Microporous and Mesoporous Materials 290 (2019) 109678

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Microporous and Mesoporous Materials

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Hydrogenation of dicyclopentadiene into endo-tetrahydrodicyclopentadie T

over supported different metal catalysts
P. Tamizhduraia,b,∗, A. Rameshb, P. Santhana Krishnanb, V.L. Mangeshc, S. Umasankarb,
S. Narayanand, C. Ragupathid, K. Shanthib,∗∗
a
National Centre for Catalysis Research, Indian Institute of Technology (IIT), Madras, Chennai, 600036, India
b
Department of Chemistry, Anna University, Chennai, 600 025, India
c
Department of Marine Engineering, Coimbatore Marine College, Coimbatore, 641035, India
d
Sriram College of Arts and Science, Perumalpattu, Veppampattu, Tiruvallur, Tamilnadu, 602 024, India

A R T I C LE I N FO A B S T R A C T

Keywords: The hydrogenation of dicyclopentadiene (DCPD) to tetrahydrodicyclopentadiene (THDCPD) has been in-
Dicyclopentadiene vestigated over 5 wt% Ni, 1 wt% Pt and 1 wt%Ru supported on SBA-15. The catalysts were characterized to
Dihydrodicyclopentadiene different phydico-chemial techniques founder standing their structural and textural properties. Interestingly, Ni/
Tetrahydrodicyclopentadiene SBA-15 and Ru/SBA-15 provided only one fully hydrogenated producttetrahydrodicyclopentadiene (THDCPD),
Ni catalysts
but Pt/SBA-15 produced both the two dihydro-products such as (3,4-and 8,9-dihydrodicyclopentadiene;
SBA-15
DHDCPD) and the complete hydrogenated THDCPD. The yield of the DHCPDs passed through maxima at dif-
Hydrogenation
ferent run times, suggesting the reaction to be a consecutive one. The 8,9-DHCPD was usually obtained in larger
amounts than the 3,4-isomer due to the greater reactivity of the 8,9-double bond in the norbornene ring. The
apparent activation energy values for the hydrogenation of DCPD to THDCPD over Pt/SBA-15, Ni/SBA-15 and
Ru/SBA-15 were found to be value of 23.8 kJ/mol 24.6 kJ/mol and 35 kJ/mol respectively catalysts.
Interestingly, the dihydro intermediates were found to be higher conversion formed upon addition of quinoline
in small amounts (0.16–0.78 mmol) to the reaction mixture in runs with Ni/SBA-15. The addition of quinoline
had no effect on runs with Ru/SBA-15. Reactions with Raney Ni catalyst were also performed, and this catalyst
also yielded the two dihydrogenated intermediates (3,4 – DHDCPD and 8,9 - DHDCPD)are found.

1. Introduction
A jet fuel is a type of aviation fuel designed for use in aircrafts
powered by gas-turbine engines. Generally, it is a mixture of a large
number of different hydrocarbons. The most common fuels are Jet A
and Jet A-1, which are produced to an internationally standardized set
of specifications. Another jet fuel that is commonly used in civilian
turbine engine-powered aviation is called Jet B [1–5]. It is a fuel in the
naphtha–kerosene region that is used for its enhanced cold-weather
performance [6]. However, Jet B's lighter composition makes it more
dangerous to handle. Military organizations around the world use a
different classification system of JP numbers [7,8]. The term of JP is a
portmanteau for Jet Propellant. Over the past decades, there has always
been a drive to extend the flight distance of aerospace vehicles. A
simple and effective approach to reach this goal is to improve the vo-
lumetric energy content of fuel [9]. High-energy fuel can provide more
propulsion energy than conventional refined fuel and promote the flight
range, payload and flight speed, which is specifically useful for volume-
limited missiles and rockets [10]. Many high-energy liquid fuels are
single compounds and have been synthesized by chemical synthesis. For
example, many polycyclic hydrocarbon fuels such as RJ-4, RJ-5, RJ-7
and JP-10 are in use, and some new hydrocarbons like alkyl-dia-
mondoids and caged compounds have been developed [11–13].
JP-10 (exo-tetrahydrodicyclopentadiene) is an important fuel in
military applications, particularly in the development of air-breathing
propulsion systems [14]. One of the main advantages of JP-10 as a fuel
is its high volumetric energy density; it also offers low freezing point
and good heat transfer properties. JP-10 is “simpler” than other jet
propulsion fuels in that it is essentially a single-component fuel [15].
Jet propellant 10 (JP-10) has been widely used in land, ship and air-
launched missiles. Actually, this fuel has been used to expand the range
of cruise missiles [16–19]. JP-10 is synthesized using endo-

∗
Corresponding author.National Centre for Catalysis Research, Indian Institute of Technology (IIT), Madras, Chennai, 600036, India
∗∗
Corresponding author.
E-mail address: Tamizhvkt2010@gmail.com (P. Tamizhdurai).

