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Catalysis Science & Technology Accepted Manuscript

ARTICLE

Comparison of glucose conversion to 5-HMF using different

modified mordenites in ionic liquid and biphasic media
Received 00th January 20xx, a a b a,b,† b,†
Accepted 00th January 20xx W. Mamo , Y. Chebude , C. Márquez-Álvarez , I. Diaz , E. Sastre
DOI: 10.1039/x0xx00000x

www.rsc.org/ Modified mordenites have been used in the direct conversion of glucose into 5-hydroxymethylfurfural (5-HMF) in two
different media: the ionic liquid 1-butyl-3-methylimidazolium bromide ([BMIM]Br) and a biphasic system composed of
water-acetone and ethyl acetate. The results revealed that there are crucial differences in the final catalytic performances.
Modified mordenite treated with 1M NH4Cl only, with a moderate Si/Al ratio of 11.2 and a high content of strong Brønsted
acid sites (TPDNH3 acidity of 1.39mmol/g), possessed the highest catalytic activity resulting in 64% 5-HMF yield with 97%
glucose conversion in the ionic liquid system. On the other hand, the mordenite treated with 1M NH4Cl and 2.4M NH4F,
with total acidity of 1.51mmol/g, mainly due to Lewis sites, gave 50% 5-HMF yield with 98% conversion in the biphasic
system. The presence of strong Lewis acidity has a major effect on catalytic activity in aqueous–organic biphasic medium,
in agreement with earlier works that showed that the reaction proceeds via a Lewis acid-catalyzed isomerization followed
by Brønsted acid-catalyzed dehydration. In contrast, the quick adsorption and strong interaction of the ionic liquid with
the zeolite, which hinders the diffusion of the products, enhances the role of zeolite mesoporosity on the catalytic activity
when the reaction is carried out in ionic liquid solution.

45% yield from glucose (starch) in acid-basic media as

Introduction
Biomass is an abundant and carbon-neutral renewable energy
resource for the production of biofuels. Using catalysts for
biomass conversion is an alternative approach, especially for
the conversion of lignocelluloses to transportation fuels and
sugars to value added chemicals [1-5]. Out of the annual
renewable biomass, 75% are carbohydrates. For the
production of 5-hydroxymethylfurfural (5-HMF), various
renewable resources may serve as starting raw materials. In
addition to monosaccharides (fructose, glucose) the
disaccharide sucrose and other polymeric materials (e.g. inulin,
starch and cellulose) can be used [6]. Therefore, extensive
research efforts are currently being undertaken to develop
efficient and sustainable methods to prepare 5-HMF [7-12].
The synthesis of 5-HMF from fructose is not by itself
problematic and has been extensively described in the
literature. The economic potential of 5-HMF is closely related
to the type of bio-feedstock used. Due to the low availability of
fructose, its cost and the fact that it is a foodstuff, other
alternatives need to be exploited.
As early as 1962, Mednick described the synthesis of 5-HMF in
catalysts, consisting of pyridine and phosphoric acid, in a
mixture of water and dioxane as solvent at high temperatures
(200-300°C) [7]. Due to the higher natural availability of
glucose, it is a better feedstock and a potential candidate as a
source of 5-HMF production compared with fructose.
However, its stable structure (pyranose form) and the required
isomerization step before dehydration hinder its utilization for
feasible 5-HMF production [13]. Many catalysts with the
combination of different solvents have been tested, such as
mineral acids, lanthanide chlorides, stannous chloride,
chromium chlorides, tungsten salts, germanium chloride,
aluminum chloride, boric acid, heteropoly acids, strong acid
cation exchange resins, tin-Beta zeolite, acid-functionalized
SBA-15, sulfated zirconia, ionic liquid (IL) supported on silica
nanoparticles, and imidazolium salts [14]. Different media,
including water, organic solvents, ILs, and water/organic
biphasic systems, have been used in the dehydration reactions
for the production of 5-HMF. HMF yields from glucose in ILs
using various catalysts were in the range of 60 to 80%. Higher
HMF yields (91%) in the [BMIM]Cl/CrCl3 system with MIBK as
the second phase or with microwave irradiation were recently
reported [15-19]. Among all the catalysts used, metal chlorides
in ionic liquids were reported to be exceptional components
capable of converting glucose into 5-HMF in high yield. Zhang
et al reported a very high yield (89%) of 5-HMF from cellulose
by the combination of chromium (II) chloride and
ethylmethylimidazolium chloride (CrCl2/EMIMCl) at 120°C for
6h [20]. Yet, the greatest challenges remain in using catalysts

