Microporous and Mesoporous Materials 171 (2013) 1423

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Microporous and Mesoporous Materials

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Characterization and performance of hybrid catalysts for levulinic acid

production from glucose
Nazlina Yaaini a, Nor Aishah Saidina Amin a,, Salasiah Endud b
a
Chemical Reaction Engineering Group (CREG), Energy Research Alliance, Faculty of Chemical Engineering, 81310 UTM, Skudai, Johor, Malaysia
b
Department of Chemistry, Faculty of Science Universiti Teknologi Malaysia, 81310 UTM, Skudai, Johor, Malaysia

a r t i c l e i n f o a b s t r a c t

Article history: In this work, a set of hybrid catalysts were synthesized, characterized and tested for the conversion of
Received 3 August 2012 glucose to levulinic acid. The hybrid catalysts with 1:1, 1:2 and 2:1 weight ratios of CrCl3 and HY zeolite
Received in revised form 19 November 2012 were prepared via the wetness impregnation method. Characterization of the hybrid catalysts using XRD,
Accepted 2 January 2013
FESEM, BET, FT-IR, TGA, NH3-TPD and FT-IR of adsorbed pyridine demonstrated the catalytic reaction of
Available online 9 January 2013
the hybrid catalysts was predominantly inuenced by the type of acid sites (Lewis acid), amount of acid
sites and strength, surface area, hierarchical porous structures and shape selectivity. Highly reactive acid
Keywords:
sites greatly inuenced the catalytic activities of glucose in producing levulinic acid. Experimental results
Hybrid catalysts
HY zeolite
revealed that the hybrid 1:1 catalyst exhibited the highest catalytic performance with 62% of levulinic
Acidity acid yield at 160 C in 180 min of reaction temperature and time. The hybrid 1:1 catalyst has potential
Hierarchical pore to be applied for biomass conversion to levulinic acid under adequate process conditions.
Levulinic acid 2013 Elsevier Inc. All rights reserved.

1. Introduction
The production of bio-based chemicals from biomass resources
have received wide attention as an alternative method for substi-
tution of fossil resources [1]. Levulinic acid is one of the potential
bio-based chemicals wherein it can be derived from glucose, a
compound from the biomass feedstock [2,3]. Levulinic acid, con-
tains ketone carbonyl and carboxylic acid functional groups, is a
versatile building block for various applications such as polymers,
resin, avour substances and fuel additives [4,5]. Several studies
were conducted to utilize the biomass for levulinic acid produc-
tion. Initially, homogeneous acids (H2SO4, HCl, etc.) as catalysts
were investigated for levulinic acid production from fructose, glu-
cose, cellulose, and lignocellulosic biomass such as water hyacinth,
wheat straw and grain sorghum [68]. The homogeneous method
was effective but caused some problems to the environment, to
the equipment and was also uneconomical [5,9]. As an alternative,
heterogeneous acid catalysts were proposed to overcome the prob-
lems with the homogeneous acids. Heterogeneous catalysts have
several advantages including highly selective, easy to handle and
low cost if the catalysts can be recovered, recycled and regenerated
for several times [5,9].
Previously, heterogeneous acids such as LZY, HY and ZRP-X type
zeolites, metal chlorides and solid superacid (S2O82/ZrO2SiO2
Sm2O3) were used to produce levulinic acid from fructose, glucose,
Corresponding author. Tel.: +60 75535579; fax: +60 75536165.
E-mail address: noraishah@cheme.utm.my (N.A.S. Amin).
cellulose and rice straw [35,911]. Low levulinic acid yields and
prolonged reaction times were reported by Jow et al. [10], Lourvanij
and Rorrer [11] and Zeng et al. [3] with 43%, 20% and 36% of levu-
linic acid yields were produced at 140 C, 15 h; 160 C, 10 h; and
180 C, 8 h of reaction temperatures and reaction times, respec-
tively. Thus, further studies were conducted by Peng et al. [5]
and Hongzhang et al. [4] by employing metal chlorides and solid
superacid. They found that these methods have enhanced the
levulinic acid yields in shorter reaction times, but high reaction
temperatures (200 C) were required. Therefore, further studies
are still necessary to evaluate the activities for the formation of
levulinic acid by discovering more reactive catalysts through cata-
lytic performance testing and physicochemical properties.
Catalytic performance testing over Y-type faujasite (LZY and
HY) and mordenite (ZRP-X) type zeolites revealed that properties
of the catalysts such as the amount of acid sites and strength,
porosity and shape selectivity have signicantly inuenced the lev-
ulinic acid production and selectivity [3,10,11]. Meanwhile, metal
halide (CrCl3) could facilitate the mutarotation and isomerization
processes of glucose towards fructose with simultaneous dehydra-
tion to hydroxymethyl furfural (HMF). The HMF was catalytically
rehydrated by hydronium ions to form levulinic and formic acids
[5,11]. Low HMF yield was reported over zeolite and metal halide
alone in the reaction systems as reported by previous study [12].
The low levulinic acid yield could also be expected in these
reaction systems since HMF is the intermediate compound before
it undergoes ring cleavage to form linear molecules, levulinic acid
and formic acid. Modication of the HY zeolite structure by

