Efficient dehydration of carbohydrates to 5-hydroxymethylfurfural in ionic liquids catalyzed by tin(IV) phosphonate and zirconium phosphonate

Article abstract of DOI:10.1007/s11426-013-4944-3

In this work, we synthesized tin(IV) phosphonate (SnBPMA) and zirconium phosphonate (ZrBPMA) by the reaction of SnCl₄·5H₂O or ZrOCl₂·8H₂O with N,N-bis(phosphonomethyl) aminoacetic acid, which was synthesized from a biomaterial glycine through a Mannich-type reaction. The SnBPMA and ZrBPMA were very efficient heterogeneous catalysts for the dehydration of fructose to produce 5-hydroxymethylfurfural (HMF), and the SnBPMA had higher activity than the ZrBPMA. The effects of solvents, temperature, reaction time, and reactant/solvent weight ratio on the reaction catalyzed by SnBPMA were investigated. It was demonstrated that the yield of HMF could reach 86.5% with 1-ethyl-3-methylimidazolium bromide ([Emim] Br) as solvent, and the SnBPMA and SnBPMA/[Emim]Br catalytic system could be reused five times without considerable reduction in catalytic efficiency. Further study indicated that the SnBPMA and ZrBPMA in [Emim]Br were also effective for the dehydration of sucrose and inulin to produce HMF with satisfactory yields.

Full text of DOI:10.1007/s11426-013-4944-3

SCIENCE CHINA
Chemistry
November 2013 Vol.56 No.11: 1578–1585
doi: 10.1007/s11426-013-4944-3
• ARTICLES •
Efficient dehydration of carbohydrates to
5-hydroxymethylfurfural in ionic liquids catalyzed by tin(IV)
phosphonate and zirconium phosphonate
NING Hui, SONG JinLiang, HOU MinQiang, YANG DeZhong,
FAN HongLei & HAN BuXing*
Beijing National Laboratory for Molecular Sciences; Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
Received March 1, 2013; accepted April 7, 2013; published online August 26, 2013
In this work, we synthesized tin(IV) phosphonate (SnBPMA) and zirconium phosphonate (ZrBPMA) by the reaction of
SnCl4·5H2O or ZrOCl2·8H2O with N,N-bis(phosphonomethyl)aminoacetic acid, which was synthesized from a biomaterial gly-
cine through a Mannich-type reaction. The SnBPMA and ZrBPMA were very efficient heterogeneous catalysts for the dehy-
dration of fructose to produce 5-hydroxymethylfurfural (HMF), and the SnBPMA had higher activity than the ZrBPMA. The
effects of solvents, temperature, reaction time, and reactant/solvent weight ratio on the reaction catalyzed by SnBPMA were
investigated. It was demonstrated that the yield of HMF could reach 86.5% with 1-ethyl-3-methylimidazolium bromide ([Em-
im]Br) as solvent, and the SnBPMA and SnBPMA/[Emim]Br catalytic system could be reused five times without considerable
reduction in catalytic efficiency. Further study indicated that the SnBPMA and ZrBPMA in [Emim]Br were also effective for
the dehydration of sucrose and inulin to produce HMF with satisfactory yields.
fructose, inulin, sucrose, dehydration, 5-hydroxymethylfurfural, heterogeneous catalysts
acid [13, 14], heteropoly acids [15, 16], ionic liquids (ILs)
1 Introduction
[17, 18], and so on. Some heterogeneous catalysts have also
been used for the dehydration of carbohydrates, such as
mesoporous niobium phosphate [19], cellulose-derived
amorphous carbon [20, 21] and ionic liquids supported on
silica nanoparticles [22], etc. In general, the homogeneous
catalysts are more effective, but the separation of the cata-
lysts from the reaction mixture is difficult. The heterogene-
ous catalysts are advantageous in that the catalysts are more
easily recovered, but the efficiency is usually lower.
Recently, mesoporous metal phosphonate hybrid materi-
als have attracted much interest because they can be used in
adsorption, separation, solar light utilization and catalysts
[23, 24]. In addition, organics with different functional
groups can be introduced into the metal phosphonates
structure by introducing desired organic compounds into a
phosphonic acid. Among various applications, using meso-
In recent years, transformation of biomass into liquid fuels
and valuable intermediates has received much attention
[1−7]. Among the processes of biomass conversion, dehy-
dration of carbohydrates to produce 5-hydroxymethylfur-
fural (HMF) is one of the most important routes because
HMF is considered to be a platform molecule for the pro-
duction of high value chemicals and biofuels [8, 9].
Up to now, many efforts have been devoted to the dehy-
dration of carbohydrates to produce HMF efficiently. Vari-
ous catalysts, including homogeneous and heterogeneous
catalysts, have been developed for the dehydration reactions.
Homogeneous catalysts include Lewis acids [10−12], boric
*Corresponding author (email: hanbx@iccas.ac.cn)
© Science China Press and Springer-Verlag Berlin Heidelberg 2013
chem.scichina.com www.springerlink.com

