DOI: 10.1002/slct.

201701955 Full Papers

1
2 z Catalysis
3
4
5
Ionic Liquid-Encapsulated Zeolite Catalysts for the
6 Conversion of Glucose to 5-Hydroxymethylfurfural
7
8 Pooja Saxena, Bharath Velaga, and Nageswara Rao Peela*[a]
9
10
11 Ionic Liquid (1-Butyl-3-methylimidazolium Bromide ([BMIM]Br) encapsulated in the zeolite. The catalytic tests were carried out
12 or Choline Chloride (ChCl)) encapsulated zeolites (HY and H- in presence of NaCl and an extraction phase to remove the
13 MOR) have been synthesized by ship-in-a-bottle strategy and formed HMF. The test results of BMIMBr H-MOR indicate that
14 tested for selective conversion of glucose to 5-Hydroxymethyl- even though there is a significant decrease in the surface area
15 furfural (HMF). Nitrogen sorption analysis showed that the with encapsulation, the yield and selectivity are higher with
16 surface area and total pore volume decreased and average this catalyst as compared to its bare zeolite counterpart. The
17 pore size increased significantly when the zeolites are encapsu- effect of the addition of NaCl and extraction phase and reaction
18 lated with ionic liquids. The major effect was found to be on conditions such as reaction time and temperature on activity
19 the microporosity whereas the mesoporosity is affected only and yield of HMF are evaluated on the best catalyst. In catalyst
20 marginally. From Thermogravimetric Analysis it is observed that stability study, the reasons for deactivation of catalyst are
21 the decomposition temperature of ionic liquids increased when identified by post-reaction catalyst characterizations.
22
23
multifunctional reactors (by combining reaction with the
24 Introduction
extraction of HMF using a biphasic system) have been used.[2b,3]
25
The fossil resources, such as petroleum, coal and natural gas, Several studies reported high yields of HMF with fructose as
26
have been the efficient promoters of economic growth for the starting reactant over various homogeneous catalysts such as
27
past several decades. Rapid depletion of such fossil resources mineral acids,[4] ionic liquids,[5] metal salts[4,6] and heterogeneous
28
and the increased environmental concerns triggered the need catalysts such as zeolites,[7] TiO2, and heteropolyacids.[8] How-
29
for alternative and renewable resources for both chemicals and ever, fructose is a costly material and economics does not work
30
energy production. In this context, biomass can be utilized as out for this reaction. Therefore, direct conversion of glucose
31
an alternative resource to produce chemicals in a sustainable and cellulose to HMF has been tested by various researchers.
32
and environmentally friendly way.[1] Particularly, lignocellulosic Conversion of glucose to HMF involves isomerization of glucose
33
biomass has attracted the attention of researchers as it is to fructose followed by dehydration of fructose to HMF. In this
34
abundantly available in the form of forest and agricultural series of reactions, isomerization is the bottleneck reaction.[9]
35
residues which do not interfere with the food supply chain. Therefore, isomerization has been studied by several research-
36
One more major advantage with this resource is that its ers and Sn-Beta zeolite is found to be the best isomerization
37
utilization does not emit any additional carbon dioxide into the solid acid catalyst.[10] However, some studies indicate that direct
38
atmosphere as it follows a closed carbon cycle. conversion of glucose to HMF is also possible.[1b,7b,11]
39
5-hydroxymethylfurfural (HMF) is recognized to be one of In general, with metal chloride catalysts the yield of HMF
40
the most important value-added chemicals with its applications from glucose is high.[4,5b,6b] Particularly the yield of HMF with
41
in several areas such as fine chemicals, fuels, polymers etc.[1b,2] CrCl3 is in the range of 10 to 80% depending on the reaction
42
One of the major components of lignocellulosic biomass is the conditions and solvent used.[6b] However, the difficulty of
43
cellulose and is a polymer of glucose. In glucose conversion to operation (due to difficulty in separation of this homogeneous
44
HMF, there may be side reactions which result in by-products catalyst) and carcinogenic nature of chromium does not allow
45
such as levulinic acid and formic acid and undesirable side- the commercial use of this catalyst. Ionic liquids have been
46
products such as humins. To minimize such side reactions, used as solvents as well as catalysts for the conversion of
47
carbohydrates into HMF.[2f,5b,12] With fructose as a substrate, the
48
HMF yields are very high up to more than 90%.[5a] However,
49
when glucose is used as a substrate the HMF yields are low in
50 [a] P. Saxena, B. Velaga, Dr. N. R. Peela
Department of Chemical Engineering the range of less than 10%. This indicates that the ionic liquid
51
Indian Institution of Technology Guwahati itself could not catalyze the glucose to HMF conversion.