1387-1811/$ - see front matter 2013 Elsevier Inc. All rights reserved.
http://dx.doi.org/10.1016/j.micromeso.2013.01.002
 N. Yaaini et al. / Microporous and Mesoporous Materials 171 (2013) 1423
combining the zeolite and metal halide (CrCl3) to form a hybrid
catalyst is expected to improve the catalytic properties and possi-
bly enhance the levulinic acid yield under adequate process
conditions.
Recent literature reviews have indicated that research utilizing
hybrid catalysts for the levulinic acid production from glucose are
not widely available [3,5,9]. Thus, in this present work, we em-
ployed hybrid catalysts comprising of CrCl3 and HY zeolite with
different weight ratios. Characterizations of HY zeolite and hybrid
catalysts were thoroughly determined using XRD, FE-SEM, BET, FT-
IR, TGA, NH3-TPD and FT-IR of adsorbed pyridine. The effect of
physico-chemical properties of catalysts in the formation of levu-
linic acid were investigated under sufcient process conditions.
The hierarchy factor of zeolite and acid sites per unit surface area
were also determined to study the effect of the different weight ra-
tios of CrCl3 and HY zeolite on the catalytic performance of the hy-
brid catalysts.
2. Experimental
2.1. Materials
HY zeolite (SiO2/Al2O3 = 30) was purchased from Zeolyst Inter-
national Inc. Chromium Chloride, CrCl3 was supplied from Merck,
Germany. Meanwhile D(+)-glucose monohydrate and sulfuric acid
(H2SO4) 9597% were purchased from QRec, New Zealand. A stan-
dard analytical grade of levulinic acid 98% (Sigma Aldrich) was
used for analysis of the desired products. Deionized water was
used in the solution reactions.
2.2. Catalyst preparation
Hybrid catalysts were prepared according to the wetness
impregnation method. Different weight ratios (1:1, 1:2 and 2:1)
for CrCl3 and HY zeolite were identied as hybrid 1:1, hybrid 1:2
and hybrid 2:1 catalysts in this study. The hybrid 1:1 catalyst
was prepared through the following method: same weight ratio
of aqueous solution CrCl3 (10 w/v%) with HY zeolite powder
(10 g) were mixed and stirred at room temperature for 2 h. Then,
the mixture was dried overnight in the oven at 120 C. Finally,
the hybrid catalyst was calcined at 400 C for 24 h to activate the
catalyst [13]. These steps were repeated for hybrid 1:2 and 2:1 cat-
alysts in different CrCl3 and HY zeolite weight ratios.
2.3. Catalyst characterization
Powder X-ray diffraction (XRD) was evaluated using a Bruker D8
Advance diffractometer system (Cu Ka radiation, 40 kV, 30 mA) and
the angle 2h between 10 and 80. The average crystallite size was
determined using the Sherrer equation; Dhkl = kk/b cos h (where
k = 0.98, k = 1.54178 , b = the half-peak width (radian) from the
full-width at half-maximum of the most intense diffraction peak
position [331] and h = the angle of diffraction peak). The morphol-
ogy of the hybrid catalyst samples was observed by eld emission
scanning electron microscopy (FESEM) using a model of JSM-6701F.
The surface area, pore size and volume of catalyst samples were
evaluated according to the standard nitrogen adsorption/desorption
at 77 K, using a Quantachrome Autosorb-1 instrument. The catalyst
samples were out gassed in vacuum for 20 h at 100 C before N2
physisorption. The surface area of the catalyst samples was
determined using Brunauer-Emmet-Teller (BET) method. The distri-
butions of the micropores and mesopores were estimated by the
t-plot and Barrett, Joyner & Halenda (BJH) methods, respectively.
The BET constants (CBET) for these isotherms were 109.99 g/m3,
114.92 g/m3, 114.22 g/m3 and , 111.44 g/m3 for HY, Hybrid 1:1,
15
Hybrid 1:2 and Hybrid 2:1 catalysts, respectively at the relative
pressure range 0.050.20. According to Aligizaki [14], the value of
CBET is frequently in between 50 to 300 when nitrogen was used
as adsorbate at 77.35 K. Therefore, the CBET for these isotherms are
within the accuracy of the BET method. Meanwhile, Dubinin-
Radushkevich (DR) method has been selected for the determination
of the micropore volume [14]. The Dubinin method is obtained
based on Eq. (1) by plotting log (V) as function of log2 (Po/P).
  
