Selective hydrogenation of D-glucose using amine functionalized nanoporous polymer supported Ru nanoparticles based catalyst

Article abstract of DOI:10.1016/j.cattod.2015.09.045

Amine functionalized nanoporous polymer (AFPS) supported Ru based catalysts were prepared by simple impregnation-chemical reduction method, wherein Ru nanoparticles dispersed on AFPS matrix. The synthesized Ru/AFPS catalysts with different Ru loading were characterized by various characterization tools such as powder XRD, HRTEM, SEM, FTIR, TGA, CO chemisorption and XPS. The catalytic performances of Ru/AFPS catalysts were evaluated in hydrogenation of D-glucose to produce D-sorbitol under aqueous phase condition. The experiments results indicated that the increase of Ru content in Ru/AFPS catalyst enhanced the formation of desire D-sorbitol and 5Ru/AFPS catalyst (having 5 wt% of Ru) showed higher conversion and high D-sorbitol selectivity (98%). In comparison to non-functionalized polymer supported Ru catalyst (5Ru/PS), the catalyst 5Ru/AFPS exhibited higher catalyst performance. The achieved TOF with 5Ru/AFPS is almost 2.5 times higher than 5Ru/PS. The catalyst nanoporous structure with wide range of pores, high specific surface area and the presence of functional group on surface are considered to be responsible for observed higher catalyst performance of 5Ru/AFPS. Moreover, the effects of reaction temperature, hydrogen pressure and reaction time on conversion and selectivity of D-glucose hydrogenation were studied and the catalyst was also reused.

Full text of DOI:10.1016/j.cattod.2015.09.045

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Selective hydrogenation of D-glucose using amine functionalized
nanoporous polymer supported Ru nanoparticles based catalyst
Aasif A. Dabbawala, Dinesh K. Mishra, Jin-Soo Hwang∗
Bio-refinery Research Center, Korea Research Institute of Chemical Technology (KRICT), Yuseong, Daejeon 305-600, Republic of Korea
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 29 June 2015
Received in revised form 7 September 2015
Accepted 9 September 2015
Available online xxx
Amine functionalized nanoporous polymer (AFPS) supported Ru based catalysts were prepared by simple
impregnation-chemical reduction method, wherein Ru nanoparticles dispersed on AFPS matrix. The syn-
thesized Ru/AFPS catalysts with different Ru loading were characterized by various characterization tools
such as powder XRD, HRTEM, SEM, FTIR, TGA, CO chemisorption and XPS. The catalytic performances of
Ru/AFPS catalysts were evaluated in hydrogenation of D-glucose to produce D-sorbitol under aqueous
phase condition. The experiments results indicated that the increase of Ru content in Ru/AFPS catalyst
enhanced the formation of desire D-sorbitol and 5Ru/AFPS catalyst (having 5 wt% of Ru) showed higher
conversion and high D-sorbitol selectivity (98%). In comparison to non-functionalized polymer supported
Ru catalyst (5Ru/PS), the catalyst 5Ru/AFPS exhibited higher catalyst performance. The achieved TOF with
5Ru/AFPS is almost 2.5 times higher than 5Ru/PS. The catalyst nanoporous structure with wide range of
pores, high specific surface area and the presence of functional group on surface are considered to be
responsible for observed higher catalyst performance of 5Ru/AFPS. Moreover, the effects of reaction tem-
perature, hydrogen pressure and reaction time on conversion and selectivity of D-glucose hydrogenation
were studied and the catalyst was also reused.
Keywords:
Hydrogenation
D-glucose
Selectivity
D-sorbitol
Nanoporous amine functionalized polymer
Ru nanoparticles
© 2015 Elsevier B.V. All rights reserved.
1. Introduction
have also been studied for the hydrogenation of D-glucose [27,28].
Such Ni based catalysts showed good catalytic activity although
The renewable feedstocks such as cellulosic biomass are con-
sidered as promising alternative to petroleum feedstock and their
catalytic conversion for the sustainable production of chemicals
and fuels are therefore received considerable interest in the recent
years [1–9]. In last few years, a variety of chemicals have been
derived by chemical or biological transformations of cellulosic
biomass and biomass derived carbohydrates [1–15]. D-sorbitol, a
popular C6 sugar alcohol, could be derived from the hydrogena-
tion of D-glucose (C6 carbohydrate) or directly from cellulose by
hydrolysis-hydrogenation [12–15]. D-sorbitol is classified as one
of the top ten versatile bio-based platform molecule having signifi-
cant applications in foods, pharmaceutical and cosmetics as well
as in the synthesis L-ascorbic acid (vitamin C) [15–20]. Also, it
could be further transformed into a series of industrially important
chemicals and polymer precursors such as isosorbide, glycols, etc.