https://doi.org/10.1016/j.micromeso.2019.109678
Received 15 April 2019; Received in revised form 19 August 2019; Accepted 22 August 2019
Available online 23 August 2019
1387-1811/ © 2019 Elsevier Inc. All rights reserved.
P. Tamizhdurai, et al.
dicyclopentadiene (DCPD) as the feedstock [20]. The synthesis proce-
dure includes hydrogenation of DCPD to tetrahydrodicyclopentadiene
(THDCPD) and then isomerization of the endo-configuration to the exo-
configuration. In this process, the hydrogenation reaction is very im-
portant because unsaturated compounds will lead to coke deposition
and catalyst deactivation in the downstream isomerization reaction
[21–26].
Endo-dicyclopentadiene (DCPD) is a clear liquid with a strong
musty odour. It is a dimer of cyclopentadiene (CPD) and is formed
during high-temperature cracking of petroleum fractions and recovered
by distillation. DCPD is obtained by distillation of pyrolysis gasoline, a
by-product of steam cracking of naphtha [27]. The usual method of
preparing dicyclopentadiene is to fractionally distill the crude, impure
dimer, and allow it to polymerize at room temperature overnight
[28–31]. This procedure is repeated a number of times, depending upon
the purity of the original material, until a fraction is obtained that
distills over at 41.5 °C the boiling point of pure cyclopentadiene [32].
When this latter material polymerizes, it yields a white, crystalline solid
[33–36]. The accepted values for the melting point and refractive index
of dicyclopentadiene are given as 31.5 °C and 1.5120 (20 °C) respec-
tively [37]. Naphtha steam crackers for the production of ethylene are
the primary source of cyclopentadiene and dicyclopentadiene, although
a small amount is still recovered from coal tar distillation [38]. The
amount of CPD/cyclopentadiene produced depends on the feedstock to
the cracker [39]. The yield from a naphtha cracker is 6–8 times of that
from a gas cracker, which uses ethane and propane feed mixture. The
cracked gas leaving the furnace section of a steam cracker contains
many chemical components [40]. They are separated by a series of
fractionation columns [41]. The bottom stream from the debutanizer
column, known as pyrolysis gasoline in the industry, contains the C5
and heavier fraction of the cracked gas. Typically, cyclopentadiene plus
dicyclopentadiene constitute 15–25 wt% of pyrolysis gasoline. Because
CPD dimerizesreadily, it is usually recovered in the form of DCPD
[42–44]. The C5 fraction of the pyrolysis gasoline is first separated as
the overhead of a depentanizer. The C5 stream is heat-soaked in a di-
merizer at about 100 °C. The CPD in the C5 stream is converted to DCPD
[45]. The separation of the low-boiling C5 components from the DCPD
is achieved by a second fractionation in which the DCPD is recovered as
the bottom product [46]. The DCPD is mainly in the endo form and has
a purity of 82–90%. Cyclopentadiene undergoes a Diels-Alder reaction
with itself, producing the dimer, dicyclopentadiene. (The Diels-Alder
reaction is a conjugate addition reaction of a conjugated diene to an
alkene to produce a substituted cyclohexene system.).
The objective of this work is to investigate catalysts for the hydro-
genation of dicyclopentadiene (DCPD), and also to selectively hydro-
genate one of the two double bonds, one in the norbornene ring (NB-
bond) and the other in the cyclopentene ring (CP-bond) of DCPD. It is
proposed to use Ni, Pt, Ru and Raney Ni supported on SBA-15 as cat-
alysts for hydrogenation. The reaction pathways followed over the
above mentioned catalysts are to be evaluated using different reaction
parameters such as temperature, pressure, catalyst loading and contact
time. The supports and catalysts are to be characterized by many
physico-chemical methods to identify the nature of the active species
present in the catalysts. The characterization results will be utilized to
understand the relative performance of the two catalysts.
1.1. Chemicals
Pluronic P123 (PEG-PPG-PEG) symmetric triblock copolymer, tet-
raethyl orthosilicate(TEOS) and hydrochloric acid were used in pre-
paration of SBA-15 support. Pluronic 123 and TEOS were procured
from Aldrich. Nickel Nitrate, Tetraammineplatinum (II) chloride hy-
drate and Ruthenium chloride were used as precursors for preparation
of Nickel, Platinum and Ruthenium catalysts on SBA-15 support. Nickel