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that are less toxic and harmful to the environment together
with a catalytic system that allows recyclability, separation and
thus lower cost [21-25]. In this direction there are still efforts
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addition in the solution, the suspension was kept stirring for 30
minutes, followed by filtering and washing with hot deionized
o
water two times. Finally, the resulting solid was dried at 100 C

o
devoted to improve the catalytic setup. Very recently, an for 12h and calcined at 550 C for 6h to obtain modified H-MOR

Catalysis Science & Technology Accepted Manuscript

interesting design involving an entrained-intensified vacuum zeolites.
reactive distillation (EIVRD) process was developed for in situ
separation of 5-HMF from imidazolium ILs [26]. Also, using Table 1. Modification treatments and properties of the final
compressed CO2 for dissolving and separating 5-HMF from catalysts.
glucose and the IL has been essayed [27]. However, even these
processes are quite energy intensive for commercial CXRD SBET SMicro SMeso Pore Vol. PVMicro PVMeso
Sample Treatment
application. Promising improvement was obtained using (%)
2
(m /g)
3
t-plot t-plot (cm /g) DFT DFT
biphasic system reactors [28]. In order to reduce the side
M-P None 100 455 430 25 0.21 0.16 0.05
reaction significantly, the water-immiscible organic solvent
3 M NH4Ac +
plays an important role in extracting the products formed M-1
2.4 M NH4F
88 492 468 24 0.23 0.18 0.05
during the reaction. It is in biphasic system where zeolites are M-2 3 M NH4Ac 63 492 468 24 0.22 0.17 0.05
showing their potential as catalysts with tunable surface
properties, suitable for high selectivity of 5-HMF [29]. Zeolites M-3 3 M NH4Cl 118 502 476 26 0.23 0.18 0.05

were reported in the early works as highly selective and active M-4 1 M NH4Ac 57 488 461 27 0.21 0.17 0.04
catalysts in the synthesis of 5-HMF given their moderate
M-5 1 M NH4Cl 84 468 449 19 0.21 0.17 0.04
acidity and high pore volumes [30]. More recently, Beta
1 M NH4Cl +
zeolites with both Lewis and Brønsted acid sites have been M-6 55 440 422 18 0.20 0.16 0.05
2.4 M NH4F
tested and it was found that zeolites with large number of 3 M NH4Cl +
M-7 52 470 451 19 0.21 0.17 0.05
Lewis acid sites showed a better performance for the 2.4 M NH4F
1 M NH4Cl +
conversion of glucose into 5-HMF, while a smaller number of M-8
2.4 M NH4F
94 455 430 25 0.23 0.18 0.05
Lewis acid centers gave better yields of furfural from xylose
[31]. A recent work showed that [Sn,Al]-Beta with a suitable Characterization techniques
Sn/Al molar ratio gave a moderate yield of 34%, but with
62.1% selectivity to 5-HMF [32]. The possibility of using Powder X-ray diffraction (XRD) patterns were collected with a
o
hierarchical microporous materials with tuned acidic and basic PANalytical X'Pert Pro diffractometer at a step size of 0.02 and
properties, hydrophilic and hydrophobic character and a counting time of 50s, using nickel-filtered CuKα radiation.
adsorption and shape-selectivity properties make zeolites Crystallinity (CXRD) was calculated using the equation [31]:
advantageous as heterogeneous catalysts compared with 



    
 


 % =  100
other catalysts. 



     

