Applied Catalysis A: General 358 (2009) 103109

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Applied Catalysis A: General

journal homepage: www.elsevier.com/locate/apcata

Contribution of hydrogen spillover to the hydrogenation of naphthalene over

diluted Pt/RHO catalysts
Honglin Chen a, Hong Yang a,*, Oladipo Omotoso b, Lianhui Ding a,

Yevgenia Briker a, Ying Zheng c, Zbigniew Ring a

a

The National Centre for Upgrading Technology, 1 Oil Patch Drive, Devon, T9G 1A8, AB, Canada
Advance Separation Technologies, 1 Oil Patch Drive, Devon, T9G 1A8, AB, Canada
c
Department of Chemical Engineering, University of New Brunswick, Fredericton, E3B 5A3, NB, Canada
b

A R T I C L E I N F O

A B S T R A C T

Article history:
Received 21 February 2008
Received in revised form 24 November 2008
Accepted 5 December 2008
Available online 20 February 2009

This paper presents the contribution of hydrogen spillover to the hydrogenation of naphthalene over Pt/
RHO catalysts. Platinum supported on RHO zeolite was prepared by adding a Pt precursor to the
synthesis gel of RHO zeolite. Pt/RHO catalysts were characterized by XRD, TEM, TPR and XPS. The
hydrogenation activity was tested using 1-hexene, 1-cyclohexene and naphthalene as model
compounds. XRD and TEM results indicated that incorporating Pt precursors into the synthesis gel
did not affect the crystal structure and the morphology of the RHO zeolite. TPR, XPS and hydrogenation
tests revealed that Pt particles were located in both RHO cages and intrazeolite spaces. In Pt/RHO
containing lower levels of cesium, a small amount of Pt was also located on the external surface of the
zeolite. The contribution of hydrogen spillover over hybrid Pt/RHO_H-Y zeolite catalysts was examined
in naphthalene hydrogenation. Naphthalene conversion increased from 21% over a Pt/RHO catalyst to
91% over Pt/RHO diluted with H-Y zeolite, clearly demonstrating the positive effect of hydrogen spillover
on the hydrogenation reaction.
Crown Copyright 2009 Published by Elsevier B.V. All rights reserved.

Keywords:
Pt/RHO
Hydrogen spillover
Hydrogenation
1-Hexene
Cyclohexene and naphthalene

1. Introduction
Hydrogen spillover refers to the migration of surface hydrogen
species produced by the dissociation of hydrogen molecules on
metal sites to an oxide support that has no activity for dissociative
hydrogen adsorption under the same conditions. The materials
generating the spillover hydrogen species and providing the sites
for the adsorption of the spillover hydrogen species are called
activators and acceptors, respectively [13]. While the phenomenon of hydrogen spillover is well conrmed, some ambiguities
still exist as to whether the spillover hydrogen species can produce
substantial catalytic effects on the support, and enhance the
chemical reactions.
Early evidence of hydrogen spillover was reported by Khoobiar
in 1964. When hydrogen was passed through a mechanical
mixture of 0.5% Pt/Al2O3 and WO3 at room temperature, the color
of WO3 changed to blue, indicating the reduction of WO3 to W4O11
by spillover hydrogen, this phenomenon was not observed over
Al2O3 and WO3 mixture in the absence of platinum [4]. Teichner
published a review on the impact of hydrogen and oxygen spillover

* Corresponding author.
E-mail address: hong.yang@bp.com (H. Yang).

on catalysis. His work summarized the effect of spillover on

catalytic reactions prior to 1989, and he concluded that the
spillover species could impact the catalytic reaction in four
different ways: (1) create a new type of reactive surface; (2) create
a new path for the catalytic reaction by modifying the reaction
intermediates; (3) clean the active sites, which were poisoned by
coke or other poisoning substances; (4) reactivate the catalytic
sites, which experienced reduced reactivity by a secondary effect of
reactants [5]. Over the past two decades, the synergy of the
hydrogen spillover activators and acceptors in catalysis has been
subjected to numerous studies [612].
An example of hydrogen spillover was given by Ohgoshi et al.
[6]. The authors investigated isobutylene hydrogenation over Pt/
KA-zeolite and Pt/KA-zeolite mixed with NaY zeolite. Pt/KA-zeolite
and NaY both had negligible hydrogenation activity because
isobutylene is too large to access the metal sites inside the zeolite
pores, and H2 cannot be activated on NaY zeolite. However, a 93%
yield of isobutane was obtained over a hybrid catalyst. Clearly,
hydrogen was activated on the Pt/KA-zeolite, and the resulting
hydrogen species spilt over to the NaY zeolite where isobutylene
was hydrogenated. Simon et al. [7] investigated the reaction path
for benzene hydrogenation over Pt supported on mordenites, they
found that hydrogenation of benzene on Pt/NaH mordenite
occurred along two parallel pathways. The rst one was the