nitrate was procured from SiscoResearch Laboratories Pvt. Ltd. and the
metal salts were obtained from Aldrich.Ni–Al alloy, Sodium hydroxide
2
Microporous and Mesoporous Materials 290 (2019) 109678
and isopropanol were procured from Sisco Research Laboratories Pvt.
Ltd. and used to prepare Raney Ni catalyst. Dicyclopentadiene (DCPD)
(Sigma-Aldrich) and n-heptane (as solvent) (Sisco Research
Laboratories Pvt. Ltd.). Quinoline (Sisco Research Laboratories Pvt.
Ltd.) was used to poison the catalyst during the hydrogenation reaction.
1.2. Preparation of the catalysts
SBA-15 was synthesized under hydrothermal conditions using the
procedure outlined by V. Meynenet al [47]. Pluronic P123 (4 g) was
dissolved in 40 ml of double distilled water and the mixture was al-
lowed to stir for 90 min till a clear solution was obtained. HCl (2 M,
50 ml) was added to the solution and the mixture was allowed to stir for
30 min. TEOS (9 g) was added dropwise to the mixture and the mixture
was kept for continuous stirring in an oil bath maintained at 40 °C for at
least 20 h. The white gel obtained after 20 h duration was transferred
into a Teflon lined autoclave or polypropylene bottle and kept for hy-
drothermal treatment at 100 °C for 48 h duration. The product after
hydrothermal treatment was filtered, washed thoroughly with water
and dried at 60 °C for 6 h. Calcination was carried out in a tubular
furnace under a continuous flow of air at 550 °C for 6 h.
The impregnation of the support with precursor slats of 5 wt% Ni,
1 wt% Ru, and 1 wt% Pt were made by a wet impregnation method
using aqueous solutions of nickel nitrate (Ni(NO3)2·6H2O), Ruthenium
(III) chloride hydrate (RuCl3.xH2O) and Tetraammineplatinum (II)
chloride hydrate respectively. After metal impregnation, the catalysts
were dried at room temperature overnight followed by drying in an
oven at 100 °C for 12 h and Ni catalyst was calcined at 450 °C for 4 h.
The catalyst was further reduced in hydrogen at the same temperature
for 4 h. The Ru and Pt catalysts were calcined at 450 °C for 4 h and
followed by reduced (in presence of hydrogen gas) at 250 °C for 2.5 h.
The prepared catalysts were labelled as Ni/SBA-15, Ru/SBA-15 and Pt/
SBA-15.For Raney Ni catalyst preparation Ni–Al alloy was taken.
5NNaOH solution was added to it, stirred well and separated using
centrifugal separator. It was then washed with excess of water and then
with isopropanol to remove water. Raney Ni was obtained and it was
stored in alcohol.
1.3. Reaction procedure
Hydrogenation of dicyclopentadiene (DCPD) was carried out using
n–heptane as solvent and Ni, Pt and Ru as catalysts supported on SBA-
15 in a high pressure batch reactor of 100 ml volume. About 0.2 g of
catalyst was used for each reaction (expect for hydrogenation reactions
with different metal support catalyst loading). After loading the feed
mixture (2 g DCPD and 30 g n-heptane) and the catalyst, the reactor was
sealed, flushed in hydrogen and its temperature increased to the reac-
tion temperature (100–200 °C) with stirring of the contents at about
800 rpm. Simultaneously, the reactor was pressurized with H2 to the
required value (10–40 bar) and sealed. At the end of the stipulated time,
calculated from the time the reactor reached the required temperature,
heating was switched off and the external furnace lowered to cool the
reactor rapidly. After the reactor cooled to near ambient temperature, it
was opened and the products were taken out. The catalyst was removed
from the reaction mixture by centrifugation. Analysis of the products
was carried out by capillary gas chromatography (Mayura Analytical
GC - Model 9800; Column: dimethylpolysiloxane (AT-1),
60 m × 0.25 mm i.d x 0.25 μm film thickness). Identification of the
products was carried out by comparing with standards and by matching
the boiling points of the products and their retention times. Product
compositions were estimated from GC areas.
1.4. Data treatment
DCPD conversion (XA) was calculated using the following the
equations
P. Tamizhdurai, et al.
XA = (FAin − FAout )/(FAin ) × 100%
where, A = DCPD reactant concentration, F = flow of the reactant.
Specific reaction rate ((SRR) r, mol g−1 s−1) was calculated using
the following equation,
SRR (r) = F0 XA/w
−1
where, F0 = molar flow rate of non-edible oils (mol s ), XA = %
conversion of DCPD and w = weight of the catalyst (g).
The Turnover frequency (TOF) was calculated using the following