2 Po
log V logqV o  D log 1
P
where V is the amount adsorbed at relative pressure P/Po, q is the
density of the liquid adsorbate, nitrogen (N2) and Vo is the micro-
pore volume. The micropore volume is obtained from the intercept
of this straight line by assuming the density of N2 was 0.808 g/m3
and D is the slope of the straight line.
Meanwhile for the structures analysis, Fourier-transformed
infrared spectroscopy (FTIR) spectra of catalyst samples were ob-
tained from powdered samples on KBr pellets using a Perkin-Elmer
Spectrum with a resolution of 4 cm1 and 10 scans in the 4000
400 cm1 of IR range. Thermal gravimetric analyses (TGA) were
conducted using a TGA (Perkin Elmer TGA 7) instrument. About
10 mg of catalyst sample was placed in a platinum pan and heated
from 30 C to 900 C under N2 ow (10 C/min).
Acid sites properties of the catalyst samples were determined
using temperature-programmed desorption (TPDRO 1100 series,
Thermo Finnigin) with ammonia as a probe molecule (NH3-TPD).
Initially, a catalyst sample (500 mg) was degassed at 393 K for
1.5 h under a constant nitrogen ow (20 ml/min). Then, the sample
was cooled to 328 K and the ammonia was adsorbed for 1 h. After
saturation, nitrogen was purged for 0.5 h at 20 ml/min to remove
excess ammonia on the catalyst surface. Finally, the catalyst sam-
ple was heated from 323 K to 1173 K under a constant helium ow
(20 ml/min). The concentration of desorption ammonia was quan-
tied by a thermal conductivity detector (TCD). Meanwhile, the
Brnsted and Lewis acid sites of the catalysts were determined
by FT-IR spectroscopy with pyridine as a probe molecule. The spec-
tra were recorded using Shimadzu 2000 FTIR spectrometer at room
temperature with a resolution of 4 cm1.
2.4. Catalyst performance
One pot catalytic reaction was carried out by dissolving glucose
in deionized water (1.0 %) and mixed with hybrid catalyst (cata-
lyst/glucose ratio, 1.0) in a closed 150 ml Scott bottle (batch reac-
tor). Then, the batch reaction system was immersed in preheated
silicon oil at the desired temperature and atmospheric pressure
at stirring speed, 300 rpm. Immediately after the reaction was
completed, 10 ml of deionized water was added in the solution
at room temperature. The reaction mixture was briskly stirred to
rehydrate and dissolve the water-soluble reaction products away
from the solid hybrid catalyst and humin. All the samples were l-
tered through a 0.45 lm membrane syringe lter and the liquid
phase was further analyzed using high performance liquid chroma-
tography (HPLC).
2.5. Product analysis
The concentration of liquid phase samples was determined by
using HPLC (Perkin Elmer Series 200) under the following conditions:
column = organic acid Aminex HPX-87H; ow rate = 0.6 ml/min;
mobile phase = H2SO4 (5 mM); detector = UV210 nm; retention
time = 60 min; column temperature = 60 C. As for glucose conversion
analysis the following conditions were used: column = Rezex RPM
Monosaccaride; ow rate = 0.6 ml/min; mobile phase = deionized
16 N. Yaaini et al. / Microporous and Mesoporous Materials 171 (2013) 1423

water; detector = refractive index detector (RID); retention time =
35 min; column temperature = 80 C. The concentration of the sam-
ples was determined using the standard levulinic acid calibration
curve with known concentrations. Glucose conversion, product yields
and selectivity were calculated according to Eqs. (2)(4):
initial glucose  glucose after reaction
Conversion wt%
initial glucose
 100%
weight of product  initial weight of glucose
Product yield wt%
 of HY zeolite due to the larger size of Cr element compared to Al
levulimic acid yield wt%
Selectivity %  100%
glucose conversion wt%
3. Results and discussion
3.1. Physical properties of catalysts
3.1.1. Crystallinity and morphology
The XRD patterns of HY zeolite and hybrid catalysts are dis-
played in Fig. 1. In the phase identication, the XRD patterns of
these catalysts were compared with the standard patterns of fauj-
asite type zeolite and Cr2O3 [15,16]. In the observation, identical
patterns of the hybrid catalysts to the respective peaks of the HY
zeolite were detected with shifted peak at a higher angle
(2h = 64). The shifted peak was identied as a crystalline phase
of Cr2O3. This reveals that the wetness impregnation method has
modied the structure of the HY zeolite. The diffraction intensity
at this plane increased remarkably when the HY zeolite (hybrid
* showed that there were strong interactions between CrCl3 and HY
Hybrid 2:1
* the HY zeolite has reduced the surface area and pore volumes of
Hybrid 1:2
Intensity (cps)
1:2) and metal salt (hybrid 2:1) loading were increased compared
to the equal weight ratio of metal salt and HY zeolite (hybrid 1:1).
The diffraction intensity of [331] and [555] planes in the hybrid
catalysts increased simultaneously when the CrCl3 was impreg-
nated in the HY zeolite. These patterns occurred due to the interac-
tion between the metal salt and HY zeolite.
The structural and crystallinity properties of HY zeolite and the
hybrid catalysts are summarized in Table 1. Unit cell parameter
2 (a0) of the HY zeolite increased simultaneously in the hybrid cata-
lysts with the highest expansion of 3.24% (hybrid 1:2). This sug-
gests that chromium was incorporated into the lattice structure
100%
3 and Si. The average crystallite size of the catalysts was estimated
at highest diffraction peak (2h = 15) by using the Scherrer equa-
tion. The average crystallite size of the hybrid catalysts relatively
4
increased to the largest size, 7.28 nm for the hybrid 1:2 catalyst.
The small differences of crystallite sizes between HY zeolite and
hybrid catalysts conrmed that the HY zeolite structure was not
modied signicantly. In addition, the relative crystallinity of the
hybrid catalysts were calculated based on the integral peak inten-
sity at 2h = 15 in comparison with the HY zeolite. The relative
crystallinity of the HY zeolite decreased after modication as the
existence of CrCl3 could destroy the zeolite framework during the
impregnation process. The reduction in crystallinity could be
attributed to the strong interaction between the cation (Cr3+) with
the oxygen atoms of the alumina tetrahedra in the zeolitic frame-
work. The increment in electropositive of the cation from Al3+ to
Cr3+ could have increased the interaction of cation with the oxygen
bond weakening the zeolite framework. The distorted structures in
the hybrid catalysts reduced the crystallinity of the HY zeolite.
The morphology of the hybrid catalysts was evaluated by FES-
EM in Fig. 2. It was clearly observed that Cr2O3 was nely dispersed
on the HY zeolite surface. The magnication up to 10000x implied
that the morphology and particle size of HY zeolite was not chan-
ged signicantly after impregnation of CrCl3 in the hybrid catalyst.
However, in this preparation route, leaching could have happened
but it was assumed at a slow rate since the characterization results
zeolite in the hybrid catalysts.
3.1.2. Surface area and porosity
The surface area and porosity of the catalysts inuenced the
glucose reaction towards levulinic acid production. The surface
area determined by BET revealed that impregnation of CrCl3 on
the hybrid catalysts (Table 2). The decrement is attributed to the