Given the known advantages of heterogeneous catalysis and
the commercial interest of this reaction, there is still room for
an optimum catalyst design for the conversion of glucose to 5-
HMF. In this work, we tried to optimize the conditions using
mordenite zeolites as catalysts. In this direction our main aim
was to tune the acidity of mordenite to survey the impact in
the yield of 5-HMF from glucose. The effect of different
modification processes on the structural, textural and chemical
properties of the mordenite is systematically analyzed. Its
impact in the catalytic performance in the conversion of
glucose to 5-HMF is studied both in ionic liquid and biphasic
media.
Experimental
Modification of Mordenite
Zeolite mordenite CBV21A (Si/Al =10.5), was purchased from
ZEOLYST. The modification treatments along with the sample
codes are collected in Table 1. For a typical modification
experiment 2g of zeolite was stirred in 26mL of 3M
o copper grid.Temperature-programmed desorption of ammonia
NH4CH3COO (NH4Ac) solution at 25 C for 30 minutes. Then
12mL of 2.4M NH4F aqueous solution was added drop-wise on
o 2920 chemisorption analyzer, equipped with thermal
the previous suspension and stirred at 80 C. After complete
2 | J. Name., 2012, 00, 1-3
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Inductively Coupled Plasma Optical Emission Spectrometry
(ICP-OES, Perkin Elmer Optima 3300 DV model) was used to
determine the chemical composition. Samples were dissolved
by alkaline fusion for analysis. N2 adsorption isotherms were
o
measured at -196 C (77K) in a Micromeritics ASAP 2420
o
sorptometer. Samples were degassed at 350 C for 16h prior to
analysis. Specific surface area was calculated by the Brunauer–
Emmett–Teller (BET) method. Total pore volume was
measured as the amount of nitrogen adsorbed at a relative
pressure of 0.96. Micro- and mesopore surface area and
volume were determined with MicroActive data analysis
software using the t-plot method and the method of non-local
density functional theory (NLDFT) with a kernel function for
slit-like pore geometry that best fitted the mesopore region of
the isotherms. JEOL 2100F transmission electron microscope
(TEM) operating at 200kV was used to evaluate and locate the
presence of mesoporosity inside the crystalline zeolites. For
the TEM observations, the samples were crushed and
dispersed in ethanol and a few drops were placed on a holey
(NH3-TPD) was performed using a Micromeritics Autochem II
conductivity detector (TCD). Typically, 100mg of sample pellets
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(20–40 mesh) were pre-treated at 550 C for 1h in helium flow
(25mL/min) and subsequently cooled to the adsorption
o
temperature (177 C). A gas mixture of 5.0 vol.% NH3 in He was
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then allowed to flow over the sample for 4h at a rate of
15mL/min. Afterwards, a 25mL/min helium flow was passed
o
over the sample, while maintaining the temperature at 177 C
for 30min to remove weakly adsorbed NH3, and, finally, the
o o
temperature was increased to 550 C at a rate of 10 C/min.
Complementary characterization of acidity was carried out by
infrared spectroscopy of adsorbed pyridine using a Thermo-
Nicolet Nexus 670 FTIR spectrometer provided with an MCT
cryo-detector. Samples were pressed into self-supporting
2
buffers of ca. 9mg/cm thickness, placed in a glass transmission
o
cell with CaF2 windows and outgassed at 450 C for 10h under
-3
dynamic vacuum (residual pressure below 10 mbar). Pyridine
o
(Fluka) was adsorbed at 150 C (equilibrium pressure ca.
10mbar) and samples were subsequently evacuated at 250,
o
350 and 400 C for 1h. Spectra were recorded in the 4,000-
-1 -1
1,000cm wavenumber range at a resolution of 4cm by
averaging 250 scans and were normalized to a sample
2 27
thickness of 9mg/cm . Al MAS NMR spectra were acquired
using a Bruker AV-400-WB spectrometer operating at 104.26
MHz with a 4-mm probe at a spinning rate of 10kHz. A π/12
pulse of 0.8μs and recycle delay of 0.5 were applied. Solid
Al(SO4)2(NH4)·12H2O was used as secondary reference with a