[21,14,22–24]. D-sorbitol is conventionally produced by catalytic
hydrogenation of D-glucose using Raney Nickel catalyst [25,26].
Due to the low cost of Ni, the supported nickel based catalysts
they require high H2 pressure and are less selective to D-sorbitol.
In addition, the requirement of special care for Raney Ni handling,
leaching of Ni, and ease deactivation of catalysts are important
issues with Ni based catalysts [29,30]. Considering the present
demand of D-sorbitol, it is desired to increase the selective produc-
tion of D-sorbitol. To overcome the drawbacks of Ni based catalysts,
the research in this field has been directed to develop the catalysts
based on other active metals such as cobalt, palladium, rhodium
and ruthenium, etc. [30–34]. Amongst the studied metal catalysts,
the supported Ru catalysts were found highly active and selective
than Raney Ni catalyst. Ru based catalysts operated at comparative
lower H2 pressure, did not show leaching and are less sensitive to
deactivation as well as recyclable. Therefore, Ru based catalysts are
suggested as capable to replace conventional nickel catalysts for
the hydrogenation of D-glucose to D-sorbitol [18,19,30,34]. It has
also been observed that the ruthenium loaded on different supports
such as activated carbon [34], Al2O3 [30,35], MCM-41 [36], TiO2 and
NiO-modified TiO2 [37] have different catalytic performance and
their activity/selectivity were varied depending on support mate-
rial used. On the other side, the Ru–B amorphous alloy catalyst has
also shown to be effective catalyst in liquid phase hydrogenation
of D-glucose [38,39]. However, the most of reports on D-Glucose
∗
Corresponding author. Tel.: +82 42 860 7382; fax: +82 42 860 7676.
E-mail address: jshwang@krict.re.kr (J.-S. Hwang).
http://dx.doi.org/10.1016/j.cattod.2015.09.045
0920-5861/© 2015 Elsevier B.V. All rights reserved.
Please cite this article in press as: A.A. Dabbawala, et al., Selective hydrogenation of D-glucose using amine functionalized nanoporous
polymer supported Ru nanoparticles based catalyst, Catal. Today (2015), http://dx.doi.org/10.1016/j.cattod.2015.09.045

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hydrogenation highlighted the influence of inorganic supports as
such or their modified forms in combination with Ru metal. The
utilization of porous polymeric support to stabilized Ru nanopar-
ticles and its application in D-glucose hydrogenation is limited in
literature [40].
The porous hypercross-linked polystyrene polymers are avail-
able commercially with different organic functionality which
possess good mechanical, thermal and chemical stability and
their applications in the field of adsorptions and catalysis
have greatly been highlighted [40–45]. Particularly, the uses
non-coordinating tertiary amine moieties (1.0–1.5 mmol N/g), non-
functionalized poly(styrene-co-divinylbenzene), 2% cross linked
polymer (PS), D-glucose, D-mannitol, D-fructose, D-sorbitol,
sodium borohydride (NaBH4) and ethanol were purchased from
M/s Sigma–Aldrich Chemicals, USA. De-ionized water is used as a
solvent. All the chemicals were used as such without further purifi-
cation. Hydrogen and nitrogen gases (99.9%) were purchased from
Deokyang Co. Ltd., Korea.
2.2. Catalyst preparation
of functionalized porous polymers as catalyst or as
a host
to stabilized metal/metal nanoparticles have been increased in
various organic transformations due their high specific sur-
face area, porosity and dual hydrophilic–hydrophobic character
[45–50]. The functionalized moieties in polymer enhance the
dispersion of metal and porous structures allow better diffu-
sion of reactants into the pores and facilitate interactions with
metal sites. Herein, we selected nanoporous hypercross-linked
polystyrene/divinylbenzene copolymer bearing non-coordinating
tertiary amine moieties (AFPS) and synthesized supported Ru cata-
lysts (Ru/AFPS) by impregnation and chemical reduction method
wherein ruthenium nanoparticles are dispersed on AFPS poly-
mer matrix. The AFPS polymer supported Ru nanoparticles based
catalysts were characterized using different techniques such as X-
ray powder diffraction (XRD), transmission electron microscopy
(TEM), scanning electron microscope (SEM), Fourier transform
infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), CO
chemisorptions and X-ray photoelectron spectroscopy (XPS). The
catalytic activity of synthesized Ru/AFPS catalysts was assessed first
time in the selective hydrogenation D-glucose to D-sorbitol under
aqueous phase reaction condition. The Ru nanoparticles are sta-
bilized and dispersed on AFPS matrix enhanced the formation of
desired product D-sorbitol. The various reaction parameters were
optimized in order to achieve maximum conversion of and selectiv-
ity. The catalyst Ru/AFPS could also be recycled without significant
loss in catalytic activity and selectivity.
