Conversion of fructose into 5-hydroxymethylfurfural catalyzed by recyclable sulfonic acid-functionalized metal-organic frameworks

Article abstract of DOI:10.1039/c3gc42414f

A series of sulfonic acid-functionalized metal-organic frameworks (MOF-SO₃H) were prepared by postsynthetic modification (PSM) of the organic linkers within the MOF with chlorosulfonic acid. The obtained MOF-SO₃H, including sulfonic acid-functionalized MIL-101(Cr) [MIL-101(Cr)-SO₃H], UIO-66(Zr) [UIO-66(Zr)-SO₃H], and MIL-53(Al) [MIL-53(Al)-SO₃H], have been systematically studied as solid acids in fructose transformation to 5-hydroxymethylfurfural (HMF). With MIL-101(Cr)-SO₃H as catalyst, a HMF yield of 90% with a full fructose conversion was obtained at 120 °C for 60 min in DMSO. The concentration of -SO₃H in MOF-SO₃H as well as the contribution of Bronsted acidity of MOF-SO₃H parallels its -SO₃H grafting rate. Under a lower -SO₃H grafting level, a good linear correlation between catalytic activity, in terms of turnover frequency, and sulfonic acid-site density of MOF-SO₃H was found. Moreover, the sulfonic acid groups, which function as the catalytic sites, are equivalent in all MOF-SO₃H for fructose-to-HMF transformation, regardless of precursor MOFs. Both conversions of fructose and selectivities towards HMF increase with the sulfonic acid-site density of MOF-SO₃H at an initial stage of fructose-to-HMF transformation. Kinetics studies reveal that the MIL-101(Cr)-SO₃H promoted fructose-to-HMF transformation may follow pseudo-first-order kinetics with observed activation energy of 55 kJ mol^-1 under the investigated conditions. Moreover, MIL-101(Cr)-SO₃H behaves as a heterogeneous catalyst and can be easily recovered and reused. The research highlights a good prospect for catalytic application of MOF-derived solid acid catalysts for biomass carbohydrate valorization. the Partner Organisations 2014.

Full text of DOI:10.1039/c3gc42414f

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ARTICLE TYPE
Conversion of Fructose into 5-Hydroxymethylfurfural Catalyzed by
Recyclable Sulfonic Acid–Functionalized Metal–Organic Frameworks
a
a,c
b
a,c
a,b
b
Jinzhu Chen,* Kegui Li, Limin Chen, Ruliang Liu, Xing Huang and Daiqi Ye
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
5
DOI: 10.1039/b000000x
A series of sulfonic acid–functionalized Metal–Organic Frameworks (MOFꢀSO H) were prepared by
3
postsynthetic modification (PSM) of the organic linkers within the MOF with chlorosulfonic acid. The
obtained MOFꢀSO H, including sulfonic acid–functionalized MILꢀ101(Cr) [MILꢀ101(Cr)ꢀSO H], UIOꢀ
3
3
6
6(Zr) [UIOꢀ66(Zr)ꢀSO H], and MILꢀ53(Al) [MILꢀ53(Al)ꢀSO H], have been systematically studied as
3 3
1
1
2
0
5
0
solid acids in fructose transformation to 5ꢀhydroxymethylfurfural (HMF). With MILꢀ101(Cr)ꢀSO H as
catalyst, an HMF yield of 90% with a full fructose conversion was obtained at 120 °C for 60 min in
3
DMSO. The concentration of –SO H in MOFꢀSO H as well as the contribution of Brønsted acidity of
3
3
MOFꢀSO H parallels its –SO H grafting rate. Under a lower –SO H grafting lever, a good linear
3
3
3
correspondence between catalytic activity, in terms of turnover frequency, and sulfonic acidꢀsite density
of MOFꢀSO H was found. Moreover, the sulfonic acid groups, function as the catalytic sites, are
3
equivalent in all MOFꢀSO H for fructoseꢀtoꢀHMF transformation, regardless of precursor MOFs. Both
3
conversions of fructose and selectivities towards HMF increase with the sulfonic acidꢀsite density of
MOFꢀSO H at an initial stage of fructoseꢀtoꢀHMF transformation. Kinetics studies reveal that the MILꢀ
3
1
01(Cr)ꢀSO H promoted fructoseꢀtoꢀHMF transformation may follow pseudoꢀfirstꢀorder kinetics with
3
−1
observed activation energy of 55 kJ mol under the investigated conditions. Moreover, MILꢀ101(Cr)ꢀ
SO H, behaves as heterogeneous catalyst, can be easily recovered and reused. The research highlights a
3
good prospect for catalytic application of MOFꢀderived solid acid catalyst for biomass carbohydrate
valorization.
well as long reaction times. In the case of acidic resins, reaction
temperature is strictly limited due to their thermal stability.
Therefore, the development of a green and efficient acid catalyst
Introduction
2
3
3
4
4
5
0
5
0
5
The production of fuels and chemicals from abundant and
renewable biomass resource has recently attracted much
attention, owning to growing concerns of the exhaustion of fossil
4,5a
is a promising research direction. Moreover, a comprehensive
5
5
6
6
0
5
0
5
study of a correlation between structure and performance to this
catalyst as well as a kinetic research for fructoseꢀtoꢀHMF
1
fuel resources and degradation of the environment. Ongoing
4k,5
transformation is highly important to this crucial progress.
research on this topic is being mainly focused on both chemical
and biological transformations of biomass into bioꢀbased
platform chemicals as an alternative to petroleumꢀbased building
blocks. Among the biomassꢀderived platform chemicals, 5ꢀ
hydroxymethylfurfural (HMF) is regarded as a versatile and key
Recently, a series of novel solid acids such as acidic ionic
4aꢀb,5a
4c
4d
liquids,
SnꢀBeta zeolite, lignosulfonic acid, biomassꢀ
4e
derived sulfonated carbonaceous materials, nafionꢀresinꢀ
modified mesocellular silica foam, polymer bound sulfonic
acids, layered niobic acid, PVP/propylsulfonic acidꢀmodified
ordered mesoporous silica and Fe O ꢀSBAꢀSO H were
4f
4g
4h
2
building block for biorefinery. HMF can be converted into a
4i
4j
3
4
3
number of valuable chemicals, including 2,5ꢀdimethylfuran, 2,5ꢀ
diformylfuran, 2,5ꢀfurandicarboxylic acid, levulinic acid, 1,6ꢀ
hexanediol, adipic acid, caprolactam, and caprolactone, with a
developed for the purpose of fructoseꢀtoꢀHMF transformation.