chemical shift of -0.4ppm with respect to 0.1M Al(NO3)3.
Catalytic test.
Synthesis of the ionic liquid
The ionic liquid was prepared using previously reported
methods [34]. In a typical synthesis, 1.2 molar equivalent of
bromobutane was added to 1-methylimidazole (15g, 0.18mol)
while stirring at room temperature. When no 1-
methylimidazole was observed by NMR analysis (at about
48h), the product was recovered and washed three times with
1,1,1-trichloroethane. The desired product, butyl-
methylimidazolium bromide ([BMIM]Br), a yellowish viscous
o
liquid, was dried under high vacuum at 60 C.
Conversion of Glucose to 5-HMF in Ionic liquid
A batch catalytic reaction was carried out in an inert gas
atmosphere (N2) in a 250ml two-necked round bottom flask
heated in a temperature controlled oil bath placed on top of a
magnetic stirrer equipped with a reflux condenser. In a typical
experiment, 16g of [BMIM]Br previously dried at 95oC
overnight, was loaded into the flask. 5g of glucose was added
and the solution stirred for 15 minutes. Then, 0.5g (∼10% with
respect to sugars) of H-MOR were added. The flask was
subsequently heated in the oil bath at 100oC and samples were
taken at 0.5, 1, 3, 6 and 12h. The withdrawn samples were first
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treated with excess sodium sulphate (Na2SO4) to remove the
water [35], extracted with ethyl acetate (10mL, 3 times) and
the organic phase was collected and distilled under reduced
pressure to obtain pure 5-HMF that was dissolved in
Catalysis Science & Technology Accepted Manuscript
1
deuterated chloroform for H NMR studies. The yellowish
residue left in the flask was dried for 2-3h and dissolved in
1 13
deuterated chloroform for H and C NMR studies.
Conversion of glucose to 5-HMF in biphasic system
In the same batch set up, these catalytic reactions were
carried out in a two-phase system containing a reactive
aqueous layer (mixture of water and acetone) and an
extracting organic layer (ethyl acetate). Prior to the tests, the
solubility of glucose and further reaction was checked at
various acetone: water weightratios (1:0, 2:1, 3:2 and 4:1), and
a 3:2 ratio was chosen for the catalytic reactions. For a typical
reaction in the best conditions: 1.25g of glucose was dissolved
by stirring in 8.0g of aqueous phase (3:2 acetone:water weight
ratio) and mixed in a 250ml round bottom flask with 12.0g of
ethyl acetate and 0.125g of the H-MOR. Then, the reactor was
heated and the reaction carried out at ambient pressure under
reflux conditions (measured reaction temperature was 65ºC).
Once the reaction temperature is reached, samples were taken
after each reaction time, and then cooled to room
temperature followed by separation under rotary evaporation.
Both, the organic phase containing the 5-HMF and the
aqueous phase containing the remaining glucose were
1 13
analyzed by H and C NMR.
Analysis of 5-HMF
1 13
The H and C NMR spectra of the different product samples
and their corresponding residues were acquired using a Bruker
13
400 Ultra-Shield 400MHz NMR. C-NMR was employed to
identify and confirm the products. For quantification of 5-HMF
1
using H-NMR, a known concentration of mesitylene (1,3,5-
trimethylbenzene) was added as an internal standard to the 5-
HMF product solution dissolved in CDCl3. The percentage of 5-
HMF yield was calculated using the integrated values of the
aldehyde proton (δ=9.58ppm) of 5-HMF and three aromatic
1
ring protons of mesitylene (δ= 6.79ppm). A standard H-NMR
spectrum of 5-HMF was used for correlating the actual
formation of 5-HMF. The glucose conversion was calculated by
1
comparing the integral area of the H NMR spectrum of the
residue left after extraction of 5-HMF with that of pure glucose
[36].
The yield, conversions and selectivity were calculated using
previously reported formulae [37]. The yield of 5-HMF was
calculated as % of the moles of 5-HMF actually produced in
each test relative to the theoretical maximum number of
moles of 5-HMF assuming 100% conversion [38]:
J. Name., 2013, 00, 1-3 | 3
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    (
%) =  100
     ℎ  