0926-860X/$ see front matter . Crown Copyright 2009 Published by Elsevier B.V. All rights reserved.
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H. Chen et al. / Applied Catalysis A: General 358 (2009) 103109

hydrogenation of benzene on the metal sites and the second was

the hydrogenation of benzene bounded to Brnsted acid sites via
spillover hydrogen from the close metal surface. In the presence of
thiophene, the metal sites were poisoned while the active sites
involving Brnsted acid were more tolerant to sulfur poisoning. In
both examples, new active sties were created on the supports by
spillover hydrogen.
In another work, Baumgarten and Maschke investigated
hydrogen spillover through gas phase using a reactor with two
compartments separated by an empty space; one compartment
contained the catalyst (metal/alumina) and the other compartment contained graphite or activated carbon [8]. Their results
indicated that the spillover hydrogen generated over metal
supported on alumina could diffuse through gas phase and
convert the graphite or activated carbon into methane. Wang
et al. [9] studied the hydrogenation of benzene, toluene and oxylene over Pt/Al2O3 diluted by powder or granular forms of silica,
alumina, MgO, ultrastable Y zeolite, HAlMCM-41 and WO3/Pt/
Al2O3. They found that the overall aromatic conversion was
remarkably enhanced by either acidic supports such as Y zeolite
and HAlMCM-41 or an n-type semiconductor (WO3) although the
diluents were inactive under the same conditions. They claimed
that the aromatic molecule was adsorbed in the form of carbonium
ion over acidic diluents, and hydrogenated by spillover hydrogen.
For WO3 as diluent, spillover hydrogen created coordinated
unsaturated tungsten sites, on which the aromatic molecule was
adsorbed and hydrogenated by spillover hydrogen.
Despite numerous positive contributions published on
hydrogen spillover, several contrary results were also reported
[1315]. In a study of hydrogenation and deuterium exchange of
ethylbenzene by spillover hydrogen over a Pt/NaA-zeolite and
H-USY system, Miller and Pei observed that spillover hydrogen
resulted in only isotopic exchange, not aromatic saturation [13].
Vannice and Neikam investigated the benzene hydrogenation
reaction over a Pd/Al2O3 catalyst mixed with different proportions of Al2O3. The reaction was conducted at a hydrogen
pressure of 1 atm and 150 8C. The turnover numbers (molecules
of benzene reacted/Pdsurface sec) were almost constant when the
ratio of Al2O3:Pd/Al2O3 changed from 0:1 to 227:1. Therefore
they concluded that hydrogen spillover did not play any role
in the hydrogenation of benzene under the conditions studied
[14].
In order to clarify these ambiguities, the contribution of
hydrogen spillover has been investigated over Pt supported on
various types of supports in our research centre. In continuation to
our published work on the contribution of spillover hydrogen to
the hydrogenation of naphthalene over Pt/KA zeolite and the
hydrogenation of 1-hexene on Pt/CMS (carbon molecular sieve)
[16,17], the present work examines the effect of hydrogen spillover
on the hydrogenation of naphthalene over Pt/RHO zeolite diluted
with H-Y zeolite. The results reveal once more that hydrogenation
activity can be signicantly enhanced by spillover hydrogen
species.
2. Experimental
2.1. Materials
1-Hexene, cyclohexene, naphthalene, n-hexadecane, colloid
silica (LUDOX1 HS30, 30 wt% suspension in water), cesium
hydroxide aqueous solution (CsOH; 50 wt%) were all purchased
from SigmaAldrich (Oakville, ON). Platinum (II) tetramine
chloride [Pt(NH3)4Cl2] was purchased from Alfa Aesar (Ward Hill,
MA). H-Y zeolite (CBV720) was obtained from Zeolyst International
(PA, US). Alumina (boehmite, Catapal1 B alumina) was obtained
from Sasol North America Inc.