52 Guwahati, Assam, India, PIN 781039. However, when an ionic liquid is used as a solvent in
53 Phone: + 91 361 2583526
combination with some catalysts containing Lewis acid sites
54 Fax: + 91 361 2582291
E-mail: peelanr@iitg.ernet.in (such as CrCl3, Zeolites) produces higher yields of HMF.[10d,13]
55
Supporting information for this article is available on the WWW under Combination of the ionic liquids (as solvent/catalyst) and
56
https://doi.org/10.1002/slct.201701955 zeolites showed interesting results with higher yields of HMF
57

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from glucose. For example, Hu et al.[2e] reported a conversion of
1
80% and an HMF yield of about 50% with Hb-zeolite (Si/Al = 25)
2
as a catalyst and [BMIM]Cl as a solvent. Xu et al.[14] obtained an
3
HMF yield of 70% from glucose in presence of Sn-MCM-41 as
4
catalyst and [EMIM]Br as solvent/catalyst., Mamo et al.[15]
5
studied the conversion of glucose to HMF with [BMIM]Br as
6
solvent/catalyst and modified zeolite mordenite as catalyst and
7
reported an HMF yield of 64% with 98% glucose conversion.
8
However, ionic liquids are high boiling solvents which require
9
high energy for HMF separation. One way to circumvent this
10
problem is to encapsulate them in the zeolites so that they are
11
intact inside the cavities of the zeolite.[16] Moreover, ionic liquid
12
encapsulated zeolites could act as bifunctional catalysts.
13
Recently, Yang et al.[17] have demonstrated that IL coated on
14
AlCl3/SiO2 gives better yields of HMF from fructose and glucose
15
substrates. It was observed that no IL dissolves into the organic
16
solvent (Methyl Isobutyl Ketone, MIBK) used in their study.
17
However, the catalytic activity decreases significantly with a
18
number of experimental cycles.
19
Herein we reported, for the first time, the production of
20 Figure 1. X-Ray Diffraction patterns of HY, BMIMBr-HY, H-MOR, BMIMBr H-
HMF from glucose using IL (Butylmethylimidazolium Bromide
21 MOR, and ChCl H-MOR catalysts.
([BMIM]Br) and Choline Chloride (ChCl)) encapsulated H-MOR
22
and H Y zeolites as catalysts. The IL ([BMIM]Br) encapsulation
23
was carried out using the ship-in-a-bottle method that is
24
reported in Ref.[18] ChCl was encapsulated using impregnation
25
method. These catalysts were tested for the conversion of
26
glucose to HMF. There are two reasons for investigating glucose
27
dehydration over IL encapsulated zeolites. One is to avoid
28
issues associated with using IL in homogenous phase. For
29
example, the IL in homogeneous phase results in separation
30
problems in post-processing steps of 5-HMF synthesis. The
31
second one is to explore the synergistic effects which result
32
from the presence of both IL and acid sites of zeolites in a close
33
proximity. To the best of our knowledge, no reports have been
34
published on the IL encapsulated zeolites for glucose con-
35
version to HMF.
36
37
38
Results and Discussion
39
40 Catalyst Characterization
41 Figure 2. Weigh loss (%) plotted as a function of temperature (TGA) for HY,
Powder X-Ray diffractogram obtained for all the conventional BMIMBr-HY, ChCl-HY, H-MOR, BMIMBr H-MOR, and ChCl H-MOR catalysts
42
as well as synthesized zeolites are shown in Figure 1. As
43
expected, FAU or MOR characteristic peaks are present and are
44
comparable with the literature.[19] Based on these results, all the
45
employed zeolites are found to be highly crystalline in nature. IL encapsulated zeolites is measured at room temperature
46
XRD patterns obtained after incorporating IL are very similar in (30oC) to 800 8C and showed two major weight loss regions.