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Catalysis Science & Technology Accepted Manuscript

#
   $%&
"  (%) =  100
'   
   (  M-8

"
  $%&
$%& 
) (
%) = M-7
  

Results and discussion
Characterization of the modified mordenites
The modification methods chosen are aiming to slightly modify
the acidity of the mordenite. Conventional cation exchange
treatments are carried out and compared with similar
treatments including chelating agents (acetate). These
treatments are all mild, with the intention of inferring small
surface changes and variations in the ratio of Brønsted to
Lewis acid sites, their strength and their vicinities. In all cases,
o
the modified mordenite was calcined at 500 C for 6h prior to
characterization. The evaluation of the crystallinity and
remaining mordenite (MOR) structure of the samples was
done by powder X ray diffraction (XRD). Figure 1 shows the
diffraction patterns following the Monoclinic Cmcm space
group of MOR [39] with no important changes observed in the
peaks intensities. In order to quantify this structural
modification, the values of the degree of crystallinity, CXRD, of
the treated samples have been calculated using the parent
commercial mordenite as the reference [33].
The quantitative analysis of diffraction data indicates a
decrease in crystallinity as it can be observed from the data
collected in Table 1. If the crystallinity of parent MOR (M-P) is
defined as 100%, a decrease up to 50% was observed upon
calcination of the treated zeolite samples. In the case of M-1,
M-3, M-5 and M-8 higher crystallinity is retained (above 84%),
and in the case of M-3, treated with 3M NH4Cl, a higher
crystallinity (118%) was found probably due to recrystallization
of the leached species. The treatment of M-1 sample,
corresponding to a mild method aiming to remove aluminum
selectively from the outer surface of the zeolite crystals
maintains 88% crystallinity. The lowest values are obtained for
samples M-6 and M-7 with 55 and 52%. This qualitatively
agrees with literature reports on the crystallinity of
dealuminated MOR [40].
Textural analysis reveals that in all the cases, the micropore
volume and the surface area increased (Table 1) probably
induced by an appreciable change in the pore size distribution
[41]. In addition, the external surface area was enlarged, which
can be attributed to the presence of mesoporosity and
probably increased surface roughness due to the treatments.
4 | J. Name., 2012, 00, 1-3
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M-6
Intensity (a.u)
M-5
M-4
M-3
M-2
M-1
M-P
5 10 15 20 25 30 35 40 45 50 55 60
2Θ( )
O
Figure 1. X ray diffraction patterns of the parent and modified
mordenite samples.
Higher concentrations of ammonium acetate or ammonium
chloride (M-1 to 5) appear to give the best combination of
microporosity, high surface and external area, and high
mesopore volume, parameters which look to be critical for this
particular reaction. Finally, systematic TEM studies of all the
modified samples revealed that the samples show different
degree of partial dissolution or presence of mesopores.
A crystalline zeolite with mesopores was obtained after the
treatment in the cases of M-1, M-3 and M-7, whereas in M-2,
M-4, M-5 and M-6, no remarkable presence of mesopores
could be observed. For instance, sample M-1 shows small
voids with few nm in dimension, as interruptions of the lattice
planes of the mordenite structure, as shown in Figure 2. On
the other hand, Figure 3 collects a representative image of
sample M-7 showing larger presence of brighter contrasts
within the crystals due to the dissolution of the framework in
those areas. These results agree with the crystallinity results,
although it is difficult to correlate this information with the
textural values, probably due to the lack of information
regarding the accessibility of the mesopores observed in TEM.
In terms of modification treatment, the three samples refer to
high concentration of ammonium salt (3M): M-1, 3M NH4Ac +
NH4F; M-3, 3M NH4Cl only, and M-7, 3M NH4Cl + NH4F.
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Catalysis Science & Technology Accepted Manuscript

M-7
Figure 2. TEM images at low (A) and high magnifications (B) in
sample M-1.
M-5

M-3

M-2

M-1

27
Figure 3. TEM images at low (A) and high magnifications (B) in Figure 4. Al MAS NMR spectra of the parent and selected
sample M-7. modified mordenite samples.

Nevertheless, the aim of the mild treatments applied is to

evaluate how this mild modification treatments may have an
Table 2. Chemical analysis (ICP), Al in the framework (NMR), and
impact in the strength of the acid sites and their vicinities, and
acidity (NH3-TPD and Py-IR)
thus an impact in the selectivity of the reaction towards 5-HMF
[42].
Total Strong
ICP-OES elemental analysis was used to quantify the final Sample
Intensity Intensity Si/AlICP Si/Al AcidityTPD
Brønsted Brønsted
composition of the samples and follow the variation of the Td (%) Oh (%) total framework (mmol/g)
sites (%)a sites (%)b
Si/Al ratio, which coupled with solid state 27Al NMR would M-P n.d. n.d. 10.50 n.d. 1.01 67
further allow to distinguish between the Al species remaining M-1 86.6 13.4 11.46 13.2 1.60 79
in the zeolite framework and those that are outside on the M-2 84.9 15.1 11.39 13.4 1.45 n.d. n.d.
pore surface (extra framework species EFAl). The results in M-3 86.2 13.8 11.18 13.0 1.49 n.d. n.d.
Table 2 indicate a mild dealumination of all samples (the Si/Al M-5 84.7 15.3 11.15 13.0 1.39 67
ratio increased from 10.5 to 12.5 maximum). The 27Al MAS M-7 85.4 14.6 12.50 14.6 1.44 n.d. n.d.
NMR spectra of selected samples are plotted in Figure 4. In the M-8 n.d. n.d. 11.41 n.d. 1.51 23
a
Percentage of total acid sites that are of Brønsted type as determined from FTIR
case of the modified mordenites, all the samples contain
spectra of adsorbed pyridine after evacuation at 250 °C
tetrahedral framework Al (55ppm) and octahedral extra a
Percentage of strong acid sites that are of Brønsted type as determined from FTIR
framework Al (0ppm). Using 27Al MAS NMR intensities and spectra of adsorbed pyridine after evacuation at 400 °C