Moreover, we recently reported a systematic study on the
conversion of fructose into HMF and alkyl levulinates using
3
high potential in fuel, polymer, and solvent applications.
4k
sulfonic acidꢀfunctionalized carbon materials.
HMF is mainly prepared from bioꢀbased hexose sugars
through acid promoted dehydration. To date, many acid catalysts
have been investigated for this important transformation,
including mineral or organic acid, zeolites, metal ions, acidic
ionic liquids, and acidic resins. Homogenous acids show
inherent drawbacks on product separation and equipment
corrosion. Solid acids suffer from low catalytic performance as
One of the core principles of green chemistry is the
application of heterogeneous and recyclable catalysis with
renewable feedstock for chemical productions. Metal–organic
frameworks (MOFs), a new class of porous crystalline materials,
are very promising candidates for application to catalyst based on
their high surface area, tunable pore sizes, and controllable
structures. Therefore, MOFꢀderived solid acid is targeted herein
2
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DOI: 10.1039/C3GC42414F
as heterogeneous catalyst for transformation of renewable
optimal conditions, a high HMF yield of 90% with a full fructose
biomass carbohydrate into HMF. In contrast to carbon materials 45 conversion was achieved with MILꢀ101(Cr)ꢀSO H (15.0%) as
3
and inorganic solids, MOFs contain an organic ligand component
which provides a potential approach for introducing functional
groups into MOFs through postsynthetic modification (PSM).
catalyst. Moreover, we present the results of a comprehensive
study of a correlation of structureꢀtoꢀperformance, kinetics, as
6
5
0
5
well as MILꢀ101(Cr)ꢀSO H recycling in fructoseꢀtoꢀHMF
3
PSM methods are, in fact, particularly attractive for the
fabrication of acidꢀfunctionalized MOFs as solid acid catalysts.
First, the presence of organic ligand component in MOFs 50 Experimental
provides a convenient employment of varieties of organic
transformation.
Materials
1
transformations. Second, the acid strength of asꢀprepared acidꢀ
functionalized MOFs basically can be precisely tuned by PSM
through grafting rate of the reaction. Moreover, the highly porous
and order nature of MOFs can presumably promote substrate
transfer within the MOF catalyst, which may facilitate the 55 hydroxymethylfurfural (HMF, 98%), Dꢀfructose (99%), Dꢀ
catalytic reaction.
Unless otherwise stated, all chemicals in this work were
commercial available and used without further purification.
Cr(NO ) ꢁ9H O (98%), Al(NO ) ꢁ9H O (98%), ZrCl (98%), 5ꢀ
3
3
2
3 3
2
4
1
glucose (99%), inulin (BC), sucrose (AR), cellobiose (98%), 1,4ꢀ
benzendicarboxylic acid (H BDC, 99%), and hydrofluoric acid
2
(38ꢀ40% solution in water) were obtained from Aladdin Industrial
Inc. (Shanghai, PR China). Chlorosulfonic acid (97%) and
phosphotungstic acid (H PW O ) was obtained from Sinopharm
60
3
12 40
Chemical Reagent Co. Ltd. (Shanghai, PR China). HꢀBeta (Si/Al
12.5), HYꢀzeolite (Si/Al ≥ 5.2) and HZSMꢀ5 (Si/Al = 25) were
commercially purchased from Nankai University Co. Ltd.
Tianjin, PR China).
=
(
65
Characterization techniques
FTꢀIR spectra of KBr pellets were recorded at room temperature
−1
in the 400–4000 cm region with a Bruker Tensor 27
spectrotometer, equipped with a Data Station, at a spectral
−1
resolution of 1 cm and accumulations of 128 scans. XRD
patterns were obtained using PANalytical X’pert Pro
70
a
multipurpose diffractometer operated at 40 KV and 40 mA, using
Niꢀfiltered CuK radiation. Potentiometric acid–base titration was
a
performed by using a Metrohm 877 Titrino plus instrument.
3
Scheme 1. (a) Synthetic routes to MOFꢀSO H, (b) Conversion of fructose
Elemental analysis of MOFsꢀSO H was obtained from an
3
into HMF.
75
Elementar Vario EL III. Scanning electron microscopy (SEM)
images were recorded by Hitachi Sꢀ4800 instrument operated at
10 KV. The BrunauerꢀEmmettꢀTeller (BET) surface area
measurements were performed with N2 adsorptionꢀdesorption
isotherms at 77 K (SIꢀMPꢀ10/PoreMaster 33, Quantachrome).
20
25
30
35
40
In a limited report on an application of MOFs as catalyst for
biomass valorization, Li and Hensen reported a selective
dehydration of fructose to HMF with phosphotungstic acid
(
PTA)ꢀencapsulated MILꢀ101(Cr), [PTA/MILꢀ101(Cr)], as solid
7a
acid catalyst. Matsuda and Kitagawa developed sulfonic acidꢀ 80 After degassed under vacuum at 423 K for 24 h and then
−6
functionalized MILꢀ101(Cr) [MILꢀ101(Cr)ꢀSO H] for cellulose
measured over the range of 10 < P/P < 0.1. The specific BET
3
0
7b
hydrolysis. Very recently, bifunctional acidꢀmetal catalysts [Ruꢀ
PTA/MILꢀ100(Cr)] containing ruthenium and PTA as active
species with a MILꢀ100(Cr) as support and encapsulation matrix,
respectively, were synthesized by us to achieve an oneꢀpot
surface areas were evaluated using the method in the p/p range
0
0.05 to 0.3.
Preparation of MOFs
7
c
8
9
10
conversion of cellobiose and cellulose into sorbitol.
85 MILꢀ101(Cr), UIOꢀ66(Zr), MILꢀ53(Al),
and PTA/MILꢀ
7
a
In the present work, to further extend a catalytic application
of MOFs for biomass conversion, the sulfonic acidꢀfunctionalized
101(Cr) (PTA 33.8 wt%) were prepared according to literature
method (see the Supporting Information for details).