equation
TOF (S−1) = (r, mol g−1 s-1) / ((quantity of sites (μmol g−1))
where, the quantity of active sites was calculated from H2 chemisorp-
tion (μmol g−1) [48].
1.5. Materials characterization
All the synthesized materials were characterization using different
physio-chemical techniques. The X-ray diffraction, N2-sorption studies,
HR-TEM, Gas Chromatography analysis and computational studies also
discussed in previously reported articles. The reduction behavior of
active metals such as Ni and Ru using H2-TPR study was carried out
QUADRASORB SI, it is an automatic analyzer the gas ratios mixture 5%
H2/95%Ar. Initially, 0.05 g of sample was taken with pre-treated at
400 °C for 2 h under He gas under flow rate 70 ml/min.
1.6. XRD studies
In order to establish the structural characteristics of the synthesized
samples, XRD studies were performed. The low angle XRD pattern of
the SBA-15, Ni/SBA-15, Pt/SBA-15, Ru/SBA-15, and Raney Ni/SBA-15
materials are shown in Fig. 1. For the SBA-15 sample, three well-re-
solved peaks at (100), (110), and (200) can be clearly seen in the range
of 2θ = 0.5–2.5°, which correspond to the well-ordered hexagonal
mesoporous structure. However, it is seen that the intensity of these
peaks decreases when the Ni, Pt, Ru, and raney Ni are loaded on SBA-
15, suggesting partial damage to the orderliness of the mesoporous.
This means that for all samples, the orderliness of the mesoporous
structure is only partly preserved after incorporation of the metals.
High angle XRD pattern of SBA-15, Ni/SBA-15, Pt/SBA-15, Ru/SBA-
15 and Raney Ni catalysts were shown in Fig. 2. XRD pattern of SBA-15
support showed a broad diffraction peak at 23° corresponding to the
Fig. 1. Low angle range of XRD powder patterns for a) SBA-15 b) Pt/SBA-15, c)
Ni/SBA-15 d) Ru/SBA-15, and e) Raney Ni/SBA-15.
Microporous and Mesoporous Materials 290 (2019) 109678
(1)
(2)
(3)
Fig. 2. High angle XRD patterns of catalysts and supports.
amorphous nature of silica. Furthermore, after impregnation different
active metals such as Ni, Ru and Pt over the supports the characteristic
peaks not appeared these phase may be well dispersed over SBA-15.
Table 1 presents the d-spacing values (dhkl) and unit cell size for the
SBA-15 support and Ni/SBA-15, Pt/SBA-15 and Ru/SBA-15 catalysts.
The d-spacing was calculated using Bragg's law.
λ = 2dhkl sin θhkl (4)
Since SBA-15 support has hexagonal structure, the following for-
mula was used to calculate the unit cell size
1/ dhkl2 = 4/3(h2 + 12 + hk )/ a2 + 12 / c 2 (5)
which reduces to a0 = 2d100/3 when the d100 plane is used (Table 1).
1.7. N2-sorption studies
The textural properties of SBA-15, Ni/SBA-15, Pt/SBA-15 and Ru/
SBA-15 were investigated using N2sorptionisotherms of the samples.
Fig. 3 presents the N2 adsorption-desorption isotherms for SBA-15, Ni/
SBA-15, Pt/SBA-15 and Ru/SBA-15. Typical type IV adsorption iso-
therms with a H1 hysteresis loops are observed. The isotherms exhibit a
sharp inflection in the P/P0 range of 0.65–0.80 characteristic of capil-
lary condensation within fairly uniform pores. The sharpness of the
inflection suggests a very uniform pore-size distribution. It is also seen
that the sharpness of the inflection seen in the case of the metal loaded
samples is similar to that of SBA-15 suggesting little changes in pore
size distribution among the samples. However, a small shift in the in-
flection maximum towards lower p/p0 values is seen in the case of the
metal loaded samples compared to SBA-15. This suggests a small de-
crease in the average pore size of the M/SBA-15 samples. Surface areas,
pore volumes and average pore diameters of the samples obtained by
N2-adsorption are presented in Table 1.
The average pore size obtained for the catalysts is found to be
slightly smaller than that for SBA-15. The surface area of SBA-15 is
896 m2/g. On loading the active components (Ni - 5 wt%, Pt - 1 wt%
and Ru – 1 wt%), the surface area of the catalysts decreases sub-
stantially. The loss in surface area on loading the metals is probably due
to damage to the pores and formation of amorphous silica during im-
pregnation and calcination procedures. This damage is also reflected as
less intense lines in the XRD-patterns for the catalysts.
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P. Tamizhdurai, et al. Microporous and Mesoporous Materials 290 (2019) 109678