47
nature to the patterns of respective parent zeolite confirming The first of which corresponds to the loss of moisture from
48
that the original crystal structure is not destroyed during the zeolite pores, by evaporation. The moisture loss zone is
49
encapsulation. However, the results show an increase in the considered to be up to 200 8C. The second region of weight
50
intensity of diffraction peaks from IL encapsulated zeolites. A loss (in the temperature range of 200–800oC) corresponds to
51
similar phenomenon is observed by other researchers al- the degradation of IL. As can be observed from the figure, the
52
so.[1a,18,20] This may be explained by the readjustment of H + ions decomposition temperature range is different for different IL-
53
(which are initially distributed randomly within crystal structure) zeolite. For pure IL, [BMIM]Br, the decomposition temperature
54
due to incoming new larger cations from the ionic liquid.[18] is 260 8C as reported by Yu et al.[18] For BMIMBr-HY, the
55
Typical TGA profiles of HY, H-MOR and their IL encapsulated decomposition step ranges from 350–486 8C while for H-MOR
56
counterparts are shown in Figure 2. The thermal degradation of the range is 425–635 8C. For choline chloride, the range falls in
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337–510 8C and 260–537 8C when encapsulated in HY and H- 196 8C and the results are summarized in Table 2. The isotherms
1
MOR zeolites, respectively. It can be observed that the thermal (which for HY and BMIMBr-HY are shown in Figure 3a, for H-
2
stability of ILs is enhanced after encapsulation within the MOR, BMIMBr H-MOR before and after recycle tests are shown
3
zeolite pores, which may be due to the strong bonding of ILs Figure 3b and for ChCl-HY and ChCl H-MOR are shown in
4
with the zeolite surface. Based on the temperature range of Figure S1, SI) displayed type – IV hysteresis loops, for all Y and
5
weight loss (in the 2nd region) it can be emphasized that the MOR zeolites confirming their mesoporosity as observed from
6
stability is more in the IL H-MOR. literature.[19a,b,d,21]
7
The weight loss in the range of 200–800 8C, which is The isotherms before and after ionic liquid encapsulation
8
considered to be weight loss due to IL decomposition, is resemble each other in terms of the type of hysteresis loop,
9
presented in Table 1. With [BMIM]Br the weight loss is higher in however, the surface area reduced significantly in the latter
10
case. As shown in Table 2, [BMIM]Br encapsulation resulted in a
11
surface area decrease of 13.2% (from 773 to 671 m2/g) for HY,
12 Table 1. Weight loss data from TGA study for various catalysts (in the and of 90.1% (from 365 to 36 m2/g) for H-MOR. Micropore
13 temperature range of 200–800 8C).
surface area and volume as calculated from t-plot data for H-
14 Weight loss (%)
S. No.
Catalyst MOR is significant (306 m2/g) but became zero in case of
15 (SiO2:Al2O3 ratio) Fresh Catalyst After Reaction
BMIMBr H-MOR zeolites. This decrease is much higher when
16
1 HY (80:1) 2.24 15.97 compared to that in the case of BMIMBr-HY (from 440 to
17 2 BMIMBr-HY 5.58 13.97 343 m2/g).
18 3 ChCl-HY 3.97 9.28
4 H-MOR (20:1) 3.31 9.88
The total pore volume decreased and the average pore size
19
5 BMIMBr H-MOR 9.04 18.97[a] increased after encapsulation of [BMIM]Br in both HY and H-
20
6 ChCl H-MOR 6.23 12.74 MOR zeolites. The decrease of pore volume (from 0.58 to 0.53
21
[a]
After recycle test. cc/g) and an increase of average pore size (from 1.50 to
22
3.16 nm) is marginal in the case of BMIMBr-HY. However,
23
changes in both total pore volume (from 0.27 to 0.15 cc/g) and
24
average pore size (from 3.00 to 16.24 nm) are significant in the
25
the case of H-MOR as compared to that in HY. A similar trend is case of BMIMBr H-MOR. Similar trends were observed for ChCl-
26
observed for choline chloride case also with lower weight loss HY and ChCl H-MOR. The [BMIM]Br encapsulation has a
27
from ChCl-HY as compared to that from ChCl H-MOR. This data significant effect on micropore surface area and micropore
28
indicates that the amount of IL (both [BMIM]Br and ChCl) volume, in both the cases (HY and H-MOR).
29
encapsulated in H-MOR is higher than that in HY. Though the Based on this data, it can be observed that HY is having
30
weight loss is more in the case of IL H-MOR, the decom- higher meso- as well as micro-pore surface area and volume
31
position temperature range is higher in the case of BMIMBr H- than H-MOR. After ionic liquid encapsulation, no micro-pore
32
MOR as compared to that in the case of BMIMBr-HY. The higher area was accessible in the case of H-MOR. This can be
33
temperature range can be correlated to the strong interaction attributed to either filling of micropores or to blockage of pore
34
between IL and the H-MOR zeolite sites. The strong interaction, entrance of H-MOR by the ionic liquid. Either way, our data
35
indeed, is favorable for stable catalyst performance. prove that ionic liquid encapsulation in HY occurred in super-
36
The specific surface area, pore volume and pore size of cages and in H-MOR it occurred in micropores. These results
37
samples were measured by nitrogen sorption analysis at – are further verified by differential pore volume Vs. pore size
38
39
40
41 Table 2. Surface area, total pore volume and average pore size determined from nitrogen sorption data
42
Catalyst Avg. Pore Size SBET[a] SDFT[b] Vp[c] Microporosity Mesoporosity
43 (nm) (m2/g) (m2/g) (cc/g) Smicro[d] Vmicro[d] Smeso[d] Vmeso[e]
44 (m2/g) (cc/g) (m2/g) (cc/g)
45
HY 1.50 773 783 0.58 440 0.23 333 0.35
46 ChCl-HY 2.15 737 na 0.40 na na na na
47 BMIMBr-HY 3.16 671 663 0.53 343 0.18 328 0.35
48 H-MOR 3.00 365 524 0.27 306 0.16 59 0.11
ChCl H-MOR 9.63 35 Na 0.09 na na Na na
49
BMIMBr H-MOR 16.24 36 24 0.15 0.00 0.00 36 0.15
50 BMIMBr H-MOR 6.55 39 26 0.13 0.00 0.00 39 0.13
51 (After recycle test)
52 [a]
Surface area estimated from BET equation
53 [b]
Surface area estimated from DFT pore size distribution method
[c]
54 Total pore volume calculated from adsorbed amount at P/Po = 0.99
[d]
55 Micropore, Mesopore area and micropore volume calculated by t-plot
[e]
Mesopore volume determined by taking Vp – Vmicro difference
56 na: Not available.