presence of Cr2O3 and the extra framework of aluminium species

within the zeolite pores and channels. Hybrid 2:1 catalyst has
the smallest surface area and pore volume, 266 m2/g and 0.1714
cm3/g, respectively due to high CrCl3 loading revealing that more
Cr2O3 and extra aluminium species framework were formed inside
the pores. The pores size of all the hybrid catalysts were almost the
Hybrid 1:1 * Table 1
Structural and crystallinity analyses of catalysts.

Catalysts a0a () Leb (%) Dcc (nm) Rcd (%)

HY zeolite 24.39 - 6.24 100
Hybrid 1:1 24.98 2.42 6.72 37
Hybrid 1:2 25.18 3.24 7.28 89
HY zeolite Hybrid 2:1 25.05 2.71 6.99 44
a
Unit cell parameter is calculated from the [331] and [555] diffraction peak
positions.
b
Lattice expansion in comparison with the HY zeolite.
10 20 30 40 50 60 70 80 c
Crystallite size is calculated from the most intense diffraction peak position,
o
2theta ( ) [331].
d
Relative crystallinity at integral peak intensity, 2h = 15 in comparison with the
Fig. 1. XRD patterns of catalysts (, pattern of Cr2O3 phase) (XRD, X-ray diffraction). HY zeolite.
 N. Yaaini et al. / Microporous and Mesoporous Materials 171 (2013) 1423 17

Fig. 2. FESEM of hybrid catalysts at (a) 5000, (b) 10,000, (c) 1000 and (d) 250 (FESEM, Field emission scanning electron microscopy).

Table 2
Surface area and porosity of catalysts.

Catalysts SBETa (m2/g) Smicrob (m2/g) Smesoc (m2/g) Vpores (cm3/g) Vmicrod (cm3/g) Vmesoe (cm3/g) Dmicrof (nm) Dmesog (nm) HFh
HY zeolite 810 576 234 0.5055 0.2923 0.2131 0.39 3.90 0.1522
Hybrid 1:1 393 265 128 0.2522 0.1405 0.1116 0.41 3.87 0.1587
Hybrid 1:2 566 387 179 0.3465 0.2033 0.1432 0.40 3.86 0.1637
Hybrid 2:1 266 181 85 0.1714 0.0954 0.0760 0.40 3.87 0.1568
a
BET surface area is obtained from N2 adsorption isotherm in the relative pressure range, 0.050.20.
b,c
Surface area of micropore and mesopore are obtained from the tplot method.
d
Volume of micropore is obtained from the DR (Dubinin-Radushkevich) method.
e
Volume of mesopore (Vpores - Vmicro).
f
Micropore size is estimated from the tplot method.
g
Mesopore size is estimated from the BJH desorption plot method.
h
The hierarchy factor (HF) is determined as (Vmicro/Vpores)  (Smeso/SBET) with Vmicro is obtained from the tplot method [19].