2.2. Catalyst preparation

Pt/RHO was synthesized using boehmite and colloid silica as Al
and Si sources, respectively. A blank RHO zeolite (RHO-B) was
synthesized according to the following procedure: 4.67 g of
alumina was dissolved in a sodium hydroxide solution (13N)
and stirred at 80 8C for 30 min. When this solution cooled to room
temperature, 12 g of cesium hydroxide solution was added and
stirred for another 10 min. Then 100 g of colloidal silica was added
to the solution to form a gel. After thorough homogenization, the
gel was aged for 24 h at room temperature followed by heating for
6 days at 80 8C under static conditions. For the synthesis of Pt/RHO,
Pt(NH3)4Cl2 solution (0.44 g of Pt(NH3)4Cl2 in 3.00 mL of deionized
H2O) was added to the mixture of sodium hydroxide, alumina and
cesium hydroxide and stirred for 30 min at room temperature prior
to the addition of colloidal silica. Two Pt/RHO catalysts were
synthesized, the rst one had a lower Cs/(Cs + Na) molar ratio
(0.09) and the second one had a higher Cs/(Cs + Na) ratio (0.12).
The Pt/RHOs were labeled as Pt/RHO-LCs and Pt/RHO-HCs,
respectively. The solid product was centrifuged and washed
repeatedly with deionized water and dried at room temperature
for several days. All the catalysts were calcined at 400 8C for 2 h
before characterization and hydrogenation testing. Table 1 summarizes the initial synthesis compositions.
2.3. Catalyst characterization
The crystal structures of RHO and Pt/RHOs were conrmed by
X-ray diffraction analysis using a Bruker D8 Advance, equipped
with multilayer optics for Co X-ray on the incident and diffracted
beam sides. Diffraction data was collected between 58 and 958 2u
with 0.028 step size. Samples were allowed to equilibrate at 20%
room humidity prior to analysis. The level of impurities, degree of
crystallinity and structural parameters were rened using the
Rietveld method implemented in TOPASTM. The bulk elemental
composition (Pt, Al, Si, Na and Cs) was measured by X-ray
uorescence (XRF) using a Bruker S4 Explorer equipped with a
wavelength dispersive spectrometer. The samples were dried at
105 8C for 2 h and subsequently ashed in air at 1000 8C for 6 h. The
ashed samples were fused with 50:50 Li-metaborate and Litetraborate mixture, with LiBr as wetting agent. Certied reference
mineral standards were used to generate calibration curves for
quantitative analysis.
Temperature programmed reduction (TPR) study was carried
out with Micromeritics Autochem 2920 unit, equipped with a
thermal conductivity detector (TCD). The sample (0.3 g) was rst
dried in situ at 300 8C for 1.5 h with a constant ow of Ar (50 mL/
min). TPR was performed using 10% H2 in Ar with a ow rate of
50 mL/min, heating from about 35 to 600 8C at a ramping rate of
5 8C/min, it was then held at 600 8C for 1.5 h. Water was trapped in
a cold trap immersed in acetone and dry ice.
A Philips EM420 transmission electron microscope, operated at
120 kV, was used to investigate the samples microstructures.
Calcined and pre-reduced catalysts (reduced at 400 8C for 6 h at a
ramping rate of 2 8C/min), were suspended in ethanol and
ultrasonically dispersed. Drops of the dispersions were applied
on a copper grid-supported carbon lm.
Table 1
Synthesis conditions of zeolite RHO and Pt/RHO.
Catalysts

Molar composition of synthesis gel

Cs/(Cs + Na)

Na2O:Cs2O:Al2O3:SiO:H22O:Pt(NH3)4Cl2
RHO-B
Pt/RHO-LCs
Pt/RHO-HCs

4.55:0.61:1.00:15.17:169.05:0
4.59:0.45:1.00:15.17:169.05:0.038
4.55:0.61:1.00:15.17:169.05:0.038