Table 1
Textual properties, Inter-planar spacing and unit cell size for supports and catalysts.
Catalyst SBETa (m2/g) SExt.b (m2/g) PV Totalc(cm3/g) PVmesod (cm3/g) Avg. Pore Size (nm) d- spacing, dhkl (nm) Unit cell size ‘a0’ (nm)

100 110 111

SBA-15 896 305 0.52 0.47 6.5 7.60 4.82 4.20 8.78
Ni/SBA-15 531 281 0.53 0.51 6.4 6.95 4.43 3.97 8.02
Pt/SBA-15 755 210 0.43 0.41 5.7 7.0 4.48 4.05 8.08
Ru/SBA-15 667 279 0.50 0.46 5.6 7.2 4.52 4.07 8.27

a
Surface areas calculated by the BET method.
b
Area obtained after subtracting t-plot micropore area from SBET.
c
N2 (liq) sorbed at p/po = 0.99.
d
Pore volume after subtracting t-plot micropore volume from PVtotal.

examined through the reduction behavior of Ni and Ru over SBA-15

Fig. 3. N2sorption isotherms of SBA-15, Ni/SBA-15,Pt/SBA-15 and Ru/SBA-15
catalysts.
1.8. Temperature programmed reduction studies
The reduction behavior of active metal oxide species and support
were investigated through H2-TPR profile. The H2-TPR profile was
catalyst on temperature range at 100–800 °C is presented in Fig. 4. The
H2-TPR profiles show the reductions behaviors of Ni and Ru active
metals over SBA-15 support. Initially, three types of reduction peaks
were displayed at 378,432,605 °C. The reduction peaks were given in
Table 2, the reductions at 378 and 432 °C were assigning to the weak
and strong interactions of Ni2+to Ni0. In the higher temperature re-
duction at 605 °C surface polyoxo species and bulk NiO(Fig. 4a).
The Ni/SBA-15 catalyst was reduced formed at hydrogen conditions
at 450°Cat 2 h the reducible ion present in the sample is Ni2+ ions. The
Ni2+ is expected to undergo reduction to Ni0. The Ni ion is present in
different structures (specie) in the catalysts, such as dispersed NiO in-
teracting with the surface, surface polyoxo species and bulk NiO. In
spite of the many species present, the TPR profile reveals mainly three
reduction peaks, though small humps are also seen. TPR peak maxima
are found at 378 °C and 432 °C with a hump at 605 °C, the high tem-
perature peak being the major one.
The reduction of pure NiO takes place at temperatures below 420 °C,
while NiO in strong interaction with SBA-15 support undergoes re-
duction temperature range at500–650 °C. The wide bump in the
500–700 °C range can be assigned to the reduction of less accessible or
strongly interacting NiO specie. As shown in Fig. 4bthe reduction be-
havior of ruthenium oxide in the as-calcined 1% Ru/SBA-15 sample is
characterized by two peaks at 157 °C and 434 °C. The main peak at
157 °C is recognized as the reduction of Ru4+ to Ru0and the small peak
at 434 °C is assigned to the reduction of low valets Ru species in strong
interaction with the support [49].

Fig. 4. a) H2-TPR profile of NiO/SBA-15 catalysts and b) Ru/SBA-15 catalyst.

4
P. Tamizhdurai, et al. Microporous and Mesoporous Materials 290 (2019) 109678

Table 2
TOF and Specific Reaction Rate for reaction name over catalysts and reaction conditions.
Catalysts a
Reduction behavior oC b
Hydrogen consumption × 10−6 g−1 quantity of active site × 10−4 g−1
c d
SRR × 10−5 mol g−1 s−1 e
TOF s−1 × 10−2

Ni/SBA-15 378,432,605 90 28 9.6 34

Pt/SBA-15 – – – 7.8 21
Ru/SBA-15 157,434 35 41 8.1 19
Raney Ni – – – 9.8 27

a&b
Reduction bevaiour and hydrogen consumption was determine by H2-TPR.
c
H2-chemisorption studies.
d & e
based on equations (2) and (3).

Fig. 5. High resolution transmission electron microscopy of a) SBA-15, b) NiO/SBA-15, c) Pt/SBA-15, and d) Ru/SBA-15 catalyst.

1.9. High resolution transmission electron microscopy (HR-TEM)
The TEM (transmission electron microscope) pictures of some of the
samples are presented in Fig. 5. SBA-15 is found to possess a very or-
dered arrangement of mesopores (Fig. 5a). When 10% reduced NiO
sample is deposited, the orderliness of the pores is decreased and also
the deposits of NiO metal are seen (Fig. 5b). The picture of a reduced
sample of Pt/SBA-15 reveals the presence of Pt particles of size less than
10 nm, revealing a reasonably good dispersion of the metal in the cat-
alyst (Fig. 5c). Fig. 5d is the TEM image of reduced Ru/SBA-15. The Ru
particles are found to be small (about 10–15 nm) comparable in size to
that of the Pt particles [50]. The average metallic size distribution for
pure SBA-15 catalyst is 27 nm, NiO/SBA-15 catalyst shows 25 nm, Pt
and Ru catalyst shows the average metallic size distribution from 20 to
40 nm.
1.10. Hydrogenation of dicyclopentadiene (DCPD)
The activity of the three catalysts such as Ni(5 wt%)/SBA-15, Pt
(1 wt%)/SBA-15 and Ru(1 wt%)/SBA-15 on hydrogenation of DCPD,
and the effect of reaction time, temperature, pressure, and catalyst
loading on conversion and product selectivity are reported [47]. Both
Ni and Ru catalysts yielded the fully hydrogenated tetra-
hydrodicyclopentadiene (THDCPD) as the single product without the
intermediate the mono-olefins 3,4- and 8,9- dihydrodicyclopentadienes
(3,4 – DHDCPD and 8,9 – DHDCPD). On the other hand, Pt(catalysts)
yielded the dihydro-compounds also as intermediates. Two more cata-
lysts that were investigated in this study are Raney Nickel and Raney Ni
supported on SBA-15. Only the hydrogenated products were obtained in
these studies. The decomposition product, cyclopentadiene and the
isomerization products exo-THDCPD and adamantane were not found
in the product.
1.11. Effect of process parameters
1.11.1. Influence of run time
Over both Ni/SBA-15 and Ru/SBA-15, only the endo-THDCPD was
formed. The influence of run time on yield of the fully-hydrogenated
product is presented in Fig. 6a. Conversion increases with time for both
the catalysts. The conversion of DCPD is 30% in 1 h for Ni(5%)/SBA-15
and 34% for Ru(1%)/SBA-15. The conversion at 5 h is 70% for Ni and
64% for Ru. Thus, conversion values and the trend in conversion are
also both similar for both the catalysts, though the Ni catalyst exhibits a
larger conversion at the longer run time, probably due to its greater
stability with duration of run.
The condensation of two cyclopentadiene molecules can in principle
lead to either the endo- or the exo-dicyclopentadiene isomer (Scheme
1). However, even though the exo-isomer is the thermodynamically
more stable product, the endo-isomer is generally formed due to kinetic
reasons arising from greater reactivity of the transition state due to
orbital symmetry considerations. The DCPD used in the present studies
is essentially the endo-isomer.