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1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
Figure 3. Nitrogen adsorption-desorption isotherms at 196 8C (77 K) for (a)
35
HY and BMIMBr-HY zeolites and (b) H-MOR, BMIMBr H-MOR and BMIMBr H-
36 Figure 4. Differential pore volume (cc/nm/g) as a function of pore size (nm)
MOR (After recycle test)
for (a) H-MOR and (b) BMIMBr H-MOR zeolite
37
38
39
plot (Figure 4) which shows that pore volume remains
40
consistent for the mesoporous region before and after [BMIM] Catalytic Performance
41
Br encapsulation in H-MOR. However, pore volume reduced
42
significantly in the micropore region which may be due to the Six catalysts (including two commercial zeolites (HY and H-
43
filling of micropores with the ionic liquid. MOR), and their IL ([BMIM]Br or ChCl) encapsulated counter
44
Figure 5 shows the TEM images obtained for H-MOR, parts are tested for glucose conversion to HMF. The conversion
45
BMIMBr H-MOR and spent BMIMBr H-MOR after 5 reaction of glucose and yields of various compounds (HMF, fructose,
46
runs. After analyzing the images, it was observed that solid levulinic acid (LA), formic acid (FA) and acetic acid (AA))
47
dense crystals of H-MOR were present in the form of obtained with different catalysts at otherwise identical con-
48
aggregates. After [BMIM]Br encapsulation the average pore ditions (Exp. #s: G_01 – G_06, Table S1, SI) are shown in
49
diameter increased as verified by BET results. The surface Figure 6. The Choline Chloride impregnated H-MOR zeolite
50
showed a form of hexagonal crystal with visible pores. Even showed the highest conversion of glucose (99.5%), however,
51
after [BMIM]Br encapsulation, the crystallinity of the zeolite is the yield of HMF is lower with this catalyst. A maximum HMF
52
preserved as shown in SAED image (attached within the image yield of 39% (and selectivity of 51%) is obtained with
53
itself). BMIMBr H-MOR at a conversion of 75%.
54
The glucose conversion (72%) and HMF yield (35%) are
55
moderate with HY catalyst. However, both are decreased after
56
incorporation of either of the ILs in HY. The effect is more
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severe in the case of ChCl. The formation of smaller molecules
1
such as LA and FA is high over HY, H-MOR and ChCl H-MOR
2
catalysts. According to a reaction mechanism suggested by
3
Lourvanij and Rorrer,[22] 0.9 nm glucose is unable to enter the
4
0.75 nm pore of Y zeolite. Hence, Brönsted acid sites present on
5
the outer surface of Y zeolite converts the glucose molecule to
6
unstable linear 1,2-enediol which then diffuses into 1.3 nm
7
super-cage of Y zeolite and dehydrates to HMF. Since from N2
8
sorption data it is evident that high micro-pore volume is
9
available for the reaction, 0.82 nm HMF molecule formed inside
10
the super-cage might not be able to diffuse out of the matrix.
11
Therefore, the HMF rehydrate to smaller linear products which
12
is confirmed by high LA and FA yields in this study. Ionic liquid
13
encapsulation further narrows the pore width and volume
14
which might have blocked the active sites responsible for the
15
reaction which resulted in the low conversion of glucose and
16
subsequent lower yields.
