are accessible for probe molecules like ammonia or carbon
monoxide. Therefore these samples exhibit IR bands of coordinatively bound
 D. L. Hoang et al. /Applied Catalysis A: General I14 (1994) 295-31 I 307

pH 1.8 pH 4.8
(Monomeric Ni 2+ ions exist in (Tetrameric Ni cations exist in the
the impregnation solution, which impreguation solution, which are too
can enter the hidden positions) large to enter the hidden positions.)

Fig. 4. Nickel species and their localization in catalysts impregnated at different pH.

ammonia and bands of carbon monoxide, bound to the different nickel species.
The scheme in Fig. 4 illustrates the nickel species and their position in catalysts
impregnated at pH 1.8 and pH 4.8, respectively.

4.2. Action of the nickel species

[H-234-5]
In our basis catalyst [ H-ZSM-51, Bronsted protons are available to catalyze the
conversion of n-hexane. n-Hexane molecules are cracked, according to the carbo-
nium ion mechanism [40] and/or to the classic carbenium ion mechanism [41].
Olefinic intermediates are oligomerized, cyclisized and finally dehydrogenated to
aromatics [ l-51. As a result, in nitrogen atmosphere comparable amounts of aro-
matics and cracking products are detected, in accordance with former investigations
[ 41. In hydrogen atmosphere, increased cracking and decreased aromatization is
observed. This is compatible with the recent investigation [ 431.

[0.5Ni1.8]
The [ 0.5Nil.81 catalyst, which was impregnated at low pH, contains nickel
predominantly as nickel ions in hidden positions. Its catalytic properties differ from
[H-ZSM-51 by an increased selectivity for aromatics, in nitrogen as well as in
hydrogen atmosphere.
It is well known that some metal cations are able to activate alkane molecules.
By hydrogen abstraction they act as dehydrogenating Lewis sites. According to
refs. [ 46-491, this can be described as follows:
( 1) H abstraction on a Lewis site:
C,H,,+,+L-+C,H,,+,+L-H+
(2) Lewis site regeneration:
308 D.L. Hoang et al. /Applied Catalysis A: General 114 (1994) 295-311

L-H+ +H+ +L+H,

( 3) Proton release from the formed carbenium:
C,H*, + I +C,H,,+H+.
Nickel ions should react in the same way. Therefore, a synergism between Bransted
sites and nickel Lewis sites could increase the dehydrogenation activity and con-
sequently the aromatization.
It should be explained, why the nickel ions, although located in hidden positions,
nevertheless are active in catalysis. In face of our IR results, we proposed above
that the formation of surface complexes with carbon monoxide and ammonia is
sterically hindered. However, one could imagine that the spacious requirements for
the hydrogen abstraction and the corresponding nickel-hydrogen complex are lower
than for the formation of complexes with carbon monoxide or ammonia. Therefore,
the nickel ions could take part in the catalytic reaction. Moreover, the reaction
temperature is considerably higher than the temperatures applied with the CO-IR
and TPDA investigations.

[OSNi4.8] and 12.ONi4.81

These catalysts [0.5Ni4.8] and [2.ONi4.8] were impregnated at higher pH.
Nickel in these catalysts mainly exists as relatively large metallic nickel particles
outside the zeolite crystallites. A minor part of nickel exists as ions and is located
at accessible positions in the main channels. In the following, we will try to explain
three remarkable results of the catalytic characterization of these two samples,
namely:
(i) the decreased total activity of these samples,
(ii) the extremely high aromatization selectivities, especially of [ 0.5Ni4.81 and
(iii) the obviously missing hydrogenolysis activity of nickel in these catalysts.

The total activity of [ 0.5Ni4.81 in nitrogen atmosphere is distinctly below that

which one would have expected taking into account the Brcdnsted acidity of this
sample: The expected B site concentration, estimated under the assumption of an
exchange of protons by Ni (OH) + ions, amounts to 0.60 mmol/g (Table 3, column
5) and differs hardly from the corresponding value of the original H-ZSM-5 (0.62
mmol/g). Hence, the low total activity of [ 0.5Ni4.81 cannot be due to the loss of
acidity by the ion exchange. The catalytic activity of [0.5Ni4.8] is even smaller
than could be estimated on the basis of the B site concentration measured by NH3-
IR (0.47 mmol/g; Table 3, column 3), although this value is probably too low
because of pore blocking. The low total activity is all the more surprising consid-
ering the presence of nickel species, which should be able to give an additional
contribution to the original catalytic activity of the basis zeolite H-ZSM-5.
The cracking activity of [ 0.5Ni4.81 is extremely low. Comparing this minimum
cracking activity with that of the unmodified [ H-ZSM-51, which contains only B
sites, one gets a clue for that portion of the total activity connected with the B sites
inside the nickel modified catalyst. This amount seems to be rather low. Hence, one
 D.L. Hoang et al. /Applied Catalysis A: General 114 (1994) 295-311 309