Ning H, et al. Sci China Chem November (2013) Vol.56 No.11
1579
porous phosphonate materials as catalysts is very attractive.
Many reactions have been conducted using metal phospho-
nates as the catalysts or the supports, such as synthesis of
adipic acid [25], methanolysis of sunflower oil [26], bio-
diesel synthesis [27], etc.
mbar using Al Kα as the excitation source (hν = 1486.6 eV)
and operated at 15 kV and 20 mA.
2.3 Analysis methods for the product
The amount of HMF was analyzed by HPLC with
Supelcosil LC-18 5ìm column, Shimadzu LC-15C pump,
Shimadzu UV-Vis SPD-15C detector at 282 nm. Before
analyzed, the reaction mixture was diluted to 1000 mL.
Methanol/water solution (50/50, v/v) was used as the mobile
phase at a flow rate of 0.8 mL/min.
As discussed above, many catalysts have been developed
for the dehydration reaction of carbohydrates to produce
HMF. However, it is still highly desirable to develop effi-
cient and cheap heterogeneous catalysts for producing HMF
from carbohydrates. In this work, we synthesized SnBPMA
and ZrBPMA using N,N-bis(phosphonomethyl)aminoacetic
acid (H5BPMA) synthesized from Mannich-type reaction of
glycine, which is a biomaterial (Scheme 1) [28, 29]. It was
found that SnBPMA and ZrBPMA were very active, selec-
tive, and stable for the dehydration reactions of some car-
bohydrates to produce HMF and could be easily recovered
and reused.
2.4 Catalyst synthesis
N,N-Bis(phosphonomethyl)aminoacetic acid [(H2O3PCH2)2-
NCH2CO2H] (H5BPMA)
The H5BPMA with a functional carboxylate group was
prepared by a Mannich-type reaction (Scheme 1). In the
reaction, glycine (15.2 g, 0.2 mol) was mixed with hydro-
chloric acid (50 mL), deionized water (50 mL) and phospho-
rous acid (65.6 g, 0.8 mol) in a flask of 500 mL. The mix-
ture was allowed to reflux at 120 °C for 1 h, then formalde-
hyde (100 g) was added over a period of 1h, and the mixture
was then refluxed for other three hours. The water was re-
moved under reduced pressure to get a white powder, which
was dissolved in water (20 mL) and recrystallized by adding
acetone (500 mL). The H5BPMA was collected by filtration
and washed using acetone and dried at room temperature.
Scheme 1 Mannich-type reaction for synthesis of N,N-bis(phosphon-
omethyl)aminoacetic acid from glycine.
2 Experimental Section
2.1 Materials
Preparation of Zr[(O3PCH2)2NCH2CO2H] (ZrBPMA) and
Sn[(O3PCH2)2NCH2CO2H] (SnBPMA)
Fructose, sucrose, inulin, and phosphorous acid were all
A.R. grade and were purchased from Alfa Aesar. Glycine,
formaldehyde (37%−40% water solution), hydrochloric acid
(38% water solution), ZrOCl2·8H2O, SnCl4·5H2O, dime-
thylacetamide (DMA) and dimethylsulfoxide (DMSO) were
A.R. grade and were obtained from Beijing Chemical Rea-
gent Company. The ionic liquids 1-ethyl-3-methylimidazo-
lium bromide ([Emim]Br) and 1-ethyl-3-methylimidazolium
tetrafluoroborate ([Emim]BF4) were provided by Lanzhou
Greenchem ILS, LICP, CAS, China, and their purity was
> 99%. All chemicals were used as received.
H5BPMA (5.26 g, 20 mmol) was dissolved in H2O (300 mL)
at room temperature with stirring, then ZrOCl2·8H2O (6.44
g, 20 mmol) or SnCl4·5H2O (7.0 g, 20 mmol) was added to
this solution. Immediately white precipitate was formed and
the reaction mixture was stirred for three days. The white
precipitate was separated by filtration, thoroughly washed
with H2O, ethanol, ethyl ether and dried at 80 °C under
vacuum for 12 h.
2.5 Catalytic reaction
Conversion of carbohydrates into HMF
2.2 Catalyst characterization
In a typical experiment, known amounts of carbohydrate,
catalyst, and solvent were loaded into a flask of 10 mL
sealed with a glass stopper. The reaction mixture was stirred
at a fixed temperature for desired time. Then the mixture
was cooled to room temperature immediately. The samples
were analyzed by HPLC to obtain the yields. Each reaction
was repeated at least two times. In the experiments to test
the reusability of catalyst SnBPMA, 5 mL of water was
added into the reaction system after the reaction. Then the
catalyst was recovered by centrifugation, washed with water,
ethanol and ethyl ether. After dried under vacuum for 12 h
at 60 °C, the catalyst was reused for the next run by adding
new carbohydrates. In the experiments to test the reusability
FT-IR spectra were recorded on Bruker Tensor 27 IR spec-
trometer and the sample was prepared by the KBr pellet
method. Scanning electron microscopy (SEM) images were
taken using a Hitachi S-4300 instrument (Japan) operated at
15 kV. The BET surface area measurement and pore analy-
sis were carried out by N2 adsorption at 77 K with Mi-
cromeritics ASAP 2020 V3.00 H (USA) surface area ana-
lyser. X-ray diffraction (XRD) measurements were con-
ducted on an X-ray diffractometer (D/MAX-RC, Japan)
operated at 40 kV and 200 mA with Cu Kα (λ = 0.154 nm)
radiation. XPS measurements were carried out on an
ESCAL Lab 220i-XL specrometer at a pressure of ~3 × 10−9