AFPS supported ruthenium nanoparticles catalyst was prepared
by simple impregnation-chemical reduction method as reported in
the literatures [10,11]. Beads of poly(styrene-co-divinylbenzene)
amine functionalized (PSN) polymer were crushed (by ball milling)
until the fine powders were formed and then sieved to 200–300
mesh before use. To incorporate Ru (1.0% by weight) on AFPS sup-
port, 1.0 g of AFPS and RuCl3·3H2O (26 mg) were placed together
with 10 mL ethanol in a round bottom flask and attached with water
condenser and nitrogen inlet. The resulting mixture was refluxed
for a period of 12 h under an N2 atmosphere. After reflux, the reac-
tion mixture was cooled to room temperature. The Ru impregnated
AFPS was then reduced by chemical reduction method. For reduc-
tion, 0.2 M solution of NaBH4 in ethanol was added drop wise to
reaction mixture with constant stirring and entire reaction mass
was stirred (500 rpm) under N2 atmosphere for 6 h at room tem-
perature. Ru (III) was reduced and the Ru (0) nanoclusters were
formed which were stabilized by AFPS polymer matrix. Finally, cat-
alyst was separated by filtration, washed with ethanol and dried to
give dark gray AFPS supported ruthenium catalyst, 1Ru/AFPS (as
shown in Scheme 1). The catalysts having different Ru contents
such as 2Ru/AFPS, 3Ru/AFPS and 5Ru/AFPS were also prepared sim-
ilar to above described method by varying RuCl3·3H2O amount.
In the entire paper, 1Ru/AFPS, 2Ru/AFPS, 3Ru/AFPS and 5Ru/AFPS
correspond to 1, 2, 3 and 5 wt% of ruthenium content. For compari-
son purpose, 5Ru/SiO2, 5Ru/TiO2 and 5Ru/Al2O3 catalysts were also
synthesized similar to above mentioned method.
2. Experimental
2.3. Catalyst characterization and product analysis
2.1. Materials
The powder XRD of catalyst samples were carried out using
an X-ray diffractometer (MO3X-HF, Model No. 1031, CuK␣ radi-
ation). Surface area measurements of catalysts were carried out
using a surface area and porosity analyzer (Micromeritics, Tristar II
Ruthenium trichloride (RuCl3·3H2O) was purchased from
Strem Chemicals, USA. Beads (d: 300–800 ␮m) of function-
alized poly(styrene-co-divinylbenzene) polymer (AFPS) bearing
Scheme 1. Preparation of AFPS supported ruthenium nanoparticles based catalysts with different Ru contents.
Please cite this article in press as: A.A. Dabbawala, et al., Selective hydrogenation of D-glucose using amine functionalized nanoporous
polymer supported Ru nanoparticles based catalyst, Catal. Today (2015), http://dx.doi.org/10.1016/j.cattod.2015.09.045

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Table 1
3
3020). For each measurement, the sample was degassed at 150 ◦C
for 4 h under vacuum prior to N2 adsorption measurements. The
specific surface areas, pore diameters, and pore volumes of cata-
lyst samples were determined from nitrogen adsorption isotherms
measured at –196 ◦C as per Brunauer, Emmett, Teller (BET) method.
The metal contents (amount of Ru loading) of the catalysts were
determined by using EDX, Quantax 200 Energy Dispersive X-ray
Spectrometer, Bruker and by an inductively coupled plasma-atomic
emission spectrometry (Thermo Scientific ICAP 6500 duo). The
surface morphology and Ru particle size were analyzed by a trans-
mission electron microscope (Tecnai G2 Retrofit) and SEM (XL30S,
Philips, Eindhoven, The Netherlands). For the electron microscopy
examination, the catalyst samples were ultrasonically dispersed in
ethanol and then deposited on carbon-coated copper grids using
capillary and dried in air for 30 min. The oxidation state of Ru on
the catalyst was analyzed by X-ray photoelectron spectroscopy
(XPS, Escalab MK II spectrometer) using an Al X-ray excitation
source (K␣ = 1487.6 eV). CO chemisorption was carried out by
using an instrument model ASAP 2020C V1.09 G. The FTIR spec-
tra were recorded over the range from 400 to 4000 cm−1 on a Jasco
FT/IR-4100. Elemental analyses of the catalysts were done by an
elemental analyzer (Thermo Fisher, Flash-2000) with a TCD detec-
tor. Thermogravimetric analyses (TGA) were performed using TA
instrument model, TGA Q500 V6.7 with heating rate of 10 ◦C/min
in N2 atmosphere.