MOFs (MOFꢀSO H) are evaluated as potential solid acid
3
Sulfonation of MOFs
catalysts (Scheme 1a) for the selective fructoseꢀtoꢀHMF
8
Before sulfonation, MILꢀ101(Cr) was degassed at 150 °C under
vacuum for 24 h. The activated MILꢀ101(Cr) (1 g) was stirred in
transformation (Scheme 1b). MOFs such as MILꢀ101(Cr), UIOꢀ
9
10
9
0
6
6(Zr), and MILꢀ53(Al) were chosen as substrate materials for
3
0 mL CH Cl at 0 °C for 20 min, ClSO H (0.5 g) in 10 mL
2 2 3
covalent ligand PSM due to their excellent chemical stability. The
asꢀprepared MOFꢀSO H with different ꢀSO H grafting rates was
CH Cl2 was dropwisely added to the mixture under vigorous
2
3
3
11c
magnetic stirring. After 30 min, the solid product was filtered
off, rinsed with ultrapure water and acetone, soaked in ethanol for
denoted as MOFꢀSO H (grafting rate) in this research. The
3
9
b,11b
grafting rate was calculated based on the literature method,
95
24 h at 70 °C and dried to give MILꢀ101(Cr)ꢀSO H with ꢀSO H
3 3
and donated as the molar ratio of sulfonic acid group (ꢀSO H) to
3
grafting rate of 15.0%. UIOꢀ66(Zr)ꢀSO H (9.5%) and MILꢀ
aromatic terephthalate units in MOFꢀSO H [based on organic
3
3
5
3(Al)ꢀSO H (8.2%) were prepared following same synthetic
linker of 1,4ꢀbenzenedicarboxylic acid (BDC)]. Under the
3
2
| Journal Name, [year], [vol], 00–00
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DOI: 10.1039/C3GC42414F
procedure as for MILꢀ101(Cr)ꢀSO H used except that MILꢀ
of bare MOF and its corresponding MOFꢀSO H are shown in
3
3
1
01(Cr) was replaced by UIOꢀ66(Zr) and MILꢀ53(Al),
Figure S2. For MILꢀ101(Cr)ꢀSO H (Figure S2b) and UIOꢀ66(Zr)ꢀ
3
respectively.
SO H (Figure S2d), their patterns are almost the same as that of
3
their corresponding precursors MILꢀ101(Cr) (Figure S2a) and
UIOꢀ66(Zr) (Figure S2c), respectively, only with some slight
variations in the Bragg intensities. These results indicate that the
structures are reserved after sulfonic acid groups inserted onto the
Fructose conversion into HMF
60
5
Fructose dehydration was performed in a thermostatted Ace
Pressure Tube. Each time, MOFꢀSO H was preꢀdried at 150 °C
under vacuum overnight before the reaction. The reactants were
always loaded into the reactor at ambient temperature. The
3
11b
framework of MILꢀ101(Cr) and UIOꢀ66(Zr). In the case of
MILꢀ53(Al)ꢀSO H (Figure S2f), despite some changes compared
3
reactor was then purged with nitrogen to expel air before heating 65 with MILꢀ53(Al), framework still retains its intrinsic porosity as
1
1b
1
1
2
0
5
0
up. In a typical run, fructose (500 mg), MILꢀ101(Cr)ꢀSO H
illustrated by Gascon and coꢀworker.
3
(15.0%) (300 mg) and DMSO (5 mL) were added to the reactor.
After the vial was closed, the reactor was placed in a preheated
oil bath at 120 °C with vigorous stirring for 60 min. After the
reaction, it was quenched by placing the vial in an ice bath at 0
°C. The mixture was filtered and then decanted into a volumetric
flask using water as diluents, and analyzed by highꢀperformance
liquid chromatography (HPLC). For the recycling experiment,
a
b
typically, fructose (500 mg), MILꢀ101(Cr)ꢀSO H (15.0%) (300
3
mg) and DMSO (5 mL) were added to a reactor. The mixture was
heated in a batch reactor at 120 °C for 60 min. The solid was
separated by filtration, washed with DMSO, dried at 150 °C
under vacuum overnight and then reused directly for the next run
by adding a fresh fructose (500 mg) and DMSO (5 mL).
c
Analysis of product
2
5
The HPLC analysis was performed on Shimadzu LCꢀ20AT
equipped with a UVꢀVis/refractive index detector and a Shodex
Sugar SHꢀ1011 column (ø8×300 mm). H SO (0.005 M) solution
was used as the mobile phase at a flow rate of 0.5 mL min , and
the column temperature was maintained at 50 °C. The amounts of
fructose and HMF were calculated based on external standard
curves constructed with authentic standards.
2
4
−1
70
Fig. 1 The proposed structures of (a) MILꢀ101(Cr)ꢀSO
3
H, (b) UIOꢀ
6
6(Zr)ꢀSO H, and (c) MILꢀ53(Al)ꢀSO H. Gray, yellow and red balls
3
3
represent carbon, sulphur and oxygen atoms, respectively. Chromium
octahedral in (a), zirconium octahedral in (b), and aluminum octahedral in
3
0
(c) are in green, dark blue, and dark green, respectively. Hydrogen atoms
75
are omitted for clarity.
Results and Discussion
Sulfonic acid-functionalized MOFs
2500
2000
1500
Previously, MILꢀ101(Cr)ꢀSO H was synthesized by a oneꢀpot
3
3
4
4
5
5
5
0
5
0
5
selfꢀassembly of chromium trioxide and 2ꢀsulfoterephthalic acid
7
b
under hydrothermal conditions. A PSM method for MILꢀ
01(Cr)ꢀSO H preparation involves sulfation of MILꢀ101(Cr)
MIL-101(Cr)-SO H (3.0%)
1
3
3
MIL-101(Cr)-SO H (15.0%)
3
with concentrated sulfuric acid (H SO , 98%) in the presence of
2
4
recovered MIL-101(Cr)-SO H (15%)
3
trifluoromethanesulfonic anhydride (Tf O) in nitromethane
2
11aꢀb
(CH NO ).
In this study, MILꢀ101(Cr)ꢀSO H was prepared by
1000
3
2
3
PSM of MILꢀ101(Cr) at the backbone phenylene units with
11c
chlorosulfonic acid as sulfonation reagent in dichloromethane.