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Ning H, et al. Sci China Chem November (2013) Vol.56 No.11
of SnBPMA/[Emim]Br catalytic system, 1 mL of water was
added into the reaction system after the reaction. Then the
mixture was extracted with ether (4 × 50 mL) to remove the
HMF produced. After extraction, the water in the SnBP-
MA/[Emim]Br mixture was removed under reduced pres-
sure at 80 oC, and the SnBPMA/[Emim]Br mixture was then
used directly for the next run by adding new carbohydrates.
presented in Figure 1(a) and 1(b), respectively. The broad
band at 3400 cm−1 corresponds to the surface-adsorbed wa-
ter. For the SnBPMA in Figure 1(a), the bands at 1170 and
1032 cm−1 are attributed to weak P−C stretching vibrations
and P−O bending vibration, respectively. The peak at 1687
cm−1 is assigned to the COOH group. For the ZrBPMA in
Figure 1(b), the band at 1043 cm−1 is the P−O bending vi-
bration. Meanwhile, the band of the COOH group at 1641
cm−1 is also observed in the ZrBPMA spectrum.
Calculation of 5-HMF yield.
The yield of 5-HMF was calculated by the following equation:
The scanning electron microscopy (SEM) was used to
characterize the SnBPMA and ZrBPMA. It can be known
from the SEM images shown in Figure 2 that the materials
were featureless with a size of submicron.
Moles of 5-HMF formed
5-HMF yield (mol%) =
100%
Moles of carbohydrate used
The power XRD patterns of the SnBPMA and ZrBPMA
are shown in Figure 3. It can be known that the catalysts
had no X-ray crystal structures. Meanwhile, each XRD pat-
tern showed one broad diffraction peak, which indicated
amorphous framework walls of the obtained materials.
3 Results and Discussion
3.1 Catalyst characterization
The FT-IR spectra of the SnBPMA and ZrBPMA are
Figure 1 The FT-IR spectra of the SnBPMA (a) and ZrBPMA (b).
Figure 2 The SEM images of the SnBPMA (a) and ZrBPMA (b).
Figure 3 The Powder X-ray diffraction patterns of the SnBPMA (a) andZrBPMA (b).