Textural Properties of support and Ru catalysts.
a
b
c
Catalyst
SABET (m2/g)
PDavg (nm)
PVtotal (cm3/g)
AFPS
1062
1047
1021
1001
961
3.64
3.50
3.25
3.17
3.14
19.9
18.8
0.89
0.85
0.83
0.80
0.76
0.008
0.006
1Ru/AFPS
2Ru/AFPS
3Ru/AFPS
5Ru/AFPS
PS
1.78
1.54
5Ru/PS
a
Surface area (BET).
Average pore diameter (BJH).
Total pore volume.
b
c
3. Results and discussion
The synthesized AFPS supported Ru catalysts (Ru/AFPS) were
characterized by different methods and obtained results are inter-
preted. The hydrogenation of D-glucose was performed in liquid
phase using Ru/AFPS catalysts. The effect of stirring rate, metal
loading, reaction temperature, hydrogen partial pressure, reaction
time and reusability of the catalysts were studied systematically in
details. The results obtained from these studies are presented and
discussed below.
3.1. Characterization of the catalyst
2.4. General procedure for the catalytic hydrogenation of
D-glucose
The BET-surface area, pore size and pore volume of AFPS support
and Ru/AFPS catalysts are listed in Table 1 with non-functionalized
polymeric support (PS) and its Ru catalyst (5Ru/PS). As such AFPS
support showed high BET surface area (1062 m2/g) and pore vol-
ume (0.89 cm3/g) with average pore diameter 3.64 nm. The BET
surface area, pore volume and average pore diameter of Ru/AFPS
catalysts were varied depending on Ru loading and were decreased
to some extent with an increase of Ru contents. The decrease in BET
surface area and pore volume of Ru catalysts is probably due to the
deposition of Ru on the AFPS matrix and thereby occupied some
pores by ruthenium at higher Ru loading. However, all Ru/AFPS
catalyst showed high surface area (1047–961 m2/g), pore volume
(0.83–0.76 cm3/g) and average pore diameter >3 nm.
The nitrogen adsorption–desorption isotherm and the cor-
responding pore size distribution curve for AFPS support and
5Ru/AFPS catalyst are shown in Fig. 1. According to Fig. 1a, the N2
adsorption–desorption isotherm of support and catalyst showed
a combination of type I and IV curve with a slight hysteresis in
the desorption branch. This can be attributed to the swelling of the
The experiments of D-glucose hydrogenations were carried
out in 100 mL of batch reactor in the temperature range from
80 to 110 ◦C at hydrogen pressure (3.5–6.0 MPa) by various stir-
ring rate (500–1100 rpm). The reactor was charged with D-glucose
(2 g, 11.1 mmol), water (48 g) and catalyst (0.1 g). The reactor was
flushed with H2 three times at room temperature and then reactor
was brought to desire reaction temperature and pressurized with
H2 at desired pressure. The reaction was initiated by stirring and
constant H2 pressure of reactor was maintained by supplying the
hydrogen during the reaction. During hydrogenation, the samples
were withdrawn via sampling valve from the reactor at different
time of intervals and the reaction products were analyzed by using
a HPLC (Younglin Instrument, Acme 9000) equipped with refrac-
tive index (RI) detector and Sugar-Pak column. Deionized water
was used as an eluent for the analysis at a flow rate of 0.4 mL/min
at 70 ◦C.
Fig. 1. N2 adsorption–desorption isotherms (a) and pore size distributions of AFPS and 5Ru/AFPS catalyst (b).
Please cite this article in press as: A.A. Dabbawala, et al., Selective hydrogenation of D-glucose using amine functionalized nanoporous
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CO chemisorption were 24 and 87.8%, respectively. TEM analysis
1600
1400
1200
1000
800
600
400
200
0
also provides the information related to Ru nanoparticles particles
size. From the given area of TEM image, the ruthenium particles
size distribution has been also estimated by the measurement of
ruthenium particles and is presented in Fig. 4d. It indicated that Ru
nanoparticles are very small in the range of 1.5–2.75 nm with aver-
age particle size around 2.0 nm. The TEM–EDX analysis showed the
presence of Ru, C and N in 5Ru/AFPS catalyst (SFig. 2). Ruthenium
content in the 5Ru/AFPS catalyst was also determined by TEM–EDX
analysis and was found 4.9%, a little less than experimental Ru
loading.