17
The situation is completely different in the case of [BMIM]Br
18
encapsulated H-MOR zeolite. Even though micropore area is
19
zero and mesopore area decreased marginally with [BMIM]Br
20
encapsulation in H-MOR, the yield of HMF (39%) is higher. This
21
clearly indicates a synergistic effect of BMIMBr H-MOR. The
22
[BMIM]Br could act as a catalyst for dehydration reaction[2f] and
23
is available readily due to its presence at the outer surface or
24
mesopores of H-MOR. Moreover, the accessibility of [BMIM]Br
25
to reactants is more in the case of BMIMBr H-MOR as
26
compared to that in the case of BMIMBr-HY. An interplay of
27
active sites ([BMIM]Br and H-MOR) may also play a role in the
28
direct conversion of glucose to HMF. In the case of BMIMBr H-
29 Figure 5. TEM micrographs of (a) H-MOR (b) BMIMBr H-MOR (c) BMIMBr H-
MOR (after recycle test)
MOR, the formation of acetic acid is suppressed to a large
30
extent. However, the formation of LA and FA enhanced
31
marginally. This clearly indicates that the micropores of H-MOR
32
are responsible for the breaking down of reactant and product
33
molecules to smaller molecules (AA) before they diffuse back
34
from the micropores. This is also in agreement with the
35
discussions in the case of IL-HY. Therefore, it can be concluded
36
from the above discussion that the microporous materials
37
without any modification are not suitable for the selective HMF
38
production from glucose. Jadav et al.[23] reported a similar
39
conversion and yield over H-ZSM-5 under similar operating
40
conditions but at a higher temperature of 195oC. Hu et al.[19b]
41
tested H-MOR catalysts for glucose dehydration in IL and
42
reported a lower glucose conversion (27.2%) and HMF yield
43
(13.1%) as compared to those obtained in this study. This could
44
be attributed to the biphasic system in combination with NaCl
45
and higher reaction temperature and time used in this study as
46
opposed to single phase and no NaCl in their study. Overall,
47
IL H-MOR zeolites are more efficient than the IL-HY used in this
48
study.
49
Various researchers (Qian, Li et al., Agirrezabal-Telleria et al.,
50 Figure 6. Conversion (X) of glucose and yields of HMF, fructose, Levulinic
etc.) described the possible pathways for glucose to HMF
51 Acid (LA), formic acid (FA) and acetic acid (AA) obtained over various
catalysts (Reaction Conditions: T = 170 8C, t = 3 h, water = 2 g, glucose conversion.[7b,11] Brönsted acid sites are strong dehydrating sites
52
weight = 0.2 g, glucose:catalyst = 3:1 (w/w), Water:MIBK = 1:2 (w/w) while Lewis acid sites are responsible for glucose isomerization
53 NaCl = 0.6 g) to fructose. Brönsted acid sites are also responsible for HMF
54
rehydration to LA and FA. Three possible routes are reported in
55
the literature, including direct HMF formation via the cyclic
56
route with the formation of transition state intermediate
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dehydration of which gives HMF or via glucose isomerization to HMF which in turn reduces the side products (levulinc acid,
1
fructose and its subsequent dehydration or via an open chain formic acid, and acetic acid) formation significantly. This could
2
mechanism.[1b] In the present study, fructose formation is not be explained by the salting-out effect of NaCl which changes
3
observed which may imply that glucose isomerization pathway the intermolecular forces between H2O and MIBK.[3b,24b,c] There-
4
is not followed. In this case, the Lewis acid sites play a minimal fore, this data clearly indicate that the presence of both NaCl
5
role. and extraction phase is highly beneficial for the improvement
6
of yield and conversion.
7
Effect of reaction conditions (time and temperature)
8 Effect of NaCl and extracting phase on the glucose conversion
First, the effect of temperature was investigated over
9 and HMF yield
BMIMBr H-MOR catalyst, keeping other operating parameters
10
Next, we investigated the effect of NaCl as well as the constant. The results (Figure 8) indicate that the conversion
11
extraction phase (Exp. #s: G_05, G_09, and G_10, Table S1, SI)
12
on glucose conversion and HMF yield for otherwise same
13
operating conditions over BMIMBr H-MOR (which is found to
14
be the best catalyst among tested). In the absence of NaCl,
15
glucose conversion (26% vs 75%) and HMF yield (6% vs 39%)
16
are significantly lower even in the presence of extraction phase
17
(Figure 7). Moreover, only in this case, a significant yield of
18
19
20
21
22
23
24
25
26
27
28
29
30 Figure 8. Conversion (X) of glucose and yields of HMF, fructose, Levulinic
31 Acid (LA), formic acid (FA) and acetic acid (AA) obtained at various
32 temperatures for a reaction time of 3 h over BMIMBr H-MOR catalyst.
33
34
35
increases with temperature but the HMF yield does not follow
36
Figure 7. Conversion (X) of glucose and yields of HMF, fructose, Levulinic
the same trend. As the temperature increased from 150 8C to
37
Acid (LA), formic acid (FA) and acetic acid (AA) obtained with different 185 8C, the conversion increased from 2% to 95%. Initially, the
38
reaction system over BMIMBr H-MOR catalyst. HMF yield increased with temperature from 1% at 150oC to
39
39% at 170 8C. However, a further increase in temperature
40
resulted in a decrease of HMF yield (to 31%) and an increase of
41
FA and LA yields. This signifies that higher reaction temper-
42
fructose (11%) was observed suggesting that addition of an atures are prone to rehydration and degradation of HMF.