MILꢀ101(Cr)ꢀSO H with different ꢀSO H grafting rates was
500
3
3
achieved by variable amount of chlorosulfonic acid added. UIOꢀ
66(Zr)ꢀSO H and MILꢀ53(Al)ꢀSO H were prepared following the
0
3
3
0.0
0.2
0.4
0.6
0.8
1.0
P / P0
same synthetic procedure as for MILꢀ101(Cr)ꢀSO H except that
3
MILꢀ101(Cr) was replaced by UIOꢀ66(Zr) and MILꢀ53(Al),
respectively. Figure 1 shows the proposed structures of MILꢀ
Fig. 2 N
2
adsorption/desorption isotherms of MILꢀ101(Cr)ꢀSO
H (15.0%) and recovered MILꢀ101(Cr)ꢀSO
with the reaction conditions described in Figure 9.
3
H (3.0%),
3
H (15.0%)
MILꢀ101(Cr)ꢀSO
3
8
0
1
01(Cr)ꢀSO H, UIOꢀ66(Zr)ꢀSO H, and MILꢀ53(Al)ꢀSO H.
3 3 3
A FTꢀIR study on the sulfonated structures confirms the
successful functionalization of MOFs with ꢀSO H (Figure S1).
Compared with the bare MOFs, the resulting pore
3
modification is also visible on the N adsorption isotherms of the
2
−1
For MOFꢀSO H, new bands, appear at 1137 and 1294 cm along
with a shoulder at 1427 cm , can be attributed to the O=S=O
symmetric and asymmetric stretching modes (Figure S1b, d and
3
MOFꢀSO H. MILꢀ101(Cr)ꢀSO H exhibits a significant decrease
3
3
−1
2
−1
8c,b
of porous surface area from 2693 m g for MILꢀ101(Cr)
to
2
−1
2 −1
85
2023 m g for MILꢀ101(Cr)ꢀSO H (3.0%) and to 1757 m g for
3
1
1c
f), which is in accordance with the literature. The XRD patterns
This journal is © The Royal Society of Chemistry [year]
Journal Name, [year], [vol], 00–00 | 3

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DOI: 10.1039/C3GC42414F
a
Table 1. Characterization of MOFꢀSO
3
H
−
1 c
Adsorption [mmol g ]
fructose
Conv. [%]
HMF
Yield
a
a
b
S content
[
grafting rate
acid density
+ −1
Run Catalyst
−1
Selec.
%]
mmol g ]
ꢀSO
3
H [%]
H [mmol g ]
fructose
HMF
[
[%]
1
2
3
4
5
6
MILꢀ101(Cr)ꢀSO
3
3
3
H
H
H
0.54
0.22
0.11
0.32
0.29
/
15.0
6.1
3.0
9.5
8.2
/
0.60
0.29
0.25
0.41
0.34
0.0060
0.0045
0.0039
0.0052
0.0023
0.0031
0.088
0.048
0.035
0.061
0.094
0.028
>99
91
91
78
76
86
80
53
90
MILꢀ101(Cr)ꢀSO
MILꢀ101(Cr)ꢀSO
71
63
85
79
24
83
UIOꢀ66(Zr)ꢀSO
3
H
>99
>99
45
MILꢀ53(Al)ꢀSO
3
H
MILꢀ101(Cr)
a
b
Based on elemental analysis. Acidꢀdensity values were determined through potentiometric acid–base titration and calculated using the amount of NaOH
c
added to the corresponding MOF material. Determined by HPLC based on corresponding concentration change of fructose and HMF in DMSO. Reaction
conditions: fructose (500 mg), MOFꢀSO H (300 mg), DMSO (5 mL), time (1 h), 120 °C.
3
5
MILꢀ101(Cr)ꢀSO H (15.0%) due to pore blocking (Figure 2).
85% (Table 1, run 4) and 79% (Table 1, run 5), respectively.
Figure 3 further shows that the catalytic performance of MOFꢀ
3
Table 1 shows a comparison of the asꢀprepared MOFꢀSO H.
3
The grafting rate of ꢀSO H in the MOFꢀSO H were calculated by 50 SO H in fructoseꢀtoꢀHMF transformation decreases with the
3
3
3
elemental analysis based on the sulfur component, the sulfonic
acidꢀsite density was estimated by the potentiometric acid–base
titration method, whereas the amount of adsorbed HMF and
following order of MILꢀ101(Cr)ꢀSO H (15.0%) > UIOꢀ66(Zr)ꢀ
3
1
1
2
2
0
SO H (9.5%) > MILꢀ53(Al)ꢀSO H (8.2%). Notably, this result is
3
3
in line with the sequence of their corresponding sulfonic acidꢀsite
fructose over MOFꢀSO H was chromatographically determined
density as described in Table 1, suggesting that MOFꢀSO H with
3
3
by corresponding concentration change of fructose and HMF. 55 the highest concentration of sulfonic acidꢀgroup proved to be
Both elemental analysis and acid–base titration experiment
most active catalyst for fructoseꢀtoꢀHMF transformation.
5
0
5
further confirmed the successful grafting of –SO H in MOFꢀ
3
SO H. The results given in Table 1 suggest that the loading level
3
100
of ꢀSO H in MOFꢀSO H as well as the contribution of Brønsted
3
3
acidity in MOFꢀSO H decreases in the order of MILꢀ101(Cr)ꢀ
3
SO H (15.0%) > UIOꢀ66(Zr)ꢀSO H (9.5%) > MILꢀ53(Al)ꢀSO H
3
3
3
80
(8.2%) > MILꢀ101(Cr)ꢀSO H (6.1%) > MILꢀ101(Cr)ꢀSO H
3
3
(
3.0%), demonstrating that the acid strength of MOFꢀSO H
3
60
parallels its ꢀSO H grafting level. Moreover, all of the MOFꢀ
3
SO H shows significant adsorption of HMF than in the case of
3
fructose, presumably owning to an interaction between an
aromatic ring on HMF and a connecting organic linker of BDC in
40
5
b
MOFꢀSO H.
3
2
0
MIL-101(Cr)-SOH(15.0%)
C
Fru
;
Y
HMF
HMF
HMF
3
Conversion of fructose into HMF
UIO-66(Zr)-SOH(9.5%)
CFru
;
Y
3
Table 1 shows the dehydration of fructose to HMF in DMSO at
MIL-53(Al)-SOH(8.2%)
CFru
;
Y
3
0
1
20 °C for 1 h with MOFꢀSO H as solid acid catalysts (Scheme
3
0
10
20
30
40
50
60
30
35
40
45
1). An initial experiment was carried out to investigate the effect
of the ꢀSO H grafting rate in MILꢀ101(Cr)ꢀSO H on the fructoseꢀ
Time/ min
3
3
Fig. 3 The comparison of catalytic performance of MOFꢀSO
3
H on
toꢀHMF transformation. For MILꢀ101(Cr)ꢀSO H with a ꢀSO H 60 fructoseꢀtoꢀHMF transformation. Conditions: fructose (500 mg), MOFꢀ
3
3
SO H (300 mg), DMSO (5 mL), 120 °C.