5Ru/AFPS
3Ru/AFPS
2Ru/AFPS
1Ru/AFPS
AFPS
FTIR-spectra of AFPS support and corresponding Ru catalysts
are shown in Fig. 5. The FTIR spectra of APFS support showed the
characteristic absorbance peaks of hypercrosslinked polystyrene
moiety functionalized with amine and matched well with reported
spectra [42,43]. The characteristic absorption bands at 3432 cm−1
,
10
20
30
40
50
60
70
80
3015 cm−1 and 2920 cm−1 are assigned to the stretch vibration of
hydroxyl group (from adsorb water), aromatic C–H and aliphatic
C–H in AFPS respectively. The absorbance peaks at 1600 cm−1 and
1450 cm−1 are ascribed for the vibration of C–C aromatic ring [42].
The absorption bands at 1652 and 1219 cm−1 are due to N–H bend-
ing and (C–N) stretching vibration respectively. FTIR spectra of Ru
catalysts were almost identical to the corresponding AFPS support
indicating further the preservation of polymer skeleton structure.
However, it can be seen that peak intensity of amine and C–N
stretching changed in the case of Ru catalysts suggesting the sta-
bilization of the Ru nanoparticles in the AFPS matrix through the
amine groups.
2θ
degree)
Fig. 2. XRD patterns of AFPS support and Ru/AFPS catalysts.
polystyrene matrix [43]. The nitrogen isotherms also gave informa-
tion related to pore structure of these samples: (i) the high uptake at
low pressures (P/Po < 0.1) indicated the presence of micropores, (ii)
the gradual increase in the region 0.1 < P/Po < 0.9 can be attributed
to the presence of mesopores and (iii) the steep increase at high
pressures (P/Po > 0.9) can be attributed to macroporosity. Over-
all, the porous polymer AFPS and Ru catalyst have wide range of
nanopores (from micro to macropores) which was reflected in the
pore size distribution (Fig. 1b).
To determine state of Ru in Ru/AFPS catalyst, the XPS analy-
sis was performed. In Fig. 6, XPS spectra of 1Ru/AFPS catalyst are
shown for Ru 3d and 3p region. The XPS spectrum of 1Ru/AFPS in
3d region showed two major peaks at binding energies of 280.3 eV
and 284.4 eV. The characteristic binding energy peaks of Ru 3d3/2
and Ru 3d5/2 energy levels are generally observed at 284.1 and
280.0 eV for metallic ruthenium [51,52]. Th observed main peak
in XPS spectrum of catalyst at 284.4 eV which could be assigned
due to Ru 3d3/2 in 1Ru/AFPS which was overlapped with C 1s of the
carbon atoms of the polymeric network. The weak peak at 280.3 eV
could be assigned due to Ru 3d5/2 photoelectron line. XPS analy-
sis of supported metal catalyst also gives information related the
nature of functional groups presence on material surface. Gener-
ally, the additional peak at >284 eV is attributed to the presence of
carbanious functional groups (such as CO, COOH, C–O–C, etc.) on
support surface. XPS spectra of Ru@Graphene nanosheets [53] and
Pd@multi-walled carbon nanotube [54] showed peaks in the range
of 286–290 eV due the presence of C–O–C, C O, C(O)O functional
groups on support surface. Therefore, it is anticipated that the addi-
tional weak peak at around 291 eV for Ru/AFPS catalyst attributed
to the presence of carbonyl/carboxyl based functional groups on
XRD patterns of support (AFPS) and Ru/AFPS catalysts are shown
in Fig. 2. It can be seen that XRD patterns of 1Ru/AFPS, 2Ru/AFPS,
3Ru/AFPS and 5Ru/AFPS samples are identical to AFPS support. The
small hump at around 43◦ in XRD pattern of Ru/AFPS catalysts
appeared which generally arises due to the presence of Ru [36].
However, the clear sharp peak could not be seen at this value in
their enlarge view (SFig. 1) indicating higher dispersion of Ru on
polymeric matrix surface. XRD pattern of catalysts also suggested
that the nature of the AFPS supported is not significantly affected
by the method pursued for the preparation of Ru nanoparticles and
insertion.
SEM images of 5Ru/AFPS are presented in Fig. 3. It can be seen
clearly that the AFPS support has layered porous structure and the
surface morphology of catalyst is similar to its corresponding AFPS
support (Fig. 3). This suggested that the incorporation of ruthenium
did not cause any change in surface morphology of AFPS support.
The TEM views showed that ruthenium particles are well dis-
persed throughout the AFPS support (Fig. 4). This is in agreement
with the results obtained from CO chemisorption. The dispersion
of metallic ruthenium and metallic surface area determined by
Fig. 3. SEM images of 5Ru/AFPS catalyst with small inset of AFPS support.
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Fig. 4. TEM (a), HRTEM images (b,c) of 5Ru/AFPS catalyst with Ru particle size distribution (d).