same with the hybrid 1:1 catalyst contained the largest micropore
and smallest mesopore sizes, 0.41 nm and 3.87 nm, correspond-
ingly. According to Xue et al. [17], hierarchical zeolite is designed
to enhance the mesopore surface area without severe loss of the
micropore volume. Therefore, hierarchy factor (HF) was calculated
to classify hierarchically structure of catalysts through the porous
characteristic [18]. The purpose to determine this factor is to eval-
uate the catalytic performance by improving transport in the cata-
lyst through the interconnections with a secondary mesopore
network of inter- or intracrystalline structure [19,20]. The hybrid
1:2 catalyst displayed the highest HF (0.1637) followed by hybrid
1:1, hybrid 2:1 and HY zeolite catalysts.
3.2. Chemical properties of catalysts
3.2.1. Infrared spectroscopy
Structural properties of HY zeolite and hybrid catalysts were
obtained by using FT-IR spectroscopy in the range of 4000
400 cm1 (Fig. 3). The vibration occurred in the hybrid catalysts
due to the modication of HY zeolite. In general, the spectra of
zeolite could be divided into two regions at 1300450 cm1 and
40003000 cm1 [21,22]. The rst region (1300450 cm1) signi-
ed the framework vibrations of lattice cell (T-O-T unit) where T
is SiO4 or AlO4 tetrahedron. Meanwhile, the second region
(40003000 cm1) was attributed to hydroxyl groups attached to
the zeolite structure. The chromium oxide bands in the zeolite
framework were observed in the rst region. The absorption band
at 1073 cm1 appeared with enhanced intensity in the hybrid cat-
alysts. This band was attributed to chromyl group (Cr = O) in the
hybrid catalysts as reported by Hadjiivanov et al. [23]. In addition,
the bands at 832 cm1 and 600 cm1 indicated the presence of Cr
O bonds in CrO2 and CrO3 phases with a lattice mode associated
with amorphous Cr2O3 [24]. However, these bands could not be
clearly observed due to the bands overlapping with the stronger
HY zeolite bands. On the other hand, the typical band of zeolite
at 3443 cm1 signied the existence of Brnsted acidic OH sites
on the catalysts. This band inferred to the vibrations of Si-OH, Al-
OH or H-bonded hydroxyl groups [22,25]. The intensity of this
band was reduced in the hybrid catalysts as the Cr cation has
interacted with the OH group of HY zeolite. As a consequence,
the Brnsted acid sites in the hybrid catalysts reduced. This struc-
tural analysis is in good agreement with the XRD analysis (Fig. 1)
18 N. Yaaini et al. / Microporous and Mesoporous Materials 171 (2013) 1423
Absorbance
4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 450.0
Wavenumber (cm-1)
Fig. 3. FT-IR spectra for HY zeolite and hybrid catalysts (FT-IR, Fourier-transformed
infrared spectroscopy).
and suggested that some crystallites were formed during the
impregnation process.
3.2.2. Thermal gravimetric analysis
Thermal gravimetric analysis (Fig. 4) showed the mass varia-
tions in the catalyst samples at a heating rate of 10 C/min from
room 30 C to 900 C under N2 ow. The temperature ranges 30
120 C was attributed to the evaporation of water molecules from
the catalyst samples. In the second stage (350650 C), there were
broad mass losses in the hybrid catalyst samples due to the ther-
mal dehydroxylation. As a result, the HCl gas was released, CrCl3
was dispersed on the HY zeolite surface in the form of Cr2O3 and
the aluminium was released from the zeolite framework to possi-
bly defect the lattice structures [26,27]. Thereby, the crystallinity
of the HY zeolite was reduced in the hybrid catalysts as previously
discussed in the XRD analysis. Over 800 C, mass losses were de-
tected in the hybrid 2:1catalyst. As reported by Li et al. [26], this
stage was desorption of adsorbed CrCl3 from the HY zeolite cage.
From this observation, the activation of hybrid catalysts at 400 C
was sufcient to verify the interaction of CrCl3 with the HY zeolite
during the impregnation process.
3.2.3. Acidity
The NH3-TPD proles of HY zeolite and hybrid catalysts are
shown in Fig. 5. The NH3 desorption peaks were classied as weak,
moderate and strong acid sites based on the desorption tempera-
ture. The desorption temperature was determined by the strength
of interaction between NH3 and the surface acid sites, and the
amount of the desorbed species were quantied based on these
peaks area [3]. The acid sites distribution for the HY zeolite was
in-line with the previous study, wherein two desorption peaks of
ammonia were detected at low and moderate temperatures,
80 C and 329 C, respectively [28]. The strength of the acid sites
slightly increased when the CrCl3 was impregnated into HY zeolite.
Hybrid 1:1 and hybrid 2:1 catalysts demonstrated the desorption
peaks of NH3 at weak and moderate acid sites. The strong acid sites
in the hybrid 1:2 catalyst suggested that the CrCl3 was well
dispersed on the HY zeolite. From the proles, the trends implied
that the amount of acid site was not directly related to the zeolite
content but it was inuenced by the interaction between the
zeolite and metal halides in the hybrid catalysts.
In addition, the amount of acid sites was quantied as tabulated
in Table 3. The total acidity of the hybrid catalysts signicantly in-
creased. The hybrid 1:2 catalyst gave the highest total acid sites
(5.65 mmol/g) at three different desorption peaks: weak
(0.40 mmol/g) moderate (3.04 mmol/g) and strong (2.21 mmol/g)
acid sites. In contrast, hybrid 2:1 showed the lowest total acid sites
(2.94 mmol/g) compared to the hybrid 1:1 and 1:2 catalysts possi-
bly due to the partially blocked pores as a result of high CrCl3 load-
ing. The presence of Cr2O3 in the hybrid 2:1 catalyst has blocked
the acid sites on the surface, and reduced the acidity of the catalyst.
As expected, the strength and distribution of acid sites were obvi-
ously inuenced by altering the CrCl3 and HY zeolite ratios in the
hybrid catalysts. Hence, the hybrid catalysts showed high total
acidity and acid sites strength in the following order; hybrid
1:2 > hybrid 1:1 > hybrid 2:1. However, when the acid sites per
unit surface area was considered in this work, hybrid 1:1 catalyst
possessed the highest acidity (13.13 lmol/m2) followed by hybrid
2:1 (11.05 lmol/m2) and hybrid 1:2 (9.98 lmol/m2) catalysts. This