0.12
0.09
0.12

H. Chen et al. / Applied Catalysis A: General 358 (2009) 103109

A Leybold Max200 X-ray photoelectron spectrometer (XPS) was

used for analyzing the surface compositions of the catalysts. Al Ka
(1486 eV) was used as the photon source for all samples. The Al Ka
was generated at 15 kV and 20 mA. The pass energy for the survey
scan was set at 192 eV and for the narrow scan it was 48 eV.
Exposure of the samples to ambient atmosphere was minimized by
transferring the samples in the vacuum. All XPS spectra were
corrected to the C1 s peak at 285.0 eV.
2.4. Hydrogenation reaction
All the catalysts were pre-reduced in AutoChem 2920 at 400 8C
for 6 h (2 8C/min) with 10% H2 in argon prior to hydrogenation test.
The gas phase system for the hydrogenation of 1-hexene and
cyclohexene is shown in Fig. 1. A stainless steel U-tubular reactor
(1.0 cm i.d. with each arm of 10.0 cm length) was used. 0.20 g of
catalyst was mixed with glass beads (6080 mesh to make up a
total volume of 2 mL. The catalyst mixture was loaded in the
middle of one arm; the other arm was lled with glass beads. The
reactor was kept in a water bath at 50  1 8C. Hydrogen gas
(20 mL min 1, NTP) was used as a carrier and simultaneously as a
reactant. The feed (1-hexene or cyclohexene) was held in a bubbler at
20 8C and introduced into the reactor via continuous hydrogen ow.
The gaseous reaction products were condensed in a cold trap
(acetone + dry ice). The condensed products were diluted with
hexadecane and analyzed by GC-FIMS.
Hydrogenation of naphthalene (5% naphthalene in n-hexadecane) was carried out in a 300 mL batch reactor (EZE-Seal,
Autoclave Engineers). Two congurations were tested for every
catalyst, in this case: (1) Pt/RHO alone, Pt/RHO powder was
palletized, crushed and sieved to 50100 mesh; (2) Pt/RHO was
mixed with H-Y zeolite in 1:1 mass ratio, the mixture was
palletized, crushed and sieved into 50100 mesh. The pre-reduced
catalyst (0.5 g for Pt/RHO and 1.0 g for Pt/RHO diluted with H-Y
zeolite) and 100 mL naphthalene solution were added to the
autoclave. The sealed reactor was rst purged with nitrogen; it was
pressurized with hydrogen to 550 psig at ambient temperature.
The autoclave was heated to the reaction temperature by an
electric furnace with a stirring speed of 480 rpm. Once the desired
temperature (300 8C) was reached, the reactor was maintained at
reaction temperature for 3 h under stirring. The reactor pressure at
this temperature was 1015 psig. At the end of hydrogenation, the
reactor was cooled down to room temperature. The liquid product
was ltered and analyzed by HPLC.
For GC-FIMS analyses, a 30 m  250 mm  0.25 mm HP1-MS
non-bonded column was used. The injection (0.2 mL; 19:1 split)
was made with the oven at 45 8C. The oven was heated at 10 8C/min
to 300 8C. After the completion of the run, the masses for hexane
(86), hexene (84), cyclohexene (82) and cyclohexane (84) were
extracted. The peaks of these compounds were integrated and the
concentrations of the corresponding compounds were calculated
using the response factors obtained from analyzing the model
compound standards at the identical conditions. For HPLC
analyses, a Water HPLC unit equipped with a Partisil 5 PAC

105

column (Wharman) and a refractive index detector was used with

100% n-heptane as the mobile phase. Since only four general
hydrocarbon groups poly-aromatics, di-aromatics, mono-aromatics and saturates could be identied by the HPLC method
employed, we could only follow the conversion of naphthalene and
production of tetralin. We were uncertain about the formation of
decalin as the results of tetralin saturation, since it eluted together
with n-hexadecane as saturate. Naphthalene conversion was used
to calculate the turnover frequency (TOF) assuming rst-order
kinetics for the hydrogenation reaction to compare the catalyst
activity based on Pt content.
3. Results and discussion
3.1. RHO compositions, structure and morphology
Robson et al. [18] investigated the effect of the initial
composition on the crystal structure of RHO zeolite, they found
that a Cs/(Cs + Na) ratio between 0.06 and 0.15 yielded purer
samples and 0.12 was the most preferable value. Higher CsOH
content resulted in the appearance of chabazite and pollucite,
lower CsOH gave faujasite. Anderson et al. [19] obtained high
purity of RHO zeolite by controlling the heating period and aging
time of the mother gel. They found that the heating period could
vary considerably depending on homogeneity of the initial gel.
According to the published results, two initial Cs/(Cs + Na) values
(0.09 and 0.12) were used in this work. The synthesis gel was rst
stirred over night at room temperature to achieve maximum
homogeneity; it was then incubated at 20 8C for 1 day and then
crystallized at 80 8C for 6 days under static condition. Highly

crystalline centric (Im3m)