can suspect that the interior of the zeolite crystallites is only to a minor degree
accessible for hydrocarbon molecules. In accordance with our explanation for the
unexpectedly low Bronsted acidity of the samples [ 0.5Ni4.81 and [ 2.ONi4.81, it
seems plausible to assume that pore blocking by nickel species is responsible for
the reduced accessibility of the main channel system and for the low total activity.
Assuming an only low portion of B site catalyzed activity (see above), the nickel
species outside the zeolite crystallites must essentially contribute to the total activ-
ity. This is easily explained by the assumption that the reduced nickel on the outer
surface of the zeolite particles is very active in a stepwise dehydrogenation and
final dehydrocyclization of n-hexane.
The most striking catalytic feature of the catalysts impregnated at pH 4.8 is their
low (or missing) hydrogenolysis activity in hydrogen atmosphere, especially if
compared with that one of the platinum modified sample [ 0.3Rl.8]. Metallic nickel
is a typical hydrogenolysis catalyst and its metallic surface area in [ OSNi4.81 (0.15
m2/g) and in [2.ONi4.8] (0.48 m*/g) is even higher than that of [ 0.3Pt1.81.
Nevertheless, the hydrogenolysis activity of [ 2.0Ni4.8 J must be, if any, several
times lower than that of [0.3Ptl.8].
One must conclude that the surface of the reduced nickel in these samples is
modified in a specific manner. Obviously the surface remained able to catalyze
structure insensitive reactions like dehydrogenation, but lost its ability to catalyze
structure sensitive reactions like hydrogenolysis.
It is well known that nickel aluminate species are hardly reducible and that
aluminate species can decorate the surface of nickel crystallites, in that way chang-
ing their properties [ 20,24,33,50,51]. In [ 20,241, we assumed that such a deco-
ration is responsible for diminished hydrogenolysis activity. In our [0.5Ni4.8]
catalyst, nickel as well as non-framework alumina exist. Thus, it can be suspected
that traces of nickel aluminate species are formed under calcination conditions.
These species can decorate the surface of the nickel crystallites formed during the
catalyst reduction, generating an ‘ensemble effect’. By this effect, large nickel
ensembles, able to catalyze the structure sensitive hydrogenolysis, are destroyed.
But the structure insensitive dehydrogenation is hardly influenced. Because of the
missing competing hydrogenolysis, the nickel surface is especially active in the
dehydrogenation of alkanes, supplying the reaction mixture with alkenes, as pre-
cursors of aromatics, very effectively.
As an alternative to the above geometric interpretation, a modification of nickel
by the formation of nickel-proton adducts like in metal/H-Y systems [52,53],
resulting in an electron deficient state of the metal, cannot be excluded. Nickel
might have lost its hydrogenolysis activity by this electronic interaction. Further
efforts are necessary to clear, whether such electronic interpretation can also be
applied to metal/H-ZSM-5 systems with higher Si/Al ratios.
310 D.L. Hoang et al. /Applied Catalysis A: General 114 (1994) 295-311

5. Conclusions

-The impregnation of H-ZSM-5 with nickel nitrate leads, depending on pH of

the impregnation solution, to different states of nickel, with the catalytic properties
being significantly influenced by these states.
- Ni/H-ZSM-5 catalysts impregnated at low pH contain nickel ions, which are
unreducible and not detectable by the probe molecules carbon monoxide and ammo-
nia. Nickel causes an increased aromatization selectivity. Interpretation: At low
pH, monomeric nickel ions exist in nickel nitrate solutions. These are able to
exchange Bronsted protons and to enter narrow hidden positions aside the ZSM-5
main channels. In these positions, they reach a stable coordination and are hardly
reducible. The coordination with carbon monoxide and ammonia is sterically hin-
dered, but not with hydrogen. Therefore these nickel ions can act as dehydroge-
nating Lewis sites, resulting in an increased aromatization.
- Ni/H-ZSM-5 catalysts impregnated ut higherpHpredominantly contain large
metallic nickel crystallites outside the zeolite crystals, besides a minor portion of
ionic nickel inside the channels. The selectivity to aromatics of these samples is
extremely high. Interpretation: At higher pH, the nickel ions exist as large tetra-
meric polyoxo cations and are not able to enter the stabilizing hidden positions.
The extremely high aromatization selectivity is caused by several reasons. Metallic
nickel catalyzes a direct aromatization of n-hexane via a stepwise dehydrogenation
and final dehydrocyclization. Moreover, the catalytic action of the cracking B sites
inside the zeolite channels seems to be decreased, due to some pore blocking by
metallic nickel. Finally, metallic nickel could possibly promote the portion of acid-
catalyzed aromatization by a ‘long distance hydrogen back-spillover’.
-The metallic nickel outside the zeolite crystals lost its hydrogenolysis activity,
probably as a consequence of an ‘ensemble effect’, caused by aluminium species,
which decorate the metallic nickel surface, or by the formation of metal-proton
adducts, being unable to catalyze hydrogenolysis reactions.

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