Ning H, et al. Sci China Chem November (2013) Vol.56 No.11
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XPS spectra were also taken to investigate the chemical
state of the SnBPMA and ZrBPMA (Figure 4). For SnBP-
MA, the Sn 3d signal of SnBPMA is composed of two sin-
gle peaks located at 487.5 eV for Sn 3d5/2 and 496.5 eV for
Sn 3d3/2, which are characteristic of Sn4+. The binding en-
ergy of P 2p at 134.0 eV is characteristic of P5+. The broad
C 1s line might be fitted by three components situated at the
binding energies of 284.8 eV, 286.8 eV and 288.7 eV,
which may correspond to the C species of C–H or C–C,
C–N or C–P and COOH bonds, respectively. For ZrBPMA,
the Zr 3d signal of ZrBPMA is composed of two single
peaks located at 182.4 eV for Zr 3d5/2 and 184.7 eV for Zr
3d3/2, which are characteristic of Zr4+. The binding energy of
P 2p at 132.5 eV is characteristic of P5+. The broad C 1s line
might be fitted by three components situated at the binding
energies of 284.8 eV, 286.5 eV and 288.5 eV, which may
correspond to the C species of C–H or C–C, C–N or C–P
and COOH bonds, respectively.
The textural parameters of the SnBPMA and ZrBPMA
obtained from N2 adsorption/desorption isotherms are pre-
sented in Table 1. The results indicate that the SnBPMA
synthesized was porous with an average pore diameter of
24.2 nm. The SnBPMA exhibited a BET surface area of
34.0 m2/g with a pore volume of 0.21 cm3/g. Meanwhile,
ZrBPMA is also porous with an average pore diameter of
18.0 nm and it exhibited a BET surface area of 85.8 m2/g
with a pore volume of 0.37 cm3/g.
3.2 Activity of the catalysts in [Emim]Br
The activity of various catalysts for the dehydration of
fructose (Scheme 2) was tested at 373 K in [Emim]Br, and
the results are summarized in Table 2. Although the dehy-
dration reaction could be proceeded without catalysts in
[Emim]Br, the yield of HMF was very low (Entry 1). Ac-
cording to the experimental data, the two heterogeneous
Figure 4 The XPS spectra of Sn 3d (a), P 2p (b), C 1s (c) regions of the SnBPMA and Zr 3d (d), P 2p (e), C 1s (f) regions of the ZrBPMA.
Table 1 The surface area, pore volume and average pore diameter of the materials
Sample a)
SnBPMA
ZrBPMA
BET surface area b) (m2/g)
Pore volume c) (cm3/g)
Pore diameter c) (nm)
34.0
85.8
0.21
0.37
24.2
18.0
a) The sample was degassed at 100 oC for 12 h; b) surface area based on multipoint BET method; c) pore volume and pore diameter based on BJH method.