zeolite RHO with rhombododecahedral
morphology was obtained with small amounts of pollucite and
chabazite in this study. The nal bulk elemental compositions of
RHO and Pt/RHOs are given in Table 2. The data also show that
higher Cs content in the synthesis gel results in lower Pt
incorporation, which probably implies that Pt and Cs competes
the same site in RHO zeolite. Rietveld renement results of the
RHO structure [30] are given in Table 3. Renement of the extra
framework cations occupation factors resulted in the largest
parameter shift and the lowest weighted R-factor. RHO-B, Pt/RHOLCs and Pt/RHO-HCs rened to Cs/(Cs + Na) ratio of 0.6 which is
close to the nal composition of RHOs showed in Table 2. The
introduction of Pt in the synthesis gel did not appear to have any
signicant effect on the structure. The presence of impurity phases
and non-crystalline content (from the degree of crystallinity given
in Table 3) preclude the use the bulk elemental composition to
improve the chances of locating Pt in the D8R sites. The X-ray
diffraction patterns of RHO-B, Pt/RHO-LCs and Pt/RHO-HCs are
shown in Fig. 2. No metallic Pt and Pt oxide were observed within
the detection limit of the diffractometer. These results are in a good
agreement with these obtained by Altwasser et al. [20] in the
preparation of 0.8 wt% Ru/RHO by adding RuCl3 to the synthesis
gel. They stated that addition of Ru precursor to the synthesis gel
had no effect on the crystal structure of RHO, and at the same time
X-ray amorphous ruthenium species with particle size in the order
of 1 nm or less was achieved. The TEM images of RHO-B, Pt/RHOLCs and Pt/RHO-HCs are presented in Fig. 3ac. Pt/RHOs are of the
same morphology (rhombododecahedral crystals) and similar size
Table 2
Final elemental composition of Pt/RHO zeolites.

Fig. 1. Gas phase hydrogenation reaction system.

Catalysts

Pt (wt%)

Na2O:CsO:Al22O3:SiO2:Pt (mol ratio)

Cs/(Cs + Na)

RHO-B
Pt/RHO-LCs
Pt/RHO-HCs

0
0.37
0.24

0.52:0.40:1.00:6.17:0.00
0.62:0.36:1.00:6.05:0.013
0.53:0.46:1.00:6.14:0.008

0.43
0.37
0.46

H. Chen et al. / Applied Catalysis A: General 358 (2009) 103109

106

Table 3
Rened occupation parameters for RHO, and Pt-RHOs (starting the structure for Rietveld renement taken from Ref. [30]).

Space group (rho)

Cell parameter (A) rho
2
wRp, x (rho)
% pollucite
% chabazite
Na 16f
Cs 12e
OH1 48k
OH2 48k
OH3 96l
OH4 12e
OH5 2a
Chemical formula from structure renement
Degree of crystallinity (%)

RHO-B

Pt-RHO-LCs

Pt-RHO-HCs

Im3m
15.0644(1)
0.11, 3.4
1.1
1.7
0.162(8)
0.321(3)
0.182(8)
0.460(6)
0.302(3)
0.776(2)
0.80(3)
(Na2.6Cs3.8
70H2O) Si36Al12O96
77

Im3m
15.0627(1)
0.10, 2.8
0.3
0.8
0.131(7)
0.289(2)
0.164(7)
0.437(6)
0.307(2)
0.82(1)
0.84(3)
(Na2.1Cs3.5
70H2O) Si36Al12O96
82

Im3m
15.0581(2)
0.11, 2.5
1.7
0.9
0.159(9)
0.321(3)
0.194(9)
0.470(7)
0.308(3)
0.78(2)
0.84(3)
(Na2.6Cs3.9
73H2O) Si36Al12O962
82

(less than 1 mm) as that of platinum free RHO-B. No differences

were observed for the calcined and reduced Pt/RHOs (Fig. 3d).
3.2. Location of Pt particles
Pt has been successfully encapsulated in the cages of NaA
zeolite and used as shape selective catalysts [6,16,21]. The main
objective of adding Pt precursors to the initial synthesis mixture is
to incorporate Pt particles into RHO cages. The framework topology
space group with a
of zeolite RHO corresponds to the cubic Im3m
unit cell consisting of an a-cage, which is connected to six
neighboring cells via double eight-rings along the octahedral
directions [22]. The primary structural difference of RHO zeolite in
comparison with NaA zeolite (LTA) is that the former is a 3dimensional network of a-cages (cubo-octahedra) connecting to
each other by octagonal prisms, whereas in the latter case, beta
(sodalite) cages are connected to each other by cubic prisms
(Fig. 4). In RHO, the pore opening of the a-cage is 0.36 nm, slightly
smaller than that of NaA (0.41 nm). In RHO, three sites with unique
coordination environments can accommodate the extra-framework cations: the single eight-ring (S8R), the single six-ring (S6R)
and the double eight-rings (D8R) sites. Each site has a distinct
coordination environment, and cations preferentially occupy one
of these sites depending upon their ionic radii and the water
content [23,24]. Techniques such as XRD, TPRXPS and hydrogenation reaction have been employed in the present work to
investigate the location of the Pt particles.