AFPS surface to a small extent. The presence of carboxyl/hydroxyl
functionalities in polystyrene based polymers is also reported by
Demirocak et al. [43]. In order to get more insight about Ru metal-
lic species on catalyst surface, XPS of Ru 3p region has also been
performed. The catalyst showed two strong peaks at 462.1 eV and
484.2 eV attributed to Ru 3p3/2 and Ru 3p1/2 respectively (Fig. 6b).
The binding energy of Ru 3p3/2 of catalyst is closer to reported value
for Ru (461.2 eV, 3p3/2) [51]. Also, Sun et al. reported binding ener-
gies 462.2 eV (Ru 3p3/2) and 484.5 eV (Ru 3p1/2) for Ru supported on
carbon nanotube (CNT) catalyst [52]. These values are well matched
with Ru/AFPS catalyst indicating the formation of Ru(0) nanopar-
ticles by the reduction of RuCl3. The shifts in binding energies in
this case further imply the strong interaction between metallic Ru
and polymeric support. It is also important to check the thermal
stability of support and corresponding catalysts. TGA analysis sug-
gested that the catalysts are stable up to 300 ◦C (SFig. 3). Therefore,
AFPS could be used as support material and is sufficiently thermally
stable.
To control the formation of such side products, low temperature,
high hydrogen pressure and ruthenium catalysts are generally used
[34–40]. The selection of support is also important beyond the
active metal selection and parametric optimization for selective
production of D-sorbitol. In our present study, we focused to uti-
lize nanoporous functionalized polymeric support and synthesized
catalysts with different Ru contents. The catalytic performances of
synthesized Ru/AFPS catalysts were tested in hydrogenation of D-
glucose using water as ‘green solvent’. In liquid phase batch type
hydrogenation, D-mannitol and D-fructose were identified as the
main side products.
Firstly, we studied the effect of agitation speed on conversion
and selectivity of D-glucose hydrogenation by varying the stirring
rates (500, 700, 900, 1000 and 1100 rpm) at 100 ◦C and 5.5 MPa
H2 pressure to confirm the impact of gas liquid mass transfer
1.2
3.2. Catalytic hydrogenation of D-glucose
5Ru/PS
1.0
0.8
0.6
0.4
0.2
5Ru/AFPS
In hydrogenation of D-glucose, an aldehyde (–CH O) group
of D-glucose is reduced to give D-sorbitol as a main product
and it looks simple process. However, in solution, the D-glucose
exists in equilibrium with cyclic pyranose form. Therefore, some
side products are also formed during hydrogenation of D-glucose
(Scheme 2). D-fructose and D-mannose are formed by Lobry de
Bruyn-Alberda van Ekenstein rearrangements and thereby produce
D-mannitol via hydrogenation [30]. The other possible by product is
5-hydroxymethylfurfural which can be generated by dehydration
of D-glucose. These all by-products affect the selective production
of D-sorbitol and also responsible for the catalyst deactivation.
In this view, the complete conversion of D-glucose with selec-
tive production of D-sorbitol is a complex process. Therefore, the
present studies in this field have been mainly focused on selectiv-
ity issues and product distribution using different catalyst systems.
3Ru/AFPS
2Ru/AFPS
1Ru/AFPS
AFPS
1219
1600
1450
3015
2920
3432
3500
3000
2500
2000
1500
1000
500
Wave number (cm-1)
Fig. 5. FTIR spectra of AFPS support and Ru catalysts.
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4600
Ru3d
3/2
Ru 3p
3/2
(b)
(a)
16000
Ru 3p
1/2
4400
4200
4000
12000
8000
4000
Ru3d
280
5/2
0
300
295
290
285
500
490
480
470
460
Binding energy (eV)
Binding energy (eV)
Fig. 6. XPS spectra of 1Ru/AFPS catalyst (a) 3d region and (b) 3p region.
resistance (SFig. 4). It was observed that the hydrogenation reac-
tion proceeded slowly at low stirring rate and was diffusion limited.
The hydrogenation experiments preformed at 500 rpm gave com-
paratively low conversion as well as low D-sorbitol selectivity. In
addition, at low stirring rates, the formation of side products was
somewhat higher due to the inefficient mixing and slow diffusion of
(Table 2). Similarly, the products selectivities were also influenced
by Ru loading. The catalyst with lower Ru content favors isomeriza-
tion of D-glucose and produces higher amount of D-mannose and
D-fructose (Table 2) where as catalyst having higher Ru loading
favors the hydrogenation of D-glucose to D-sorbitol. Therefore, D-
sorbitol selectivity was enhanced with an increase of Ru contents.
The D-glucose conversion and D-sorbitol selectivity were low at
low Ru content (1%) and were improved with an increase in Ru
content (5%). These results corroborate that active metal center is
Ru as the conversion and selectivity varied with Ru contents. One
hydrogenation experiment was also carried out using as such AFPS
(without Ru) at similar reaction condition. No hydrogenation of D-
glucose can be occurred even after 4 h reaction time (Table 2, entry
1).