total Si/Al ratio ((Si/Al)tot) from the ICP-OES analysis, the Si/Al
ratio of the framework Al ((Si/Al)fr) was calculated using the
intensity ratio of tetrahedral (IAltet) and octahedral aluminum
(IAloct) by the following previously reported formula [43]:
(Si/Al)fr = (Si/Al)tot (IAltet + IAloct)/IAltet
As shown in Table 2, the bulk Al content is always higher than
the framework aluminum content for all the modified
mordenites. Only 15% of the total aluminum exists in the extra
framework and more than 80% in the framework. The Si/Al
ratio of the framework is greater than the total as expected,
since some of the Al species are found in the extra framework
of the structure.
The total amount of acidic sites (Brønsted + Lewis) in the
samples, measured by NH3-TPD is given as well in Table 2. As
expected, the acid site distribution does not change
significantly with the degree of dealumination. Relatively small
acidity is observed in M-5, which was treated by ammonium
chloride only. The total acid site distribution determined by
temperature programmed desorption (TPD) of NH3 does not
change significantly with the surveyed treatments. In order to
assess in a more accurate manner whether the ratio between
Brønsted and Lewis sites has varied and how this would
influence the final catalytic activity of the obtained
mordenites, Pyridine-IR studies have been carried out on

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selected samples. Figure 5 shows difference FTIR spectra Conversion of glucose into 5-HMF in ionic liquid
showing characteristic pyridine ring vibration bands of The results for conversion of glucose to 5-HMF and the yield
pyridinium species formed by protonation on Brønsted sites obtained using modified mordenites in the presence of the IL
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(B) and pyridine coordinated to Lewis sites (L).

Catalysis Science & Technology Accepted Manuscript

are collected in Table 3. Despite the similar acid properties
observed in M-P, M-1 and M-5, their performance is rather
B+L
different. While M-P and M-1 give low yields both at 3h and
0.5
B L B 6h, M-5 converts almost 30% of glucose into 5-HMF at 3h.
L

M-P
Table 3. Conversion and Yield of 5-HMF and LA (Levulinic acid) in
+ -
[BMIM] Br at 100°C for 6h (in parenthesis data for 3h).

Conversion Yield Selectivity Yield Selectivity

Catalyst
(%) 5-HMF (%) 5-HMF (%) LA (%) LA (%)
Absorbance

M-P 93 28(4.8) 30 8 9

M-1
M-1 97 18(4.5) 18 4 4
M-2 97 14(5) 14 3 3
M-3 97 25(6.5) 25 15 16
M-4 58 14(5.5) 25 4 6

M-5
M-5 98 64(30) 66 0.1 0.1
M-6 98 32(8) 33 0.3 0.3
M-7 97 32(9.5) 32 0.1 0.1
M-8
M-8 91 4(1) 4 2 2

Reaction conditions: Catalyst 10 % (0.5 g), 100 °C, Nitrogen atmosphere.

1650 1600 1550 1500 1450
-1
wavenumber (cm )
Figure 5. Difference FTIR spectra of mordenite samples after
o
pyridine adsorption at 150 C and desorption at increasing
o
temperatures (top to bottom: 250, 350 and 400 C). The spectra of
the corresponding pre-treated samples have been subtracted.
In all cases, the spectra show that the intensity of bands
assigned to adsorbed pyridinium species decreases as the
desorption temperature increases, while the intensity of those
corresponding to pyridine coordinated to Lewis sites remains
nearly constant. These results indicate that an important
fraction of total Brønsted sites are of medium strength, while
most of the Lewis sites show strong acidity. The number of
both type of sites has been estimated by integration of the
-1 -1
bands at 1545cm (B) and 1455cm (L) using the extinction
coefficients reported by Emeis [44]. Total concentration of acid
sites was determined from the spectra collected after
o
desorption at low temperature (250 C) while content of strong
acid sites was calculated from the amount of pyridine retained
o
by the catalysts after evacuation at high temperature (400 C).
As shown in Table 2, samples M-P, M-1 and M-5 show similar
total Brønsted to Lewis sites ratio, while sample M-8 exhibits
significantly lower fraction of Brønsted sites. This difference is
even more pronounced when comparing strong acidity, as the
content of Brønsted sites of sample M-8 corresponds to less
than 10% of the total strong sites, well below the 50% level
shown by the other samples.
A maximum of 64% yield of 5-HMF, in the conditions surveyed
in this work, was obtained using M-5 at 6h (Figure 6A).
Levulinic acid (LA) and folic acid (FA) were detected in the
modified mordenite catalyzed reactions in different
percentages indicating the different selectivity of the catalysts.
However, using M-5 almost no LA (0.1%) was identified at 6h.
In this particular reaction, relatively low acidity is required for
the dehydration step; this could explain why sample M-P with
strong Brønsted acid sites yields higher LA. Usually, increasing
the acidity of the catalysts leads to secondary reactions.
However, this does not explain the performance of M-5
treated only by 1M NH4Cl, which leads only to cation exchange
but very little dealumination and small increment in acidity
and mesoporosity. On the other hand, the selectivity is
thought to increase by increasing the Si/Al ratio, i.e. increasing
the hydrophobicity. The ionic liquid is quickly adsorbed in the
zeolite where it seems to be highly retained, indicating that
the diffusion of the products may be hindered [45]. This effect
could be the reason of the induction period observed in the
formation of 5-HMF. After that time, the conversion towards 5-
HMF increases rapidly to reach a maximum, and then decreases by
its transformation in secondary products. In such scenario, the
acidity of the zeolite plays a secondary role since the possible
effect in yield would be determined by the diffusion out of the
channels of the mordenite that are filled with IL. A final
attempt to rationalize the selectivity results is in terms of
mesoporosity. The influence of the small variation in
mesoporosity of the catalysts on the selectivity to 5-HMF is
shown in Figure 7. The catalysts with lower mesoporous