Fig. 2. XRD patterns of RHO-B and Pt/RHOs.

The locations of Pt particles in zeolites Y, b, L and ZSM-5 have

been successfully characterized by TPR technique [2528]. Park
et al. [25] and Foger et al. [26] found that platinum ions in the
supercage of Y zeolite were reduced at a lower temperature
(Tr = 100 8C) than those in the sodalite cage or in the hexagonal
prism (Tr = 250 8C). The platinum oxides located on the external
surface were reduced near or below the room temperature [27,28].
To our knowledge, there is no result published on the TPR of Pt
supported on RHO. The Pt/RHO catalysts used in this work were
calcined at 400 8C for 2 h prior to the TPR experiments. The TPR
experiment were conducted from 35 to 600 8C at a ramping rate of
5 8C/min. Fig. 5 presents the TPR proles of RHO-B, Pt/RHO-LCs and
Pt/RHO-HCs. Quantitative results are summarized in Table 4. There
is non-reduction peak for the platinum-free RHO (RHO-B), whereas
a low temperature peak at about 170210 8C and a high
temperature peak at about 370450 8C are detected for Pt/RHOLCs and Pt/RHO-HCs. From the structural characteristics of RHO
and the hydrogenation test results discussed below, we believe
that the low temperature peak attributes to the reduction of Pt
particles situated between zeolite crystals or Pt particles situated
in mesopores or channels due to the structure defect; the high
temperature is due to the Pt particles in a-cage or D8R prism.
Table 4 also shows that the total H2/Pt is between 1 and 2 for both
catalysts which indicates that Pt species exist in both Pt2+ and Pt4+
oxidation states. Due to the space constrain, Pt ions located in D8R
prism may coordinate to SiOAl and form Pt4+ species. In RHO, the
a-cages are directly connected by D8R prism through 8-member
ring, the facile migration cations between a-cages and the D8R
might be responsible for the comparable reducibility of Pt particles
in a-cage or D8R prism.
The cations relocation in RHO has been observed by several
research groups [24,29,30]. Lee et al. [23] using in situ synchrotron
X-ray and neutron powder diffraction studies found that upon
heating, cations exchanged into zeolite RHO underwent large shifts
in their positions within the pores. In the fully hydrated RHO, all
the divalent cations investigated (Ca2+, Sr2+, Ba2+, Pb2+, and Cd2+)
resided in the a-cage near the S8R site. When RHO was partially
dehydrated after heating up to 100 8C, the unbound water was lost
from the a-cage, which did not affect signicantly the cations
position. However, when heated from 200 to 400 8C, the water in
the D8R prism was removed, which resulted in a migration of
cations from the S8R sites to the D8R prism sites. Change of RHO
framework from the centric form to the distorted acentric form
was always accompanied with the relocation of cations from the acage to the D8R.
Bieniok and Baur [29] observed that the Sr-exchanged RHO
changed from a high temperature form with a contraction of unit
cell volume after heating from 100 to 200 8C under a vacuum.
Rietveld-type renement of the RHO structure (Powder X-ray

H. Chen et al. / Applied Catalysis A: General 358 (2009) 103109

107

Fig. 3. TEM images of RHO-B (a), Pt/RHO-LCs (b), Pt/RHO-HCs (c) and Pt/RHO-HCs reduced at 400 8C for 6 h (d).

diffraction data) showed that the two forms differed in the

distribution of Sr atoms. In the low temperature form, Sr atoms
were located in the S8R sites, and in the high temperature form, the
Sr atoms migrated to the middle the D8R prism and pulled them
together, which resulted in a contraction of unit cell. All this
evidence of cations migration supports our assumption that
hydrogen reduction of Pt2+ or Pt4+ in a-cage and in the D8R prism
are indistinguishable. Our result is in good agreement with the
published ndings for Y zeolite [25]. The authors suggested that Pt
particles in hexagonal prism and sodalite cage were more difcult
to reduce over those in the supercage. In Y zeolite, the supercage is
formed by 10 sodalite cages connecting through hexagonal prisms.
The main opening of the supercage is a 12-member ring, although
it can also be accessed via a 6-member ring from the sodalite cage
and via a 4-member ring from the hexagonal prism. Due to the
smaller openings connecting to the supercages from hexagonal
prism and sodalite cage in Y zeolite, it is reasonable to assume that
cations in Y zeolite are less mobile than these in RHO. As a
consequence, the reduction behavior of Pt particles in the sodalite
cage and hexagonal prism could be different from those in the
supercage.