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Ning H, et al. Sci China Chem November (2013) Vol.56 No.11
3.4 Influence of reaction temperature and time
Figure 6 shows the effect of reaction temperature on the
dehydration of fructose to produce HMF in [Emim]Br cata-
lyzed by SnBPMA at 353 K and 373 K. It can be seen that
the yield at 373 K was higher than at 353 K because the
dehydration reaction was accelerated by increasing temper-
ature, which was favorable to achieving higher yield in a
short reaction time.
Scheme 2 Dehydration of fructose to produce HMF.
When the reaction was conducted at 373 K, the yield in-
creased dramatically with time at the beginning, and
reached the maximum (86.5%) at 1.5 hours with a fructose
conversion of 98%. Then the yield decreased slightly with
prolonged time, which may be due to the rehydration of the
HMF produced. When the reaction was 353 K, the reaction
reached equilibrium at 3 hours with the yield of 83.0% and
a fructose conversion of 99%.
Table 2 Dehydration of fructose catalyzed by various catalysts a)
Entry
1
Catalyst
None
Conversion (%)
26
Yield (%)
19.1
2
3
4
5
SnCl4·5H2O
ZrOCl2·8H2O
ZrBPMA
98
99
90
93
76.4
82.3
70.0
83.3
SnBPMA
a) Reaction conditions: 0.1 g fructose, 25 mg catalyst, 1 g [Emim]Br,
reaction time 1 h, reaction temperature 373 K.
3.5 Influence of substrate/solvent weight ratio
The dependence of HMF yield on the fructose/[Emim]Br
weight ratio was also investigated and the results are
demonstrated in Figure 7. In the experiment, the weight
ratio of substrate to the catalyst was fixed at 4. When the
fructose/[Emim]Br weight ratio was increased from 0.05:1
catalysts (ZrBPMA and SnBPMA) had similar catalytic
activity with the homogeneous lewis acid catalysts
(SnCl4·5H2O and ZrOCl2·8H2O) and the SnBPMA had a
higher activity than ZrBPMA under the same condition.
According to the results of Wang et al. [19], both the Lewis
and Brönsted acid sites in the phosphate salts can promote
the dehydration of fructose to HMF. The high catalytic ac-
tivity of the ZrBPMA and SnBPMA was due to the
Brönsted acid group COOH and Lewis acid nature of Sn4+
and Zr4+, which coexisted in the heterogeneous catalysts.
Further more, we chose SnBPMA as catalyst to study the
effects of various conditions on the reaction, and the results
are discussed in the following.
3.3 Effect of solvents
Several commonly used solvents were chose to investigate
the solvent effects on the reaction using the SnBPMA as the
catalyst and the results are shown in Figure 5. The reaction
did not occur when water was used as the reaction solvent.
While in dimethylacetamide (DMA) and dimethylsulfoxide
(DMSO), the yields of HMF were 0.8% and 19.1%, respec-
tively. We also studied the reaction in different ionic liquids
[Emim]BF4 and [Emim]Br. It can be known from Figure 5
that a HMF yield of 83.3% was achieved in [Emim]Br
while the yield is 4.3% in [Emim]BF4. Compared with
SnCl4 in [Emim]BF4 [11], SnBPMA in [Emim]BF4 was less
efficient because the structures of SnBPMA and SnCl4 are
different, and they showed different performances in the
same IL. The [Emim]Br may interact with fructose and the
intermediates through hydrogen bonding and show nucleo-
philic effect to activate fructose and stabilize intermediates,
which is favorable to producing HMF [30, 31]. This could
be the main reason that the best reaction activity and selec-
tivity was achieved in [Emim]Br.
Figure 5 Effect of different solvents on the yield of HMF. Reaction
conditions: 0.1 g fructose, 25 mg SnBPMA, 1 g solvent, reaction tempera-
ture 373 K, reaction time 1 h.
Figure 6 Influence of reaction temperature and reaction time on the
reaction. Reaction conditions: 0.1 g fructose, 25 mg SnBPMA, 1 g [Em-
im]Br.