5
P. Tamizhdurai, et al. Microporous and Mesoporous Materials 290 (2019) 109678

Fig. 6. a) Comparison of Ni/SBA-15 and Ru/SBA-15 for DCPD hydrogenation (Reaction Conditions: Catalyst loading – 0.2 g; temperature 130 °C; hydrogen pressure
20 bar), b) Effect of run time for DCPD hydrogenation using Pt/SBA-15 catalyst (Reaction Conditions: Catalyst loading – 0.2 g; temperature 130 °C; hydrogen pressure
20 bar), c) Effect of Temperature on Conversion of DCPD over Ni/SBA-15 and Ru/SBA-15 catalysts and d) Effect of temperature on yield of THDCPD and DHDCPD
isomers over Pt/SBA15catalysts (Reaction Conditions: catalyst loading – 0.2 g; hydrogen pressure - 20 bar; run time – 3 h).

The double bonds in the DCPD molecule are in the 8,9- (in nor-
bornene ring; NB = ) and 3,4- (cyclopentene ring; CP = ) positions. The
NB = is thermodynamically less stable due to greater strain and is likely
to be more easily hydrogenated [51]. Therefore, one would expect more
of the 8,9-dihydrodicyclopentadiene (Scheme 2). However, it should
also be noted that greater steric hindrance due to the norbornene ring
system could also hinder the hydrogenation of the 8,9-double bond on
some surfaces.
Though Ni and Ru (74.8 and 78.6%) yielded only the fully hydro-
genated product (THDCPD), Pt(80.5%) yielded the mono-hydrogenated
products also. The results obtained over Pt(1%)/SBA-15 are presented
in Fig. 6b. It is found that the yield of THDCPD increases continuously
with time, but those of the DHDCPD going through maxima at different
run times. The occurrence of maxima at different times suggests that the
hydrogenation to THDCPD is a consecutive reaction with the dihydro-
products as intermediates, the rates of hydrogenation of the double
bonds being different. The reason for the earlier occurrence of the
maximum in the case of the 3,4-hydrogenated isomer is probably due to
steric hindrance to the hydrogenation of the NB = . The8,9-dihydroi-
somer being the thermodynamically more stable isomer, ultimately
prevails and is present in larger amount in the product.
The yield of THDCPD at 5 h run time over Pt/SBA-15 is 73% com-
pared to 70% for Ni and 64% for Ru. In addition, about 7% of the
intermediate products (3,4 – DHDCPD and 8,9 – DHDCPD) are also
formed. Essentially, 1% Pt catalyst possesses a greater hydrogenating
activity than 5% Ni and 1% Ru catalysts. The formations of the dihy-
droproducts over the Pt catalyst suggest that the mode of adsorption of
DCPD on Pt may be different than those over Ni and Ru, leading to

Scheme 1. Condensation of cyclopentadiene into the two dicyclopentadiene products.