3
grafting rate of 15.0%, an HMF yield of 90% was obtained with a
full fructose conversion (Table 1, Run 1). With a decrease of the ꢀ
Figure 4 shows the influence of reaction temperature and
time on the conversion of the fructose into HMF with MILꢀ
01(Cr)ꢀSO H (15%) as solid acid. Generally, the yield of HMF
3
SO H grafting rate to 6.1%, the HMF yield was 71% (Table 1,
3
Run 2). A further decrease of the ꢀSO H grafting rate to 3.0%
3
1
resulted in an HMF yield of only 63% (Table 1, Run 3),
6
5
increased with time. The HMF yield increased slowly to 63%
after 60 min at 100 °C, while it increased quickly to 78% after 20
min at 140 °C, confirming that raising the reaction temperature
promotes the fructoseꢀtoꢀHMF transformation. The slight
decrease of the HMF yields with prolonged reaction time after 24
min at 140 °C may be attributed to a further polymerization of
HMF to form oligomers under the relatively high temperature.
We further compared our results with another type of MOFꢀ
derived solid acid PTA/MILꢀ101(Cr). According to the literature,
an HMF yield of 63% with fructose conversion of 82% was
suggesting the catalytic performance of MILꢀ101(Cr)ꢀSO H as a
3
function of the ꢀSO H loading level as well as the sulfonic acidꢀ
3
site density. Polymeric humins were found as the main byꢀ
products in the reaction. Moreover, the MILꢀ101(Cr)ꢀSO H was
3
substantially more active than bare MILꢀ101(Cr). MILꢀ101(Cr)
produced an HMF yield of 24% with a fructose conversion of
70
4
5% under the investigated conditions (Table 1, Run 6).
Apart from MILꢀ101(Cr)ꢀSO H (15.0%), UIOꢀ66(Zr)ꢀSO H
3
3
(
9.5%) and MILꢀ53(Al)ꢀSO H (8.2%) were also evaluated as
3
solid acid for fructose dehydration, producing HMF yields of
4
| Journal Name, [year], [vol], 00–00
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Green Chemistry
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DOI: 10.1039/C3GC42414F
obtained in 30 min with PTA/MILꢀ101(Cr) (PTA 33.8 wt%) as
catalyst in DMSO at 130 °C. In our case, under similar
conditions, an HMF yield of 84% with fructose conversion of
After a data fitting as shown in Figure 4, the linear
relationship between Ln(1ꢀX) and reaction time (t) (Figure 5a)
thus supported the hypothesis as pseudoꢀfirst order for fructoseꢀ
toꢀHMF transformation. Figure 5a further shows that the
observed rate constant (k) of fructoseꢀtoꢀHMF transformation
7
a
9
4% was obtained with MILꢀ101(Cr)ꢀSO H (15%) at 120 °C.
3
4
5
5
6
6
5
0
5
0
5
5
Moreover, the maximum HMF yield of 90% with a full fructose
conversion was achieved at 120 °C after a reaction time of 60 min,
further demonstrating a comparable catalytic performance of
−1
increases from 2.01 to 11.3 h as the increased reaction
temperature from 100 to 140 °C, which quantitatively confirms
that raising the reaction temperature promotes fructose
MILꢀ101(Cr)ꢀSO H (15.0%).
3
3
transformation. Figure 5b plots the (Lnk) versus (1/T × 10 ) based
on the Arrhenius equation, demonstrating that the observed
activation energy (Ea) and preꢀexponential factor (A) for the
100
−1
7
−1
fructose transformation were 55 kJ mol and 8.95 × 10 h ,
respectively. In contrast, an observed activation energy of 70
kJ/mol was obtained with molecular sieve HZSMꢀ5 (Si/Al = 25)
as catalyst under the investigated conditions, further suggesting a
80
high efficiency of MILꢀ101(Cr)ꢀSO H (15%) over HZSMꢀ5
3
60
(Si/Al = 25). Moreover, a bifunctional catalyst designed by
sulfonic acidꢀ and ionic liquidꢀfunctionalization over mesoporous
silica nanoparticles (MSN) was recently prepared for fructose
40
5a
dehydration to HMF in DMSO. Activation energies of 67.5 and
o
−1
1
40 C
C
Fru
;
Y
HMF
HMF
HMF
80.05 kJ mol were obtained with and without the bifunctional
20
o
1
20 C
CFru
;
Y
catalyst, respectively. In our case, the observed activation energy
o
−1
1
00 C
CFru
;
Y
of 55 kJ mol for MILꢀ101(Cr)ꢀSO H (15%) further indicates
3
0
MOFꢀSO H catalyst can efficiently lower the activation energy
3
0
10
20
30
Time/min
40
50
60
and lead to a relatively higher reaction rate.
1
0
Fig. 4 Effect of temperature and reaction time on fructoseꢀtoꢀHMF
transformation. Conditions: fructose (500 mg), MILꢀ101(Cr)ꢀSO H (15%)
300 mg), DMSO (5 mL).
3
a 5
(
4
Kinetics studies
y = 11.34026x-0.08927
2
R = 0.91043
1
2
2
5
0
5
Kinetics studies of fructoseꢀtoꢀHMF transformation were
y = 4.02479x+0.56536
3
2
R
= 0.98817
investigated with MILꢀ101(Cr)ꢀSO H (15%) as catalyst.
3
According to ongoing research, transformation of fructose into
2
1
0
5
a
HMF may obey pseudoꢀfirst order process. This assumption is
supposed under the conditions that 1) HMF is sole product of
fructose dehydration, and 2) HMF is stable enough under the
investigated conditions without further degradation. Under the
above conditions, the rate of fructose transformation (r[fructose])
can be expressed as the following equation as a first order
reaction:
y = 2.0149x-0.43439
2
R
= 0.99325
O
O
O
100
120
140
C
C
C
0.0
0.2
0.4
0.6
0.8
1.0
Reaction time / h
b
2
.4
.0
2
[
fructose] and [HMF] indicate molar concentrations of fructose
and HMF, respectively; whereas, k is the rate constant of fructose
1.6
3
0
dehydration at a certain temperature.