43
inorganic salt such as NaCl not only acts as a promoter but also Effect of reaction time is studied for the same catalytic
44
alters the actual reaction pathway followed. This could be system. From Figure 9, it is apparent that the reaction time also
45
explained by the fact that the Na + forms a complex with has a significant effect on glucose conversion as well as on
46
glucose, resulting in a positively charged molecule which upon HMF yield. As the time increased from 1 h to 4 h the conversion
47
interacting with water facilitate dehydration reaction.[24] A increased slowly in the first two hours and from 2 h to 3 h the
48
similar effect of these salts for the heterogeneous catalyst (H- increase in conversion was rapid (from 17% to 75%) and then it
49
ZSM-5) was reported by Moreno-Recio et al.[25] and with was leveled off at longer reaction times (at 4 h it was 78%). On
50
alumina doped MCM-41 by Jiménez-Morales et al.[26] This effect the other hand, the HMF yield passed through a maximum at a
51
was not observed with fructose as the reactant.[3b] reaction time of 3 h. The decrease in HMF yield at longer times
52
The benefit of adding an extraction phase (along with NaCl) can be attributed to the formation of side products (LA and FA)
53
to the reaction system was also tested. The HMF yield and from HMF which is clearly visible from Figure 9. A dark colored
54
conversion are increased from 9% to 39% and from 57% to tar-like substance (humins) was observed both at longer
55
75%, respectively. The improvement in conversion and yield reaction times and higher temperatures which are known to be
56
can be attributed to an effective continuous extraction of the
57

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off in the range of 42–45%. The HMF yield also followed a
1
nearly similar trend (i. e. from the first run to the second run
2
there was a considerable decrease and from second run
3
onwards it was leveled-off). To find out probable reasons for
4
the initial deactivation of the catalyst, characterizations have
5
been carried out on the recycled catalyst.
6
As shown in Figure 3b and in Table 2, there are no
7
observable changes in the surface area and pore size. The
8
FETEM images (Figure 5e and f) show that after recycling for
9
four times, the catalyst showed multi-crystallinity as opposed
10
to the single-crystalline structure of the fresh catalyst. Also,
11
some needle-shaped appearances and high molecular weight
12
(e. g. humin) depositions can be found in these images. TGA
13
data (Table 1 and Figure S2, SI) also support this notion. The
14
weight loss from the catalyst after use for recycle test is much
15
higher as compared to that of fresh BMIMBr H-MOR catalyst
16
(23.4% in the former case and 9% in the latter case, in the
17
temperature range 200–800oC). The above data clearly signify
18 Figure 9. Conversion (X) of glucose and yields of HMF, fructose, Levulinic
Acid (LA), formic acid (FA) and acetic acid (AA) obtained at various times at a
that the major reason for the deactivation of the catalyst is the
19
temperature of 170oC over BMIMBr H-MOR catalyst. deposition of some high molecular weight reaction products
20
such as humins.
21
22
23 Conclusions
generated due to condensation reactions of HMF and is
24
another reason for the decrease in HMF yield. In conclusion, the ionic liquid encapsulated zeolites, particularly
25
[BMIM]Br encapsulated H-MOR, are highly effective in selec-
26
tively converting glucose to HMF. The ionic liquids are
27 Catalyst stability
encapsulated successfully and are highly stable in the pores of
28
As a next step in understanding the catalyst behavior, the the zeolite, as observed from the XRD, TGA, and nitrogen
29
stability of the best catalyst (BMIMBr H-MOR) obtained in sorption analysis. Moreover, the crystal structure of the zeolites
30
above experiments was tested by recycling the same used is not disrupted due to ionic liquid encapsulation. From
31
catalyst for 4 more times and the results are shown in Figure catalytic tests, the BMIMBr H-MOR showed synergism with
32
10. There is a considerable decrease in the conversion of higher yields of HMF even after micropore-blocking as
33
glucose from the first run (75%) to the second run (42%). indicated by nitrogen sorption analysis. The best catalyst
34
However, from second run onwards the conversion is leveled- (BMIMBr H-MOR) showed an HMF yield of 39% (and a
35
selectivity of 51%) with a glucose conversion of 75%, at
36
temperature 170oC and reaction time 3 h. The recycle tests of
37
the best catalyst showed that after second recycle the catalyst
38
is nearly stable for next 4 runs. The major reason for the
39
decrease in activity after the first cycle (as depicted from TGA
40
and FETEM analysis) is the formation of high molecular weight
41
compounds (humins) on the catalyst.