indicates that hybrid 1:1 catalyst contained more reactive acid
sites on the catalyst surface compared to hybrid 2:1 and hybrid
1:2 catalysts.
3.2.4. Infrared spectroscopy of adsorbed pyridine
Infrared spectroscopy of adsorbed pyridine was used to differ-
entiate between Brnsted and Lewis acid sites as shown in Fig. 6.
It was observed that the Brnsted acid sites exhibited band at
1545 cm1 and at 1450 cm1 the pyridine was bound to Lewis acid
sites. In addition, a band at 1490 cm1 was associated to both acid
sites: Brnsted and Lewis acid sites [29]. According to Niwa et al.
[30], the Brnsted acid sites can be generated from the hydroxyl
groups and Al framework. Meanwhile, the Lewis acid sites can be
observed on the zeolite with defects, amorphous parts and extra-
framework of Al species. Hybrid catalysts exhibited high Lewis acid
sites compared to Brnsted acid sites. This result agrees with the
XRD pattern and FT-IR spectra whereby impregnation of CrCl3 on
the HY zeolite has reduced the crystallinity of the HY zeolite, re-
placed the hydroxyl groups and formed extra-framework of Al
species.
3.3. Catalytic Performance
The catalytic performance of the hybrid catalysts was evaluated
by varying the reaction temperature (100200 C) at 180 min of
reaction time. Fig. 7ac reveal the distributions of products (levu-
linic acid, HMF and formic acid) by using the hybrid 1:1, hybrid 1:2
and hybrid 2:1 catalysts, respectively. High levulinic acid yield and
low HMF and formic acid yields were produced with the reaction
temperatures. This implies that the HMF molecule (0.82 nm) was
trapped in the micropores with size 0.40 nm. The addition of
water in the system after dehydration process could also facilitated
the rehydration of HMF into levulinic acid and formic acid. Accord-
ing to Peng et al. [5], HMF was unstable in water and it could sub-
sequently converted into levulinic acid and formic acid under the
reaction conditions. Small amount of HMF was detected on the cat-
alyst surface and it was classied as unreacted HMF during the
rehydration reaction process. Meanwhile, theoretically, the formic
acid is formed in an equal ratio with levulinic acid [10]. However in
this study, low formic acid yield was observed suggesting that the
formic acid tended to decompose into CO2, H2, CO and H2O in the
heat and acids mediums [31]. At 160 C, high levulinic acid yields
were obtained by using the hybrid 1:1 (63%) and hybrid 2:1
(47%) catalysts. Conversely, at higher reaction temperature
(200 C), the levulinic acid yield rapidly decreased due to the
 N. Yaaini et al. / Microporous and Mesoporous Materials 171 (2013) 1423
100
90
80
70
Mass losses (wt%)
HY zeolite
60
100
90
80
70
Hybrid 1:2
60
0 200 400
Fig. 4. TG and DTG analysis of catalysts. (TG, Thermal gravimetric and DTG, Differential thermal gravimetric).
formation of carbonaceous residue (humin), or deposition of coke
on the catalyst surface and pores.
Glucose conversion and selectivity of levulinic acid is depicted
in Fig. 8 with 100% glucose conversion achieved at 160 C. The glu-
cose conversion linearly increased with increasing temperature.
The rate of chemical reactions rapidly accelerated with increasing
reaction temperature and drove the glucose reaction towards com-
pletion. Nevertheless, this reaction condition was not recom-
mended since undesired side reactions may also formed at the
same time [7].The highest levulinic acid selectivity (63%) was re-
ported over hybrid 1:1 catalyst at 160 C (Fig. 8a). The distinction
of product yields, glucose conversion and levulinic acid selectivity
among the hybrid catalysts emphasize that the physico-chemical
properties of catalysts have inuenced the catalytic activity. The
distributions of products were reliant on the acid sites, porosity
and the shape (reactant and product) selectivity properties of the
hybrid catalysts.
Large number of acid sites was required in all the reaction path-
ways involved (isomerization, dehydration and rehydration) for
glucose conversion to levulinic acid. Lewis acid sites were more
predominant in the formation of levulinic acid rather than Brn-
sted acid sites as reported by Weingarten et al. [32]. They demon-
strated that Lewis and Brnsted acid sites played different
functions in dehydration of xylose into furfural. Lewis acid sites
could lead to further reaction of furfural to produce decomposition
products which are levulinic acid and formic acid. The highest
19
-1
TG
DTG
-2
Mass losses rate (wt% min-1)
Hybrid 1:1
-1
-2
Hybrid 2:1
600 800 0 200 400 600 800
Temperature (oC)
levulinic acid yield was observed in the hybrid 1:1 catalyst and
presumably it is related to the highest acid sites per unit surface
area. The reactive acid sites on the surface of hybrid 1:1 catalyst
could facilitate the catalytic dehydration of glucose towards levu-
linic acid production. From the observation, reactive and moderate
acid site strength in the hybrid 1:1 and hybrid 2:1 catalysts have
greatly inuenced the reaction activities for the formation of levu-
linic acid from glucose. This result was consistent with the previ-
ous report wherein the levulinic acid formation was related to
the amount of acid sites [3]. The HMF can undergo dehydration
and ring cleavage under strong acidic conditions to form linear
molecules: levulinic acid and formic acid [10].
Meanwhile, the porosity of the hybrid catalysts has signicant
effect on the glucose reactions towards levulinic acid production.
The sizes of micropores among the hybrid catalysts were smaller
than the glucose (0.90 nm) and the intermediate product, HMF
(0.75 nm) which indicate the shape selectivity of the catalysts.
The molecular sieve capability of these catalysts could produce
high yield and selectivity of levulinic acid. This shape selective
property of the hybrid catalyst can be explained in the proposed
schematic reaction scheme of glucose as depicted in Fig. 9. Initially,
isomerization reaction of glucose into fructose molecule might oc-
cur either by a proton transfer or by an intramolecular hydride
shift due to the presence of the Cr metal in the zeolite framework
[33]. Then the balance of glucose and fructose rings was further
opened over the Lewis acid sites into a linear 1, 2enediol molecule
20 N. Yaaini et al. / Microporous and Mesoporous Materials 171 (2013) 1423