1
.2
.8
Slope = -6.59807
Intercept = 18.31002
2
R
0
= 0.94999
According to the above Arrhenius equation, the original equation
is transformed into the following equation with the [fructose] in
terms of conversion X. Herein, t and C are the reaction time and
an arbitrary constant, respectively.
2
.4
2.5
2.6
2.7
3
5
1/T*1000 / 1/K
Fig. 5 (a) The kinetics profiles of fructose dehydration to HMF (fitted by
70 first order assumption) with MILꢀ101(Cr)ꢀSO H (15%) as catalyst. (b)
3
Arrhenius plots for fructose dehydration to HMF. Conditions: fructose
3
(500 mg), MILꢀ101(Cr)ꢀSO H (15%) (300 mg), DMSO (5 mL).
4
0
Correlation between structure and performance of MOF-
SO H
3
This journal is © The Royal Society of Chemistry [year]
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DOI: 10.1039/C3GC42414F
Figure 6a shows
a
strong correlation between fructose
catalytic performance of MOFꢀSO H mainly comes from sulfonic
3
conversion/HMF selectivity and the sulfonic acidꢀsite density of 35 acid groups of MOFꢀSO H for fructoseꢀtoꢀHMF transformation.
3
MOFꢀSO H. Whereas, Figure 6b plots fructose conversion/HMF
Moreover, the sulfonic acid groups, function as the catalytic sites,
3
selectivity versus S content of MOFꢀSO H. Under a fixed
are equivalent in all MOFꢀSO H for fructose dehydration,
3
3
5
reaction of 10 min, HMF selectivity (about 84%) and fructose
conversion (about 62%) is highest for catalyst MILꢀ101(Cr)ꢀ
regardless of precursor MOFs. An arbitrary extrapolation of the
plot in Figure 7b further suggests that MILꢀ101(Cr)ꢀSO H with a
3
SO H (15.0%) with the highest Brønsted sulfonic acidꢀsite 40 higher ꢀSO H grafting rate of 15.0%, corresponding to a higher
3
3
−1
density (Figure 6a). Figures 6a and 6b further indicate an increase
in selectivity towards HMF as well as conversion of fructose with
an increase in Brønsted acidity contribution from MOFꢀSO H.
sulfonic acidꢀsite density of 0.60 mmol g , should have a TOF of
about 8.3 h which is, however, in sharp contrast with an
observed value of 6.2 h . This behavior may be explained as a
result of the increase in the sulfonic acidꢀgroup density of MOFꢀ
−1
−1
10
3
45
SO H on the one hand and the decrease in the micropore volume
3
a
as well as porous surface area of MOFꢀSO H on the other hand as
3
80
70
60
50
40
30
7c,5c
ꢀ
SO H grafting rates increase.
3
a
0.60
0.6
0.5
0.4
0.3
8
TOF
Acid density
6.2
0.41
6
5.2
0.34
C
Fru
0.29
SHMF
4.0
4
2
0
0
.25
3.2
0
.2
.1
0.3
0.4
0.5
0.6
2.6
-
1
Acid density / mmol g
0
b
0.0
8
7
6
5
4
3
0
0
0
0
0
0
b

ꢀ
8
7
6
5
4
3
C
Fru
SHMF
0.1
0.2
0.3
0.4
0.5
-
1
S content / mmol g
Fig. 6 The conversion of fructose and selectivity towards HMF at reaction
time of 10 min versus acid density of MOFꢀSO (a) and S content of
MOFꢀSO H (b). Conditions: fructose (500 mg), MOFꢀSO H (300 mg),
DMSO (5 mL), 120 °C, 10 min.
15
3
3
3
0
.3
0.4
0.5
0.6
Acid density / mmol g-1
Recently, we revealed a linear correspondence between the
catalytic activity and acid density for sulfonic acidꢀfunctionalized
carbon materials in fructose dehydration to HMF. Herein, a
similar structure of precursor MOFs with the same sulfonation
50
Fig. 7 (a) The comparison of sulfonic acidꢀsite density and turnover
frequencies (TOFs) of MOFꢀSO H for fructoseꢀtoꢀHMF transformation.
b) TOFs of MOFꢀSO H versus sulfonic acidꢀsite density of MOFꢀSO H.
TOFs for the fructoseꢀtoꢀHMF transformation were measured at t = 10
4
k
3
20
25
30
(
3
3
(
method makes MOFꢀSO H an ideal model to quantitatively 55 min, given as amounts of consumed fructose per amounts of MOFꢀSO H
3
3
investigate the relationship between structure and performance in
fructoseꢀtoꢀHMF transformation. Figure 7a shows a comparison
of sulfonic acidꢀsite density and turnover frequencies (TOFs) of
per hour. Conditions: fructose (500 mg), MOFꢀSO
3
H (300 mg), DMSO (5
mL), 120 °C, 10 min.)