42
43
44 Supporting Information Summary
45
Supporting information contents: (1) detailed experimental
46
details of catalyst preparation, characterization, and testing
47
from glucose hydrolysis to 5-HMF. (2) Nitrogen adsorption-
48
desorption isotherms of ChCl-HY and ChCl H-MOR. (3) TGA of
49
fresh and recycled BMIMBr H-MOR. (4) Complete experimental
50
conditions used for catalyst tests.
51
52
53 Acknowledgements
54
Figure 10. Conversion (X) of glucose and yields of HMF over BMIMBr H-MOR The financial support provided by the Science and Engineering
55
catalyst reused in five cycles. Reaction conditions are same as those given in Research Board (File Number: YSS/2015/000911), New Delhi, India
56 Figure 6. is gratefully acknowledged.
57

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 Full Papers
Conflict of Interest Deval, R. S. Assary, E. Nikolla, M. Moliner, Y. Romn-Leshkov, S. J. Hwang,
1 A. Palsdottir, D. Silverman, R. F. Lobo, L. A. Curtiss, M. E. Davis, Proc. Natl.
2 Acad. Sci. U. S. A. 2012, 109, 9727–9732; d) R. Bermejo-Deval, M. Orazov,
The authors declare no conflict of interest. R. Gounder, S.-J. Hwang, M. E. Davis, ACS Catal. 2014, 4, 2288–2297.
3
[11] a) Y. Zhang, J. J. Wang, X. C. Li, X. H. Liu, Y. J. Xia, B. C. Hu, G. Z. Lu, Y. Q.
4
Wang, Fuel 2015, 139, 301–307; b) A. Osatiashtiani, A. F. Lee, D. R. Brown,
5 Keywords: [BMIM]Br · Glucose to 5-Hydroxymethylfurfural · J. A. Melero, G. Morales, K. Wilson, Catal. Sci. Technol. 2014, 4, 333–342.
6 Ionic liquid encapsulated zeolites · reactive extraction · Ship-in- [12] M. Maldonado, M. D. Oleksiak, S. Chinta, J. D. Rimer, J. Am. Chem. Soc.
7 a-bottle strategy 2013, 135, 2641–2652.
[13] C. M. Lew, N. Rajabbeigi, M. Tsapatsis, Ind. Eng. Chem. Res. 2012, 51,
8
[1] a) C. Chatterjee, F. Pong, A. Sen, Green Chem. 2015, 17, 40–71; b) H. Li, Z. 5364–5366.
9 [14] G. Yong, Y. Zhang, J. Y. Ying, Angew. Chem. 2008, 120, 9485–9488.
Fang, R. L. Smith Jr, S. Yang, Prog. Energy Combust. Sci. 2016, 55, 98–194.
10 [2] a) Y. J. Pagn-Torres, T. Wang, J. M. R. Gallo, B. H. Shanks, J. A. Dumesic, [15] W. Mamo, Y. Chebude, C. Marquez-Alvarez, I. Diaz, E. Sastre, Catal. Sci.
11 ACS Catal. 2012, 2, 930–934; b) Y. Romn-Leshkov, J. N. Chheda, J. A. Technol. 2016, 6, 2766–2774.
Dumesic, Science 2006, 312, 1933–1937; c) R. Otomo, T. Yokoi, T. Tatsumi, [16] P. Gallezot, Chem. Soc. Rev. 2012, 41, 1538–1558.
12
ChemCatChem 2015, 7, 4180–4187; d) T. Wang, M. W. Nolte, B. H. Shanks, [17] J. Yang, K. De Oliveira Vigier, Y. Gu, F. Jrme, ChemSusChem 2015, 8,
13 269–274.
Green Chem. 2014, 16, 548; e) H. Zhao, J. E. Holladay, H. Brown, Z. C.
14 Zhang, Science 2007, 316, 1597–1600; f) S. Lima, P. Neves, M. M. Antunes, [18] M. N. Catrinck, E. S. Ribeiro, R. S. Monteiro, R. M. Ribas, M. H. P. Barbosa,
15 M. Pillinger, N. Ignatyev, A. A. Valente, Appl. Catal., A 2009, 363, 93–99; R. F. Tefilo, Fuel 2017, 210, 67–74.
g) S. Dutta, S. Pal, Biomass Bioenergy 2014, 62, 182–197. [19] a) Q. Xu, Z. Zhu, Y. Tian, J. Deng, J. Shi, Y. Fu, BioResources 2014, 9,303-
16
[3] a) J. S. Luterbacher, J. M. Rand, D. M. Alonso, J. Han, J. T. Youngquist, C. T. 315; b) L. Hu, Z. Wu, J. Xu, Y. Sun, L. Lin, S. Liu, Chem. Eng. J. 2014, 244,
17 137–144; c) C. Moreau, R. Durand, S. Razigade, J. Duhamet, P. Faugeras,
Maravelias, B. F. Pfleger, J. A. Dumesic, Science 2014, 343, 277–280; b) Y.