The 5Ru/AFPS catalyst showed higher conversion of D-glucose
(69%) with high D-sorbitol selectivity (98%). The catalytic behav-
ior of Ru based catalysts changed with support materials used. To
understand the efficiency of AFPS support, the catalytic perfor-
mance of 5Ru/AFPS was then compared with Ru catalysts of non
functionalized porous polymeric support (PS), carbon and other
inorganic metal oxide based supports. The hydrogenation exper-
iments of D-glucose were performed using Ru based catalysts with
distinct support materials by keeping similar Ru loading (5%) and
reaction conditions. For proper comparison, the catalyst activities
of all studied Ru catalysts in term of turn over frequency (TOF) were
determined. The initial TOFs were calculated at D-glucose conver-
sion in the range of 20–35%. The obtained results of all studied
Ru based catalysts are presented in Fig. 7. The results pointed out
that the catalytic behavior (catalyst activity and D-sorbitol selec-
tivity) of Ru based catalysts were changed depending on support
materials used. The formation of side products was also influenced
by the nature of support used for Ru catalyst. Ru supported on
SiO2 (5Ru/SiO2) showed initial TOF 108 h−1, however D-sorbitol
yield (37.3) and selectivity (83%) were low in reaction time of
1 h. The catalysts of 5Ru/TiO2 and 5Ru/Al2O3 exhibited compara-
tive higher catalyst performance than 5Ru/SiO2 with almost the
similar TOFs value (172 h−1 for 5Ru/TiO2, 163 h−1 for 5Ru/Al2O3).
Both the catalysts gave D-sorbitol yield up to (51–52%) with D-
sorbitol selectivity (93%). The 5Ru/C catalyst showed higher TOF
(181 h−1 than inorganic metal oxide based Ru catalysts with 95%
of D-sorbitol selectivity. Interestingly, the high D-sorbitol selectiv-
ity (98%) was achieved with porous polymeric supports (PS and
AFPS). From the results of porous polymeric Ru based catalysts
, it can be seen that the formation of side products were low com-
pared to inorganic metal oxides and carbon based catalysts (Fig. 7b).
But, D-glucose conversion and D-sorbitol yield were found to
H2 gas to liquid. The increase in stirring rates from 500 to 1000 rpm
led to enhance D-glucose conversion and D-sorbitol selectivity. This
indicated that the higher stirring rate is required for rapid diffusion
of H2 in the liquid and to achieve more desirable product D-sorbitol.
On further increasing the stirring rate from 1000 to 1100 rpm, no
significant changes in D-glucose conversion and D-sorbitol selec-
tivity were observed. Beyond an agitation speed of 1000 rpm the
D-glucose conversion was independent of stirring rate. Therefore,
the stirring rate was fixed at 1000 rpm in all hydrogenation exper-
iments in order to avoid the gas liquid mass transfer limitation.
The Ru present in Ru/AFPS catalysts is active metal center and
variation in Ru loading can alter product selectivity. The Ru con-
tents were varied from 1 to 5% in Ru/AFPS catalysts and the effect
of Ru loading was evaluated for D-glucose hydrogenation by keep-
ing temperature (100 ◦C) and H2 pressure (5.5 MPa) constant. From
the experimental results, it can be seen that the conversion of
D-glucose was found to increase with increase of Ru contents
HO
OH HO
O
HO
OH
Isomerization/
Rearrangement
D-Glucose
Rearrangement
H2
O
OH HO
HO
OH HO
HO
OH HO
O
HO
HO
HO
OH
HO
OH
HO
OH
D-Fructose
D-Mannose
D-Sorbitol
Isomerization
H2
H2
HO
OH HO
HO
HO
OH
D-Mannitol
Scheme 2. Hydrogenation of D-glucose to D-sorbitol with possible side products.
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Table 2
Hydrogenation of D-glucose using Ru/AFPS catalysts with different Ru contents.a
Entry
Catalyst
Ru (%)
Conv (GL)b (%)
Selectivity (%)
SB
MN
FR
NI
1
2
3
4
5
–
–
1
2
3
5
0
15
31
50
69
–
94
96
98
98
–
3
2
1.0
1.5
–
2
1
0.5
–
–
1
1
0.5
0.5
1Ru/AFPS
2Ru/AFPS
3Ru/AFPS
5Ru/AFPS
a
Reaction conditions: D-glucose = 11.10 mmol, catalyst = 0.1 g, water = 48 g, temp. = 100 ◦C, pH2 = 5.5 MPa, stirring rpm = 1000, reaction time = 60 min.