Comparison MOF-SO H and other solid acids in fructose
3
MOFꢀSO H for fructoseꢀtoꢀHMF transformation. Notably, both
3
conversion
sulfonic acidꢀsite density and TOFs of MOFꢀSO H increase as
3
6
0
In addition to MOFꢀSO H, solid acids such as PTA/MILꢀ101(Cr)
3
grafting rate of ꢀSO H in MOFꢀSO H. Moreover, Figure 7b plots
3
3
7a
(PTA 33.8 wt%), HꢀBeta (Si/Al = 12.5), HYꢀzeolite (Si/Al ≥
fructose transformation rates in terms of TOF against the sulfonic
5
.2) and HZSMꢀ5 (Si/Al = 25) were subjected to fructose
acidꢀsite densities of MOFꢀSO H. Interestingly, the sulfonic acidꢀ
3
dehydration for comparison purpose. Figure 8a shows the
catalytic activity for fructose dehydration at 120 °C decreases
site density of MOFꢀSO H shows a good linear correspondence
3
to fructose transformation rate under a grafting rate of ꢀSO H
3
65
with the order of MILꢀ101(Cr)ꢀSO H (15.0%) > PTA/MILꢀ101
3
lower than 9.5% in MOFꢀSO H. This result reveals that the
3
6
| Journal Name, [year], [vol], 00–00
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Green Chemistry
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DOI: 10.1039/C3GC42414F
(
PTA 33.8 wt%) >
selectivity to HMF versus conversion of the fructose in fructose
dehydration over different solid acids. In these reactions, the
selectivity to HMF generally increased with an increase of
fructose conversion. Notably, the highest selectivities to HMF
a
100
25
were observed over MILꢀ101(Cr)ꢀSO H (15.0%) with a constant
3
8
6
4
2
0
0
0
0
0
fructose conversion; whereas, the lowest selectivities to HMF
were found over PTA/MILꢀ101 (PTA 33.8 wt%). According to
the literature, PTA/MILꢀ101(Cr) (PTA 33.8 wt%) corresponds to
a loading level of approximately three PTA clusters per cage of
3
0
7a
the MILꢀ101(Cr) MOF. A relatively high loading level of PTA
clusters in PTA/MILꢀ101(Cr) could, on the one hand, increase
acidity as well as catalytic acitivity of PTA/MILꢀ101(Cr) towards
fructose dehydration. On the other hand, bulky and abundant
MIL-101(Cr)-SO3H
PTA/MIL-101(Cr)
HZSM-5
H-Beta
HY-Zeolites
35 PTA clusters in the cage of the MILꢀ101(Cr) might lead to
serious diffusion limitations. It has been established that mass
transfer limitations often lead to a reduced selectivity for
0
10
20
30
40
50
60
Time / min
5c
exothermic reactions. In this case, the observed low selectivities
towards HMF over PTA/MILꢀ101(Cr) can presumably be related
to diffusion limitations of fructose within PTA/MILꢀ101(Cr).
b
80
60
40
20
0
40
Catalyst recycling
In order to demonstrate the reusability of MILꢀ101(Cr)ꢀSO H
3
(15.0%), a fiveꢀcycle experiment was performed, and the results
are shown in Figure 9. Notably, the measured yields of the HMF
only slightly reduced from 90 to 85%. The decrease in catalytic
activity could be presumably attributed to minor leaching of
MIL-101(Cr)-SO3H
PTA/MIL-101(Cr)
HZSM-5
H-Beta
HY-Zeolites
4
5
5
5
0
5
acidic proton from MOFꢀSO H or the adsorption and
3
accumulation of oligomeric products on the acid site of highly
0
10
20
30
40
50
60
4k,7c
microporous catalyst.
Notably, the observed reusability of
Time / min
MILꢀ101(Cr)ꢀSO H is still far higher than that achieved with
3
regards to recently reported PTA/MILꢀ101(Cr) (PTA 33.8 wt%).
For PTA/MILꢀ101(Cr)ꢀcatalyzed fructose dehydration, a fast
deactivation process with time was observed due to the leaching
c
80
60
40
7
a
of active species from PTA/MILꢀ101(Cr) into solvent.
100
90
90
90
89
85
MIL-101(Cr)-SO3H
PTA/MIL-101(Cr)
HZSM-5
80
H-Beta
HY-Zeolites
60
0
20
40
60
80
100
Fructose Conversion / %
5
4
0
0
0
Fig. 8 (a) Fructose conversion versus time; (b) HMF yield versus time; (c)
selectivity to HMF versus fructose conversion over solid acid catalysts.
2
Reaction conditions: fructose (500 mg), catalyst [MILꢀ101(Cr)ꢀSO
15.0%), PTA/MILꢀ101(Cr) (PTA 33.8 wt%), HꢀBeta (Si/Al = 12.5), HYꢀ
zeolite (Si/Al ≥ 5.2) and HZSMꢀ5 (Si/Al = 25), 300 mg], DMSO (5 mL),
20 °C.
3
H
(
1
0
1
1
2
3
4
5
Run
HZSMꢀ5 (Si/Al = 25) > HYꢀzeolite (Si/Al ≥ 5.2) > HꢀBeta (Si/Al
12.5). In case of HMF formation (Figure 8b), the highest HMF
Fig. 9 Catalyst recycling. Conditions: fructose (500 mg), MILꢀ101(Cr)ꢀ
=
SO H (15%) (300 mg), DMSO (5 mL), 120 °C, 60 min.
3
yield was observed over MILꢀ101(Cr)ꢀSO H (15.0%) among the
3
To check the contribution of released acidic proton from
1
5
solid acid catalysts under the investigated conditions. Whereas,
the catalytic performance of PTA/MILꢀ101 (PTA 33.8 wt%) for
HMF production was comparable to HZSMꢀ5 (Si/Al = 25) and
HYꢀzeolite (Si/Al ≥ 5.2). This result suggested that the higher
acid strength, the cubic crystal, threeꢀdimensional and highly
6
0
MILꢀ101(Cr)ꢀSO H (15.0%) to homogeneous reactions, MILꢀ
3
1
01(Cr)ꢀSO H was removed from the reaction medium by
3
filtration after 5 min of reaction (at an HMF yield of 12%) and
the experiment proceeded with the filtrate under the same
conditions as described in Figure 10. As expected, the reaction
2
0
porous system of MILꢀ101(Cr)ꢀSO H could presumably promote
3
65
slowly proceeded after the removal of MILꢀ101(Cr)ꢀSO H,
3
the dehydration of fructose to HMF. Figure 8c shows the
producing an HMF yield of only 35%. Notably, without using
This journal is © The Royal Society of Chemistry [year]
Journal Name, [year], [vol], 00–00 | 7

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Page 8 of 9
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DOI: 10.1039/C3GC42414F
MILꢀ101(Cr)ꢀSO H, the contribution of the blank experiment
reached 46%, which is slightly higher than the HMF yield of 44%
3
gave an HMF yield of 24% (Figure 10). Moreover, the blank 35 obtained from sucrose (Table 2, Runs 1–2). These results indicate
experiment showed a similar trend to the catalyst filtration
that MILꢀ101(Cr)ꢀSO H catalyzes the hydrolysis of sucrose and
3
reaction upon the removal of MILꢀ101(Cr)ꢀSO H. The above
inulin without the need for higher temperature or longer reaction
times. When glucose, cellobiose, and cellulose were subjected to
our reaction conditions, the HMF yield was remarkably inferior
(Table 2, Run 3–5). This result clearly indicates that only fructose
in sucrose and inulin was converted to HMF and MILꢀ101(Cr)ꢀ
3
5
0
5
0
results thus indicate that a slight increase in HMF yield from 12%
to 35% in catalyst filtration reaction may be attributed to the
contribution of the blank experiment, rather than released acidic
40
proton from MILꢀ101(Cr)ꢀSO H. Moreover, the recovered MILꢀ
3
1
01(Cr)ꢀSO H after a fiveꢀcycle experiment showed almost
3
SO H does not catalyze the isomerization of glucose to fructose.