Ning H, et al. Sci China Chem November (2013) Vol.56 No.11
1583
to 0.1:1, the HMF yield increased slightly from 82.9% to
86.5%. As the fructose/[Emim]Br weight ratio increased
from 0.1:1 to 0.15:1, the HMF yield was independent of the
ratio. However, when the fructose/[Emim]Br weight ratio
increased from 0.15:1 to 0.3:1, the HMF yield decreased
substantially to 69.7%. Therefore, the suitable fructose/
[Emim]Br weight ratio for our catalytic system was from
0.1:1 to 0.15:1.
3.6 Reusability of catalyst
Figure 7 Influence of fructose/[Emim]Br weight ratio on the yield of HMF.
Reaction conditions: reaction temperature 373 K, reaction time 1.5 h.
The reusability of SnBPMA and SnBPMA/[Emim]Br cata-
lyst system was studied in this work and the results are pre-
sented in Table 3. Obviously, the decrease of the activity of
SnBPMA was not considerable after reused five times. In
the reusing, the activity decrease of the catalyst/[Emim]Br
system was less than that the catalyst, which may be due to
less loss of the catalyst in the separation process when the
SnBPMA/[Emim]Br system was reused. The SnBPMA re-
covered from SnBPMA/[Emim]Br system after reused five
times was also characterized by FT-IR, XPS, XRD and
SEM, and the results are shown in Figure 8. It can be known
by comparing Figures 1−4 and 8 that the properties of the
SnBPMA were not changed after reused, which is consistent
Table 3 The reusability of the SnBPMA and SnBPMA/[Emim]Br system a)
Yield (%)
Run
SnBPMA
84.0
SnBPMA/[Emim]Br system
84.0
1
2
3
4
5
82.0
79.3
79.5
78.8
83.1
82.6
82.3
82.9
a) Reaction conditions: 0.5 g fructose, 125 mg catalyst, 5 g [Emim]Br,
reaction time 1.5 h, reaction temperature 373 K.
Figure 8 The characterization of the catalyst SnBPMA after reused five times. (a) FT-IR, (b) XPS Sn 3d, (c) XPS P 2p, (d) XPS C 1s, (e) XRD and (f) SEM.

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Ning H, et al. Sci China Chem November (2013) Vol.56 No.11
with that fact that the yields of the products in different runs
were nearly unchanged, as shown in Table 3.
[Emim]Br as the solvent. High yield of 86.5% has been
achieved from dehydration of fructose in [Emim]Br cata-
lyzed by the SnBPMA. The SnBPMA and SnBPMA/
[Emim]Br catalytic system can be reused five times without
considerable reduction in the reaction activity and selectivi-
ty. In addition, the catalysts can also be used to promote the
dehydration of sucrose and inulin to produce HMF effi-
ciently. We believe that the simple, efficient, and easily
recyclable catalytic system has potential application for
producing HMF from dehydration of carbohydrates.
3.7 Dehydration of other carbohydrates
The SnBPMA/[Emim]Br catalytic system was also used to
catalyze the dehydration of other carbohydrates, and the
results are illustrated in Figure 9. As expected, the sucrose
and inulin with fructose unit in the molecular structures
gave moderate HMF yield of 45.3% and 48.8%, respective-
ly. When the yields of HMF reached maximum, the conver-
sions of sucrose and inulin were 99% and 97%, respectively.
Reaction times for reaching the maximum HMF yield from
sucrose and inulin were 2 hours and 3 hours, respectively.
This work was supported by the National Natural Science Foundation of
China (21003133, 21173234).
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In summary, porous SnBPMA and ZrBPMA have been
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Yield (%)
Time Temperature
Entry Substrate
(h)
(K)
SnBPMA
ZrBPMA
54.2
1
2
3
4
Fructose
Fructose
Inulin
3
1.5
3
353
373
373
373
83.0
86.5
48.7
45.3
78.1
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a) Reaction conditions: 0.1 g substrate, 25 mg catalyst, 1 g [Emim]Br.

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