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volume M-5, M-6, and M-7 were the most selective whereas reaction intermediates and is thereby protected against
M-1 and M-3 having slightly larger mesoporosity seem to be degradation reaction; however, most extracting solvents used
less selective. Thus in this case, most probably the better show poor partitioning of 5-HMF into the organic phase,
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necessitating large amount of solvent and hence large energy

Catalysis Science & Technology Accepted Manuscript

performance of M-5 could be attributed to the mild
modification produced only in the external surface of the
crystals since the rest of the properties of this catalyst (acidity
and porosity) does not allow for a straightforward relationship
between acidity and yield to 5-HMF.
A
B mordenite (8%) and the other modified mordenites. In this
consumption to purify the diluted 5-HMF product. An initial
optimization step implied studying the solubility and
conversion of glucose in mixtures acetone:water in order to
obtain a system with minimum use of water, including a
volatile solvent that may enhance the separation of the
products [55]. Therefore, several acetone:water mixtures were
tested and good solubility was finally observed using a 3:2
weight ratio. Ethyl acetate was added to extract 5-HMF as it is
produced and to form the biphasic layer. Table 4 summarizes
the results obtained using the different treated mordenite
samples in the conversion of glucose to 5-HMF in
acetone:water/ethylacetate at 65oC. All modified synthetic
mordenite catalysts gave higher yield than the unmodified
mordenite. M-8 gave a much better result than the parent
case M-8, treated by1 M NH4 Cl and 2.4 M NH4F, which gave
the lowest yield in the reaction performed inIL solution, gave
the highest yield (50 %) whereas M-1 rendered only 24%, and
M-5 yielded negligible amount of 5-HMF.

Table 4. Conversion of glucose, yield and selectivity to 5-HMF

in biphasic system at 65°C for 9h.

Figure 6. Evolution of the formation of 5-HMF with time A)

o
using sample M-5 in IL at 100 C; and B) using sample M-8 in
o
biphasic medium at 65 C. Catalyst Conversion (%) Yield 5-HMF (%) Selectivity 5-HMF (%)