TPR curves in Fig. 5 and Table 4 show that low temperature peak
of Pt/RHO-HCs is substantially smaller than that of Pt/RHO-LCs,
which indicates that much fewer Pt ions are located between
zeolite crystals and mesopores or channels due to the structure
defect. As indicated in Table 3, despite higher Pt content, Pt/RHOLCs has lower total hydrogen consumption as compared to that of
Pt/RHO-HCs, which is probably due to the overlook of the external
surface Pt particles on Pt/RHO-LCs. Since our TPR experiment
started from 35 8C because of the limitation of the equipment setup, we might have underestimated the Pt ions on the external
surface which could have been reduced at lower temperature. To
examine whether there is any Pt particles located on the external
surface of Pt/RHOs, the XPS spectra of reduced Pt/RHO-LCs and Pt/
RHO-HCs were collected. The results are presented in Fig. 6. The Pt
4d and 4f core levels are, in principle, suitable for the XPS study of

Fig. 4. Framework structures of RHO (left) and LTA (right).

Fig. 5. TPR proles of RHO-B, Pt/RHO-HCs and Pt/RHO-LCs.

H. Chen et al. / Applied Catalysis A: General 358 (2009) 103109

108
Table 4
TPR results on Pt/RHO catalysts.
Catalyts

Pt/RHO-LCs
Pt/RHO-HCs

Low temperature
peak

High temperature
peak

Total H2/Pt

LT/HT

T (8C)

Area

T (8C)

Area

(mol)

(area)

178
189

0.0987
0.0329

411
431

0.0715
0.1353

1.34
1.89

1.38
0.24

platinum-containing zeolites [31]. No Pt 4d line (314331 eV) was

observed for both samples. In the Pt 4f region, a small peak
corresponding to that of metallic Pt peak (about 71 eV) was
observed only for Pt/RHO-LCs. The XPS results support our
assumption that there exists a small amount of external Pt
particles over Pt/RHO-LCs, which could not be detected during TPR
reduction. Slightly lower Pt particles dispersion (H/Pt molar ratio)
was obtained over Pt/RHO-LCs (0.44) than over Pt/RHO-HCs (0.48),
which is another indication of Pt particles on the external surface of
the former catalyst.
3.3. Hydrogenation of 1-hexene and 1-cyclohexene
Cyclohexene and 1-hexene were used as probe molecules to
test the hydrogenation activity of Pt/RHOs. Fig. 7 compares the gas
phase hydrogenation of 1-hexene over Pt/RHO-HCs, RHO-B and
that of cyclohexene over Pt/RHO-LCs. While cyclohexene is
completely converted over Pt/RHO-LCs, a much lower average
conversion of 1-hexene (5%) is obtained over Pt/RHO-HCs. The Pt
free RHO-B has no hydrogenation activity. The kinetic diameters of
1-hexene and cyclohexene are 4.3 and 6.0 A respectively, while the
opening of the D8R in RHO is 3.6 A [32]. Both molecules are unable
to access the Pt particles inside of the a-cage and in the D8R prism,
the conversions of these two molecules are due to both Pt particles
located on the external surface of Pt/RHO and the Pt particles
located between zeolite crystals or Pt particles situated in
mesopores or channels due to structural defects (defective sites).
The much higher hydrogenation activity obtained over Pt/RHO-LCs
is in good agreement with the TPR and XPS results discussed in the
section above, which indicate that more Pt particles are situated on
external surface areas and defect sites in Pt/RHO-LCs than Pt/RHOHCs. For Pt/RHO-HCs, the conversion is probably due to the Pt
particles located in the defect sites, since XPS results reveal non-Pt
particles on the external surface. Altwasser et al. investigated the
competitive catalytic hydrogenation of 1-hexene and 2,4,4trimethyl-1-pentene over 0.8 wt% Ru/RHO catalyst prepared by
incorporating Ru precursors into the synthesis gel [20]. Their
results showed that the yield of hexane was signicantly higher