3
1
1
2
identical sulfonic acidꢀsite density to the fresh one, further
In addition to DMSO, when ionic liquid 1ꢀbutylꢀ3ꢀ
methylimidazolium chloride [BMIM]Cl was used as solvent,
suggesting the stability of MILꢀ101(Cr)ꢀSO H and verifying the
3
heterogeneous catalysis of MILꢀ101(Cr)ꢀSO H. ICP–OES
3
45 similar results for HMF formation were observed (Table 2, Runs
–10).
analysis showed that only 0.01% of the total amount of Cr had
6
leached from MILꢀ101(Cr)ꢀSO H after the first run. BET analysis
3
2
−1
indicates that the specific surface area decreases from 1757 m g
Conclusion
2
−1
for the fresh MILꢀ101(Cr)ꢀSO H (15.0%) to 1146 m g for the
3
recovered one (Figure 2), suggesting the adsorption of humins on
the surface of the catalyst. Therefore, the slightly reduced activity
In summary, MOFꢀSO H, prepared by covalent PSM of the
3
backbone phenylene units within the MOFs with chlorosulfonic
of MILꢀ101(Cr)ꢀSO H in catalyst recycling can reasonably be 50 acid resulted in active solid acid catalysts. The MOFꢀSO H was
3
3
related to the adsorption and accumulation of oligomeric products
effective for catalytic fructoseꢀtoꢀHMF transformation. A high
on the catalyst surface.
HMF yield of up to 90% with a full fructose conversion was
obtained with MILꢀ101(Cr)ꢀSO H as catalyst. Both the
3
concentration of –SO H in MOFꢀSO H and the contribution of
Brønsted acidity of MOFꢀSO H can be precisely tuned by –SO H
3 3
3
3
1
00
5
6
6
5
0
5
grafting rate of MOFꢀSO H. Under lower –SO H grafting levers,
3
3
8
6
4
2
0
0
0
0
0
the relationship between the catalytic activity in terms of TOF
and sulfonic acidꢀsite density of MOFꢀSO H shows a good linear
3
with MIL-101(Cr)-SO
removal of MIL-101(Cr)-SO
after the arrow
without MIL-101(Cr)-SO
3H
3H
correspondence. Moreover, the sulfonic acid groups are
equivalent in all MOFꢀSO H for fructoseꢀtoꢀHMF transformation,
3
3H
regardless of precursor MOFs. Our studies also reveal that the
MILꢀ101(Cr)ꢀSO H promoted fructoseꢀtoꢀHMF transformation
3
filtration of the catalyst
may obey pseudoꢀfirstꢀorder kinetics with observed activation
−1
energy of 55 kJ mol . Moreover, MILꢀ101(Cr)ꢀSO H, behaves as
3
heterogeneous catalyst, can be recovered and reused.
0
10
20
30
40
50
60
Time / min
Acknowledgements
Fig. 10 Effects of the removal of MILꢀ101(Cr)ꢀSO
dehydration. Conditions: fructose (500 mg), MILꢀ101(Cr)ꢀSO
300 mg), DMSO (5 mL), 120 °C.
3
H on the fructose
This work was financially supported by National Natural Science
Foundation of China (21172219, 21207039 and 21101053),
National Basic Research Program of China (973 Program,
2012CB215304), 100 Talents Program of the Chinese Academy
of Sciences, and Guangdong Provincial Key Laboratory of
Atmospheric Environment and Pollution Control.
25
3
H (15.0%)
(
Conversion of other feedstocks to HMF
70
a
Table 2. Conversion of other feedstocks to HMF
Run
Substrate
Solvent
T [°C]
Yield [%]
Notes and references
1
2
3
4
5
6
7
8
9
Inulin
DMSO
DMSO
DMSO
DMSO
120
120
120
150
150
120
120
120
150
150
46
44
7
24
trace
57
49
8
Sucrose
Glucose
Cellobiose
Cellulose
Inulin
Sucrose
Glucose
Cellobiose
Cellulose
a
CAS Key Laboratory of Renewable Energy, Guangzhou Institute of
7
8
8
9
5
0
5
0
Energy Conversion, Chinese Academy of Sciences. Guangzhou 510640
(
PR China). E-mail: chenjz@ms.giec.ac.cn. Tel./Fax: +86-20-3722-3380.
Guangdong Provincial Key Laboratory of Atmospheric Environment
DMSO
b
[Bmim]Cl
[Bmim]Cl
[Bmim]Cl
[Bmim]Cl
[Bmim]Cl
and Pollution Control, College of Environment and Energy, South China
University of Technology, Guangzhou 510006 (PR China)
c
University of Chinese Academy of Sciences. Beijing 100049 (PR China).
27
trace
†
Electronic Supplementary Information (ESI) available: [details of any
1
0
supplementary information available should be included here]. See
DOI: 10.1039/b000000x/
a
Reaction conditions: substrate (100 mg), MILꢀ101(Cr)ꢀSO
3
H (15.0%)
‡
Footnotes should appear here. These might include comments relevant
(60 mg), solvent (DMSO 2 mL or [Bmim]Cl 2 mL), time (2 h).
to but not central to the matter under discussion, limited experimental and
spectral data, and crystallographic data.
30
Besides fructose, the MILꢀ101(Cr)ꢀSO H was further extended to
inulin, sucrose, glucose, cellobiose, and cellulose, and the results
are presented in Table 2. When inulin was used, the HMF yield
3
1
a) P. Gallezot, Chem. Soc. Rev. 2012, 41, 1538–1558; b) A. Corma,
S. Iborra, A. Velty, Chem. Rev. 2007, 107, 2411–2502; c) G. W.
Huber, S. Iborra, A. Corma, Chem. Rev. 2006, 106, 4044–4098; d) J.
N. Chheda, G. W. Huber, J. A. Dumesic, Angew. Chem. Int. Ed.
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Sulfonic acidꢀfunctionalized MetalꢀOrganic Frameworks are efficiently used as recyclable solid acid catalysts for the fructoseꢀtoꢀHMF
transformation.
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