M-P 95 8 8
M-1 96 24 26
60
M-2 97 30 31

50
M-3 99 29 30
M-4 90 2 -
HMF yield %

40
M-5 95 4 -

30
M-6 98 30 31
M-7 97 2 -
20
M-8 98 50 51

10 Reaction conditions: Catalyst 10 % (0.125 g), 65 °C.

0
0.042 0.044 0.046 0.048 0.050
3
mesopore volume (cm /g)
Figure 7. Effect of mesoporous volume on the selectivity to 5-
HMF over modified mordenites
Conversion of glucose to 5-HMF in biphasic system
The use of a biphasic system with two immiscible solvents can
overcome the diffusion problems because 5-HMF produced in
the aqueous phase can migrate into the organic phase to avoid
further reaction [46-54]. The optimum results obtained in
biphasic system reached 70% yield of 5-HMF, using again toxic
Cr(III) salts [52]. The use of less toxic and environmentally
friendly catalyst such as zeolites is again worth investigating. In
these systems, the product is separated from the reactant and
0.052 As it can be observed in the best system (M-8) plotted in
Figure 6B, the reaction is rather slow compared to the IL
systems. With the best catalyst, M-8, at 6h only 7% of 5-HMF
was formed, which reaches an optimum yield of 5-HMF of 50%
at 9h with 51% selectivity to 5-HMF. Further increment of the
reaction time did not offer additional 5-HMF yield, possibly
due to the preferential formation of soluble polymers and
humins, as well as the deposition of residues formed from
intermediates condensation on the active sites. In fact, in the
biphasic system no LA and FA formation was observed but the
residue contained dark colored tarry solids, which is attributed
to the formation of soluble polymers and insoluble humin. This
could be due to the strong acid sites [56]. On the contrary,
sample M-8 shows very low decrease in crystallinity and no
variation in surface area or textural properties compared with

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the parent zeolite, but a significant change of acidity. In this
scenario, most probably the presence of more Lewis sites,
together with lower fraction of Brønsted sites and probably
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more hydrophobic pore surface is leading to higher yield and
selectivity, which agrees with the reported results using
modified zeolite Beta [29].
In summary, Figure 8 plots the different performance of the
treated zeolites in the two systems allowing concluding that in
the IL the best performance was obtained with mordenite
modified with 1M NH4Cl only, with a moderate Si/Al ratio of
11.2 and large number of strong Brønsted acid sites (TPDNH3
acidity of 1.39mmol/g). This zeolite exhibited the highest
catalytic activity resulting in 64% 5-HMF yield with 97%
glucose conversion at a reaction temperature of 100oC within
6h in the ionic liquid system. This yield of 64% is the highest
obtained using zeolitic catalysts in IL system, being only
surpassed by Cr(III) salts in ionic liquids [15-19]. On the other
hand the mordenite treated with 1M NH4Cl and 2.4M NH4F,
with total acidity of 1.51mmol/g, but mainly due to Lewis sites
gave 50% 5-HMF yield with 98% conversion and 51% selectivity
to 5-HMF at a temperature of 65oC within 9h in the biphasic
system. In any case, the 50% yield of 5-HMF obtained using
modified mordenite, is higher than the yield obtained using
Sn,Al-Beta in similar reaction conditions [32] and only below
the excellent catalytic reactor designed by Nikolla et al. in
which Sn-Beta was used as catalyst [29].
Figure 8. Comparison of the performance of the different
o
modified mordenite samples in both systems: in IL at 100 C
o
and 6h (dark grey) and biphasic at 65 C and 9h (light grey).
Conclusions
Mordenite zeolite has been tested as catalyst for the
conversion of glucose to 5-hydroxymethylfurfural in both
biphasic aqueous–organic and ionic liquid reaction media. Mild
modification treatments with ammonium and/or fluoride
solutions have been shown to alter acidic and textural
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properties of the zeolite and influence catalytic activity. 5-HMF
yield as high as 64% was obtained for the reaction carried out
in 1-butyl-3-methylimidazolium bromide solution catalyzed by
mordenite treated with 1M NH4Cl solution. In biphasic
Catalysis Science & Technology Accepted Manuscript
acetone:water/ethylacetate medium, the maximum yield
reached 50% and was obtained using mordenite treated with
1M NH4Cl and 2.4M NH4F solution. It is found that the
presence of strong Lewis acidity has a major effect on catalytic
activity in aqueous–organic biphasic medium, in agreement
with earlier works that showed that the reaction proceeds via
a Lewis acid-catalyzed isomerization followed by Brønsted
acid-catalyzed dehydration. In contrast, the quick adsorption
and strong interaction of the ionic liquid with the zeolite,
which hinders the diffusion of the products, enhances the role
of zeolite mesoporosity on the catalytic activity when the
reaction is carried out in ionic liquid solution. Thus, zeolite
mesoporosity and ratio of Lewis and Brønsted active centers of
different acid strength must be optimized depending on the
reaction medium in order to maximize the production of 5-
HMF.
Acknowledgements
The authors acknowledge Spanish Government, MINECO
(MAT2012-31127) and the Spanish Research Council CSIC
(COOPB20082), for funding. ID acknowledges the CSIC for the
research leave at Addis Ababa University. WM acknowledges
Dilla University for support. The Chemistry Department, Addis
Ababa University is also acknowledged for financial support.
Dr. Antonio Chica ITQ-CSIC is also acknowledged for valuable
discussions.
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