18 Roman-Leshkov, C. J. Barrett, Z. Y. Liu, J. A. Dumesic, Nature 2007, 447, P. Rivalier, P. Ros, G. Avignon, Appl. Catal., A 1996, 145, 211–224; d) C. A.
19 982–985. Emeis, J. Catal. 1993, 141, 347–354.
[4] a) M. E. Zakrzewska, E. Bogel-Łukasik, R. Bogel-Łukasik, Chem. Rev. 2011, [20] M. Besson, P. Gallezot, C. Pinel, Chem. Rev. 2014, 114, 1827–1870.
20
111, 397–417; b) P. Bhaumik, P. L. Dhepe, RSC Adv. 2013, 3, 17156–17165. [21] K. Foger, J. V. Sanders, D. Seddon, Zeolites 1984, 4, 337–345.
21 [22] V. V. Ordomsky, J. van der Schaaf, J. C. Schouten, T. A. Nijhuis, ChemSu-
[5] aB. Xie, J. Song, L. Ren, Y. Ji, J. Li, F.-S. Xiao, Chem. Mater. 2008, 20, 4533–
22 4535; b) A. Herbst, C. Janiak, New J. Chem. 2016, 40, 7958–7967. sChem 2013, 6, 1697–1707.
23 [6] a) P. Bhaumik, P. L. Dhepe, Catal. Today 2015, 251, 66–72; b) J. Wang, J. [23] H. Jadhav, E. Taarning, C. M. Pedersen, M. Bols, Tetrahedron Lett. 2012,
Xi, Q. Xia, X. Liu, Y. Wang, Sci. China:Chem. 2017, 60, 870–886. 53, 983–985.
24
[7] a) M. Cheng, T. Shi, H. Guan, S. Wang, X. Wang, Z. Jiang, Appl. Catal., B [24] a) J. S. Luterbacher, D. Martin Alonso, J. A. Dumesic, Green Chem. 2014,
25 16, 4816–4838; b) M. Moreno-Recio, I. Jimnez-Morales, P. L. Arias, J.
2011, 107, 104–109; b) K. Nakajima, R. Noma, M. Kitano, M. Hara, J. Mol.
26 Catal. A: Chem. 2014, 388, 100–105; c) E. Nikolla, Y. Romn-Leshkov, M. Santamara-Gonzlez, P. Maireles-Torres, ChemistrySelect 2017, 2, 2444–
27 Moliner, M. E. Davis, ACS Catal. 2011, 1, 408–410; d) C. Wang, L. Zhang, T. 2451; c) R. Karinen, K. Vilonen, M. Niemel, ChemSusChem 2011, 4, 1002–
Zhou, J. Chen, F. Xu, Sci. Rep. 2017, 7, 40908; e) L. Qi, Y. F. Mui, S. W. Lo, 1016.
28
M. Y. Lui, G. R. Akien, I. T. Horvth, ACS Catal. 2014, 4, 1470–1477. [25] S. Jia, K. Liu, Z. Xu, P. Yan, W. Xu, X. Liu, Z. C. Zhang, Catal. Today 2014,
29 234, 83–90.
[8] a) F. C. d. Melo, R. F. d. Souza, P. L. A. Coutinho, M. O. d. Souza, J. Braz.
30 Chem. Soc. 2014, 25, 2378–2384; b) M. I. Alam, S. De, B. Singh, B. Saha, [26] I. Jimnez-Morales, M. Moreno-Recio, J. Santamara-Gonzlez, P. Mair-
31 M. M. Abu-Omar, Appl. Catal., A 2014, 486, 42–48. eles-Torres, A. Jimnez-Lpez, Appl. Catal., B 2015, 164, 70–76.
32 [9] A. J. Crisci, M. H. Tucker, J. A. Dumesic, S. L. Scott, Top. Catal. 2010, 53,
1185–1192.
33 Submitted: August 24, 2017
[10] a) M. Moliner, Y. Romn-Leshkov, M. E. Davis, Proc. Natl. Acad. Sci. U. S. A.
34 2010, 107, 6164–6168; b) Y. Romn-Leshkov, M. Moliner, J. A. Labinger, Revised: October 24, 2017
35 M. E. Davis, Angew. Chem., Int. Ed. 2010, 49, 8954–8957; c) R. Bermejo- Accepted: October 26, 2017
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ChemistrySelect 2017, 2, 10379 – 10386 10386  2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

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Freitag, 10.11.2017
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