6
P. Tamizhdurai, et al.
Scheme 2. Products of hydrogenation of dicyclopentadiene to dicyclopentadiene.
different mechanistic pathways.
1.12. Mechanism of Ni (111) and Pt (111) catalyst
The minimum energy configuration for adsorption of DCPD over a
clean surface layer of Pt(111) and Ni(111) surfaces obtained by theo-
retical calculations [52] reveal that the adsorption modes on the two
metals are different (Fig. 7a and b). Over Ni(111) surface, the minimum
energy configuration is adsorption at the 2,6-single-bond (not at the
double bonds), while on Pt(111), the adsorption takes place at NB = .
This difference in the mode of adsorption of DCPD over the two metals
may be the reason for the observed differences in catalytic activities of
the two metals. More studies on the energetic of adsorption and kinetics
will be necessary for an understanding of the mechanism of the reaction
over the two metals.
1.13. Influence of reaction temperature
The influence of temperature on the hydrogenation of DCPD over
the three catalysts was investigated by carrying out the reactions
at110 °C, 120 °C and 130 °C at 20 bar total pressure, with reaction time
of 3 h and 0.2 g catalyst loading. The results of these studies are pre-
sented in Fig. 6c and d.
The conversion of DCPD increased with temperature as expected for
(Ni-SBA-15, Ru-SBA-15 and Pt/SBA-15) all the catalysts. Only THDCPD
was formed over both Ni and Ru at the reaction three temperatures
(110–130° C) (Fig. 6c). But, over Pt, the DHDCPD isomers were also
found at all the temperatures (Fig. 6d). Apparent activation energy (Ea)
values were calculated for the Ni, Ru, and Pt (from data of Figs. 8 and
Fig. 7. Minimum energy configurations of adsorbed DCPD over a) Ni(111) and b) Pt(111) surfaces.
7
Microporous and Mesoporous Materials 290 (2019) 109678
9). The Arrhenius plots for Ru and Ni are presented in Fig. 8a and b and
for Pt presented in Fig. 9. The Ea values calculated form the above plots
are 35 kJ/mol, 24.6 kJ/mol and 23.8 kJ/mol for Ru/SBA-15, Ni/SBA-
15, and Pt/SBA-15respectively catalysts.
In the case of Pt/SBA-15 catalyst endo-THDCP, 3,4-DHDCPD, and
8,9-DHDCPD were found at different temperatures. However, only the
yields of THDCPD and the thermodynamically more stable 8,9-
DHDCPD increased with temperature. The yield of the less stable 3,4-
DHCPD went through a maximum at 120°C. The amount of the 3,4-
hydrogenated isomer is greater than that of the 8,9-hydrogenated
isomer at 110°C and 120°C, but less than the stable isomer at 130°C. The
8,9-/3,4-hydrogenated isomer ratios at the three temperatures are:
0.44 at 110°C, 0.50 at 120°C and 5.0 at 130°C. The greater yield of75%
the 8,9-hydrogenated isomer at higher temperatures is due to its greater
thermodynamic stability. The greater presence of the 3,4-hydrogenated
isomer at lower temperatures 100°C reveals the possibility of kinetic
effects (like, for example, steric hindrance of the NB = ) favoring the
hydrogenation of the 3,4-bond at lower temperatures.
1.14. Influence of total H2pressure
The studies were carried out at a constant temperature of 130°C and
keeping other parameters the same, but varying the pressure (10, 20
and 30 bar). Again as in earlier studies, only THDCPD was formed over
Ni, Ru and Pt catalyst the hydrogenated products were formed on Pt.
The results are presented in Fig. 10a and b. It is found (Fig. 10a) that
pressure increases conversion significantly in the case of both Ni and
Ru, the increase being more for the Ni catalyst. At 30 bar pressure,
conversion is 80% over Ni compared to 64% over Ru. At 10 bar, Ru is
P. Tamizhdurai, et al.
Fig. 8. a)Arrhenius plot for 1% Ru/SBA-15.Figure b) 5% Ni/SBA-15.
Fig. 9. Arrhenius plot for 1% Pt/SBA-15.
more active than Ni, the conversion being 31% compared to 24% for Ni.
At 20 bar, both catalysts possess similar activities. The difference in
activities at different pressures could be due to differences in the re-
lative strengths of adsorption of H2, the reactant and product over the
two catalysts.
All the three hydrogenated products Endo-THDCPD were formed
over Pt/SBA-15 at the different pressures. A sharp increase in the yield
(78.5%) of THDCPD is seen on increasing pressure from 20 bar to 30 bar
(Fig. 10b). In the case of DHDCPD, the yield of the 3,4-hydrogenated
isomer remains constant, but that of the 8,9-hydrogenated isomer goes
through a maximum at 20 bar. Apparently, pressure does not affect the
formation of the 3,4-hydrogenated isomer, but has a significant effect
on the 8,9-hydrogenated isomer. The increased formation of the 8,9-
hydrogenated isomer on increasing pressure from 10 to 20 bar is due to
increase in preferential hydrogenation of the NB = with pressure. But,
beyond 20 bar, the hydrogenation of the CP = also occurs rapidly to
form THDCPD.
8
Microporous and Mesoporous Materials 290 (2019) 109678
1.15. Effect of catalyst loading
The influence of catalyst loading was investigated over Ni/SBA-15
and Ru/SBA-15 keeping the version parameter except catalyst amount
same (Fig. 10c). It is seen from Fig. 10c that conversion increases with
catalyst loading. The increase in conversion with catalyst loading is due
to greater availability of active sites. A blank run without any catalyst
gave a conversion of 6.5%. This small conversion could be due to the
presence of minor amounts of catalytic materials used in previous runs
sticking to locations that are not accessible for cleaning, and due to the
activity of the reactor material (stainless steel). Conversion of DCPD
reached a maximum of 62% for 0.3 g Ni/SBA-15 catalyst, with the
corresponding conversion for 0.3 g Ru/SBA-15 catalyst being about the
same, viz. 59%. But, at 0.1 g catalyst loading, Ni/SBA-15 gave a much
higher conversion (40%) than Ru/SBA-15 (23%). The figure also shows
that beyond 0.2 g catalyst loading, the influence becomes less.
1.16. Reaction with Raney Ni
The commercial amorphous Ni-alloy catalyst (SRNA-4) and reported
[53] the formation of the intermediate DHDCPDs. It was therefore be-
lieved that Raney Ni (prepared from Ni–Al alloy by leaching with al-
kali) will also yield the intermediates. The results of the studies carried
out using Raney Ni are presented in Fig. 10d. The reaction conditions
were 130 °C, 20 bar, 0.5 g Raney Ni and 2 g DCPD in 30 g n-heptane. It
is seen (Fig. 10d) that a high conversion of 72% of THDCPD is obtained
at 3 h run time. The concentration of the intermediates is high at 1 h
and 2 h run time being about 10% for the 3,4-hydrogenated isomer and
about 6% for the 8,9-hydrogenated isomer. These isomers undergo
further hydrogenation and their concentration is about 3% each at 3 h
run time. The yield of THDCPD is 43% at run time of 2 h and 72% at 3 h
run time. As a sharp increase in conversion with time is noticed, it is
likely that the conversion would have reached close to 100% if the run
had been carried out for longer durations.
The results obtained over the Raney Ni catalyst are surprising for
two reasons: 1) supported Ni did not yield any DHDCPD isomers, while
bulk Ni (Raney Ni) yielded the isomers and 2) the concentration of the
less stable 3,4-hydrogenated isomer is more at short run times. The
reasons are not clear now. It is probably due to the large size of the Ni-
crystallites in Raney Ni and differences in the types of planes exposed
by them in the supported and un-supported catalysts. In order check if
the suppression of the dihydro-isomers in the Ni/SBA-15 catalyst was
P. Tamizhdurai, et al. Microporous and Mesoporous Materials 290 (2019) 109678