B B+ L L

(d)

(c)

Absorbance
(b)

0 200 400 600 800 (a)

Temperature (C)

Fig. 5. NH3-TPD proles of catalysts; (a) HY zeolite, (b) hybrid 1:1, (c) hybrid 1:2,
(d) hybrid 2:1. (NH3-TPD, Temperature programmed desorption of ammonia.).

1560 1540 1520 1500 1480 1460 1440 1420

on the catalyst surface. Next, 1, 2enediol diffused through the Wavenumber (cm )
-1

micropores and dehydrated into HMF over the Lewis acid sites
within the mesopores. The intermediate product, HMF was trapped
within the pores and could not exit the cage until it was further
dehydrated to the linear molecules (levulinic acid and formic acid)
by strong acidic medium. These molecules were small enough to
diffuse through the micropores [10]. Small size of mesopores
(3.9 nm) in the catalysts were sufcient since the mesopores
with large pore size can increase local protonic acidity that would
promote some side reactions (fragmentation and polymerization);
consequently, reducing the levulinic acid yield [3,12].
Besides porosity, surface area also inuenced the catalytic activ-
ity. The large surface area of the HY zeolite catalyst could provide
more catalytic sites for the reactions of glucose. However, the high-
est levulinic acid yield was produced over the hybrid 1:1 catalyst
as more reactive acid sites were available on the hybrid 1:1
catalyst compared to the other catalysts. Hybrid 1:1 and hybrid
2:1 catalysts were more selective due to the smaller mesopore
volume [34]. High mesopore volume through large pore channels
can increase the local protonic acidity. Thus, it would promote
some side reactions (fragmentation and polymerization); conse-
quently, reducing the levulinic acid yield [3,12]. Moreover, possible
Fig. 6. FT-IR spectra of adsorbed pyridine of catalysts; (a) HY zeolite, (b) hybrid 1:1,
(c) hybrid 1:2, (d) hybrid.
leaching of small amount of chromium in the reaction solution
could occur under rigorous reaction conditions and yet it could
be considered that the chromium ions were also involved in the
catalytic reaction [35].
The catalytic performance over hierarchical character of HY
zeolite and hybrid catalysts as depicted in Fig. 10a shows a linear
relationship of the levulinic acid yield with the hierarchy factor
(HF) except for the hybrid 1:2 catalyst. The linear trend demon-
strates that the catalytic reaction towards levulinic acid production
were inuenced by both the introduced mesopores and distributed
micropores [19]. This evolution was discussed in detail by Verbo-
ekend and Perez-Ramirez [18] and Verboekend et al. [36]. They re-
ported that the changes in the hierarchical zeolite properties might
occur due to chemical composition, distribution of acid sites and
effects of catalyst surface which could have inuenced the catalytic
performance of the hybrid 1:2 catalyst. In this work, we found that
high relative mesopority with low relative micropores were

Table 3
Acidity of catalysts.

Catalysts Weak acidity Moderate acidity Strong acidity Total acidity (mmol/g) Acid sitesb (lmol/m2)
Tda (C) Amount (mmol/g) Td (C) Amount (mmol/g) Td (C) Amount (mmol/g)
HY zeolite 80 0.86 329 0.56 - - 1.42 1.75
Hybrid 1:1 74 0.30 482 4.86 - - 5.16 13.13
Hybrid 1:2 86 0.40 510 3.04 721 2.21 5.65 9.98
Hybrid 2:1 85 0.17 465 2.77 - - 2.94 11.05
a
Desorption temperature, acidity of catalysts are determined using NH3TPD measurement.
b
Acid sites per unit surface area.
 N. Yaaini et al. / Microporous and Mesoporous Materials 171 (2013) 1423 21

70
60 (a)
100 (a) 100
Product yields (%)

50 80 80

Conversion (%)
40 60 60

Selectivity (%)
30
40 40
20
20 20
10
0 0 0
100 120 140 160 180 200 100 120 140 160 180 200
Temperature (C) Temperature (C)

70
60 (b) Levulinic acid
100 (b) 100

HMF 80 80
Product yields (%)

Conversion (%)
50 Formic acid

Selectivity (%)
40 60 60

30 40 40
20
20 20
10
0 0 0
100 120 140 160 180 200 100 120 140 160 180 200
Temperature (C)
Temperature (C)

70
100
(c) 100
60 (c)
80 80
Product yields (%)

Conversion (%)

50

Selectivity (%)
40 60 60

30 40 40
20 Conversion
20 20
10 Selectivity
0 0
0 100 120 140 160 180 200
100 120 140 160 180 200
Temperature (C)
Temperature (C)
Fig. 8. Glucose conversion and selectivity of levulinic acid versus reaction
Fig. 7. Product yield versus reaction temperature at 180 min of reaction time for (a) temperature at 180 min of reaction time for (a) hybrid 1:1, (b) hybrid 1:2 and (c)
hybrid 1:1, (b) hybrid 1:2 and (c) hybrid 2:1 catalysts. hybrid 2:1 catalysts.