Fig. 7. Gas phase hydrogenation of 1-hexene over Pt/RHO-HCs, RHO-B and

hydrogenation of cyclohexene over Pt/RHO-LCs.

than that of 2,2,4-trimethylpetane. They claimed that the Ru

particles were predominately incorporated inside the pores of the
8-membered ring in RHO. However, as we mentioned early, the
kinetic diameter of 1-hexene is considerably lager than the pore
opening of the RHO zeolite, therefore it is hard to conclude that the
conversion of 1-hexene is attributable to the Pt particles located in
the pores. It may be caused by Pt particles positioned in the
mesopores or channels, formed due to the structural defects.
3.4. Hydrogenation of naphthalene and hydrogen spillover
contribution
Because of the high hydrogenation reactivity of 1-hexene and
cyclohexene, both were not used as probe molecules to examine
the hydrogen spillover contribution, and naphthalene was used in
our study. Hydrogenation of naphthalene was conducted in an
autoclave at 300 8C and 1015 psig for 3 h, H-Y zeolite was used as
diluent (1:1) to study the effect of hydrogen spillover. Table 5
summarizes naphthalene conversions and TOF values over
different catalyst congurations. First, it can be seen that the Pt
free H-Y zeolite and reactor wall have no hydrogenation activity.
Naphthalene conversions over Pt/RHO-LCs and Pt/RHO-HCs were
21% and 6% separately. The 6% conversion over Pt/RHO-HCs reveals
that Pt particles sitting in the defective sites are even accessible to
molecules as large as naphthalene. The higher conversion over Pt/
RHO-LCs demonstrates again that it has more Pt particles located
on the external surface and in the defective sites. When Pt/RHOLCs was diluted with H-Y zeolite, the naphthalene conversion
increased to 91%. A similar trend was observed over Pt/RHO-HCs,
however, the conversion increased to a less degree. These results
clearly demonstrate the contribution of spillover hydrogen to the
hydrogenation reaction and agree to our previous results obtained
over a hybrid Pt/KA zeolite_H-Y_alumina catalyst and Pt/CMS_H-Y
catalysts [16,17]. Our results also suggest that the contribution to
Table 5
Comparison of hydrogenation of naphthalene activities over Pt/RHO catalysts.

Fig. 6. XPS spectra in the Pt 4f range for reduced Pt/RHO-HCs and Pt/RHO-LCs.

Catalyst congurations

Naphthalene conversion (%)

TOF (s

None
HY
Pt/RHO-LCs
Pt/RHO-LCs + HY
Pt/RHO-HCs
Pt/RHO-HCs + HY

0
0a
21
91
6
29

0
0
0.06
0.27
0.02
0.09

Ref. [16].

H. Chen et al. / Applied Catalysis A: General 358 (2009) 103109

109

hydrogen spillover by the more accessible Pt particles is greater

than that due to Pt particles conned in the a-cage and D8R prism.

for HPLC analysis. The editorial assistance of Norman Sacuta is

greatly appreciated.

4. Conclusion

References

At the concentration used in this work, Pt incorporation did not

affect the crystallinity and crystal phase of RHO obtained. Higher
Cs content resulted in a lower level of Pt incorporation, which
suggested that Cs and Pt may occupy the same sites in RHO. Two
TPR temperature peaks were observed for Pt/RHOs. High
temperature (410430 8C) was attributed to the reduction of Pt
particles sitting in the a-cage and D8R prism. A low temperature
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on the external surface, between zeolite particles or in the
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naphthalene due to the lack of shape selectivity. Naphthalene
conversion was increased signicantly when Pt/RHOs was diluted
with HY zeolite. Finally we conclude that recent research work
conducted at our centre clearly demonstrates the participation of
hydrogen spillover in hydrogenation reactions. This phenomenon
happened over a wide range of activators/acceptors (Pt/KA, Pt/
CMS, Pt/RHO HY zeolite, alumina and activated carbon), different
reaction system (xed bed/autoclave, atmospheric\high pressure,
alkene\aromatics). Our contributions should shed more light on
how to use this concept to design catalysts for various reactions
such as hydrogenation, isomerization, reforming and oxidation
and to enhance the overall reaction rate by supplying spillover
hydrogen.

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[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
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Acknowledgments
Partial funding for this work has been provided by the Canadian
Program for Energy Research and Development (PERD), the Alberta
Research Council and The Alberta Energy Research Institute. The
authors gratefully acknowledge Dr. Kevin J Smith, The University of
British Columbia, for XPS analysis and NCUT analytical group staff

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