Fig. 10. a) Effect of pressure on conversion of DCPD over Ni/SBA-15 and Ru/SBA-15 (Reaction Conditions: DCPD reactant: n-heptane solvent Catalyst loading – 0.2 g;
temperature 130 °C; run time 3 h), b) Effect of Pressure on yield of the products using Pt/SBA-15 catalyst(Reaction Conditions: DCPD reactant: n-heptane solvent
Catalyst loading 0.2 g; temperature 130 °C; run time 3 h), c) Effect of catalyst loading on conversion of DCPD over Ni/SBA-15 and Ru/SBA-5 (Reaction Conditions:
Hydrogen pressure 20 bar; temperature 130 °C; run time 3 h), d) Effect of run time on the yield of products using 0.5 g Raney Ni catalyst (Reaction Conditions:
Catalyst loading 0.2 g; temperature 130 °C; hydrogen pressure 20 bar).

due to the presence of SBA-15, a mixture of Raney Ni and SBA-15 was
prepared and tested in the hydrogenation reaction. The reaction was
performed at 130 °C, 20 bar pressure and a run time of 1 h with 0.2 g
catalyst. The results showed the formation of the dihydro-isomers to a
small extent (4% and 6% yield of 3,4-DHDCPD and 8,9 –DHDCPD re-
spectively) revealing that the support did not suppress the formation of
the dihydro-products and that the nature of the Ni-metal was different
in the supported catalyst and Raney Ni.
2. Conclusion
Three different catalysts 5 wt% Ni/SBA-15, 1 wt%Pt/SBA-15 and
1 wt%Ru/SBA-15 were prepared by hydrothermal method. The TPR
studies reveal the presence of many types of metal oxide specie and the
presence of interaction between metal oxide species and the support.
Increasing the run time increased the conversion of DCPD and yield of
the products for 3 h. The temperature at 130 °C was found to be higher
conversion and yield. The apparent activation energy values calculated
from the data gave Ea values of23.8 kJ/mol for Pt/SBA-15, 35 kJ/mol
for Ru/SBA-15 and 24.6 kJ/mol for Ni/SBA-15. The 30 bar H2 pressure
was found to be high conversion of DCPD is about 80%. Increase in
catalyst loading from 0.1 to 0.3 g also increases the conversion of DCPD
with Ni/SBA-15 and Ru/SBA-15, only one product THDCPD was
formed for Ni/SBA-15. However, the Pt/SBA-15 catalyst was appeared
both the dihydrogenated intermediates (3,4- DHDCPD and 8,9-
DHDCPD) and THDCPD. The thermodynamically more stable 8,9-hy-
drogenated isomer was found in larger amounts over the catalyst Pt/
SBA-15 catalyst, its concentration increasing with temperature. The
formation of the dihydro-products over Pt/SBA-15 could be due to a
mechanistic pathway different from those over Ni/SBA-15 and Ru/SBA-
15 catalysts. A Raney Ni catalyst was prepared using Ni–Al alloy, and
reactions were performed at different run times. Both the intermediate
dihydodicyclopentadienes were formed over this catalyst. An increase
in the yield of THDCPD with increase in run time was observed. The
yield of the DHDCPD was larger at run times of 1 h and 2 h and de-
creased substantially at 3 h. The difference in product selectivity over
the bulk Ni-catalyst (Raney Ni) and the supported catalyst (Ni/SBA-15)
is surprising. Quinoline added in small amounts
(0.16 mmol–0.78 mmol) to the reaction mixture caused the formation
of the dihydro intermediates over Ni/SBA-15. The concentration of
these intermediates went through a maximum at moderate quinoline
loadings and decreased at high loadings though the yield of the
THDCPD remained constant. The addition of quinoline to Ru/SBA-15
did not produce DHDCPD.
Acknowledgment
The authors are thankful to Prof. S. Sivasanker for his guideline sand

9
P. Tamizhdurai, et al. Microporous and Mesoporous Materials 290 (2019) 109678

constant support for carrying out the reactions and thank Prof.B.
Viswanathan NCCR, IIT-Madras for providing laboratory and char-
acterization facilities.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.micromeso.2019.109678.
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