process through its porosity and shape selectivity properties

preferable in producing higher levulinic acid yield as shown in the
hybrid 1:1 and 2:1 catalysts results (Fig. 10b). This suggests that
the relative mesopores might inuence the glucose reaction to-
wards levulinic acid formation. Meanwhile, the relative micropores
might inuence the efciency of levulinic acid diffusion through-
out the catalyst pores. These results were consistent with the
previous studies [18,19,36] wherein the catalytic dehydration of
glucose to levulinic acid required mesopores and micropores with
the appropriate pore size and volume.
As a comparison, further analysis was conducted at conditions
of almost 100% glucose conversion (160 C and 180 min) for the
HY zeolite, CrCl3 and physical mixing of HY zeolite and CrCl3 cata-
lysts. In the observation, 15%, 20% and 50% of levulinic acid yields
were produced by using these respective catalysts. Based on these
results, modications of HY zeolite by introducing the metal
chloride, CrCl3 gave levulinic acid yield to 62% over the hybrid
1:1 catalyst. These results indicated that CrCl3 played an important
role to facilitate the mutarotation and isomerization processes of
glucose towards fructose before the glucose was simultaneously
dehydrated and rehydrated into HMF and levulinic acid [5].
Meanwhile the HY zeolite exhibited its valuable role in the reaction
[10,11]. Chemically prepared catalyst showed more signicant
results in producing high levulinic acid yield compared to the
physically prepared one. The results indicated that the interaction
of CrCl3 and HY zeolite have produced a catalyst with new proper-
ties over which more signicant results were obtained compared
to individual catalyst. Therefore, it can be concluded that chemi-
cally prepared hybrid catalyst through the wetness impregnation
method with equal HY zeolite and CrCl3 ratios could enhance the
levulinic acid yield compared to the individual catalyst (HY zeolite
or CrCl3) and physical mixing method. The results of this study
suggested that the catalytic reaction of the catalysts were predom-
inantly inuenced by the type of acid sites (Lewis acid), amount of
acid sites and strength, surface area, hierarchical porous structures
and shape selectivity properties.
4. Conclusions
Hybrid catalysts at weight ratios of 1:1, 1:2 and 2:1 between
CrCl3 and HY zeolite were prepared using the wetness impregna-
tion method. Thermal gravimetric analysis (TGA) indicated
22 N. Yaaini et al. / Microporous and Mesoporous Materials 171 (2013) 1423

Aqueous phase

H
H Catalyst surface Catalyst pores
HO O
HO
HO H
H OH
H OH
D-fructose O
H OH
OH
H O H3C
HO coke LA
HO H O
H OH mesopores
H OH (~3.90 nm)
+
D-glucose O
1,2-enediol
(0.9 nm) OH O
OH OH HOC CH2OH
C C C C C CH2OH H OH
H OH OH FA
O
HOC CH2OH +
HMF
H2O
HMF +
(0.82 nm) 3H2O

O
micropores
OH (~ 0.40 nm)
H3C
LA
O
+
O

H FA OH
+
H2O

Fig. 9. Proposed reaction scheme of glucose over hybrid catalyst.

(a) (b)
70 0.53
HY

H11
60
0.52
H12
Levulinic acid yield (%)

Relative microporosity

50
H21
0.51
40

30 H12 0.50

20
H21
HY 0.49
10 H11

0.150 0.155 0.160 0.165 0.170 0.29 0.30 0.31 0.32 0.33
Hierarchy factor (HF) Relative mesoporosity

Fig. 10. The catalytic performance of catalysts versus hierarchy factor (a) and relative microporosity versus relative mesoporosity (b) at 160 C and 180 min of reaction
temperature and time for HYHY zeolite; H11hybrid 1:1; H12hybrid 1:2 and H21hybrid 2:1 catalysts.

interaction of CrCl3 with the HY zeolite during the impregnation strength, surface area, hierarchy factor and shape selectivity. Hy-
process. Hybrid catalysts properties revealed that the catalytic brid 1:2 catalyst displayed the highest HF (0.1637) followed by hy-
reaction of the hybrid catalysts were predominantly inuenced brid 1:1, hybrid 2:1 and HY zeolite catalysts. However, hybrid 1:1
by the type of acid sites (Lewis acid), amount of acid sites and catalyst contained more reactive acid sites (13.13 lmol/m2) on the
 N. Yaaini et al. / Microporous and Mesoporous Materials 171 (2013) 1423
catalyst surface and exhibited the highest catalytic performance
with 62% of levulinic acid yield at 160 C in 180 min of reaction
temperature and time.
Acknowledgements
The authors would like to express their gratitude for the nan-
cial support from the Ministry of Higher Education (MOHE) under
the Fundamental Research Grant Scheme (FRGS) vote number
78681 and 78687. The Ministry of Science, Technology and Innova-
tion (MOSTI) is also acknowledged for sponsoring one of the
authors, (NY) under the National Science Fellowship (NSF). We
would also like to thank to Centre of Excellence for Catalysis Sci-
ence and Technology (PutraCAT), Universiti Putra Malaysia (UPM)
for the catalyst characterization work.
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