Conversion of D-glucose.
b
SB: D-sorbitol, MN: D-mannitol, FR: D-fructose, NI: non identified products.
depend on type of polymeric support used (functionalized and non-
functionalized) and its nanoporous structure. Non-functionalized
5Ru/PS having macroporous structure produced 38% sorbitol yield
with TOF of 95 h−1. In comparison to 5Ru/PS, 5Ru/AFPS (functional-
ized polymeric support having range of pores; micro, meso as well
as macropores) showed considerably higher catalyst performance
than 5Ru/PS as well as other metal oxides and carbon based Ru
catalysts. Notably, high initial TOF (235 h−1) and higher yield of D-
sorbitol (67.6%) were achieved using 5Ru/AFPS catalyst (Fig. 7). The
observed TOF with 5Ru/AFPS is almost 2.5 times higher than 5Ru/PS
catalyst. The achieved results with 5Ru/AFPS catalyst clearly point
out the influence of functionalized organic moieties and impor-
tance of texture properties of catalyst in enhancement of catalyst
performance. The functional amine groups present in AFPS poly-
mer surface have various role, (i) stabilize Ru nanoparticles and
enhance the dispersion of Ru nanoparticles (see CO chemisorption
data, STable 1 and TEM images of 5Ru/PS and 5Ru/AFPS, SFig. 5),
(ii) the AFPS based catalysts have better wettability compared to
Ru/PS catalyst due to the presence of hydrophilic amine functional
groups and is therefore easily mixed with water compared to Ru/PS
catalyst (SFig. 6).
In view of textural properties, the 5Ru/AFPS catalyst has high
specific surface area and porous structure with wide range of
nanopores. The presence of micro pores in AFPS catalyst is expected
to control size of Ru nanoparticles. Due to the presence of meso-
pores, the substrate molecules can easily approach to Ru active
metal center without diffusion limitation. In turn, the remarkable
catalyst activity can be realized with 5Ru/AFPS catalyst. On the
other hand, 5Ru/PS showed lower catalytic activity and produced
D-sorbitol with low yield even though it has macroporous struc-
ture. The low catalytic activity of 5Ru/PS may be ascribed to its
low surface area and organophilic character of catalyst which lim-
its the accessibility of active sites as hydrogenation of D-glucose
is performed in aqueous media. In addition, the dispersion of Ru
nanoparticles was low in the case of 5Ru/PS based catalyst due
to the absence of functionalized N containing organic groups (CO
chemisorption showed only 4% of Ru dispersion, STable 1). In order
to study effect of various parameters (like temperature, pressure
of hydrogen and reaction time) on D-glucose conversion and selec-
tivity of D-sorbitol, the hydrogenation experiments using 5Ru/AFPS
catalyst were carried out by varying these parameters.
The effect of reaction temperature on catalytic activity and
selectivity of D-glucose hydrogenation was studied by varying reac-
tion temperature in the range of 80–110 ◦C at constant H2 pressure
(5.5 MPa). Fig. 8 shows the influence of reaction temperature on
catalytic activity (TOF) and selectivity. From Fig. 8, it can be seen
that the temperature had significant effect on catalytic activity, D-
sorbitol yield and selectivity. With an increase of temperature the
hydrogenation of D-glucose proceeded faster and led to improve
TOF and D-sorbitol yield. The initial TOF for D-glucose was 95 h−1
at lower reaction temperature (80 ◦C). An increase of temperature
from 80 to 110 ◦C, the initial TOF was increased considerably from
95 to 308 h−1 indicating catalyst activity increased by a factor of ∼3.
Similarly, the yield of D-sorbitol was low (34.6%) in 60 min at lower
temperature (80 ◦C) but escalated significantly up to 76.8% with an
increase of reaction temperature. However, at high reaction tem-
perature (110 ◦C), it was observed that the D-sorbitol selectivity
was decreased (from 98 to 96%) due to the formations of side prod-
ucts. Therefore, the optimum reaction temperature was selected as
100 ◦C for further study.
The influence of hydrogen pressure on D-glucose hydrogena-
tion was studied at 100 ◦C under different hydrogen pressure
Fig. 7. Catalytic performance of distinct Ru catalysts in hydrogenation of D-glucose; (a) TOF calculated at 20–35% conversion of D-glucose, (b) yield and selectivity of D-sorbitol
for reaction time of 1 h; D-glucose = 11.10 mmol, catalyst = 0.1 g, water = 48 g, temp. = 100 ◦C, pH2 = 5.5 MPa, stirring rpm = 1000.
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Yield SB(%)
Selec. SB (%)
100
80
60
40
20
0
300
(b)
(a)
250
200
150
100
50
0
80
85
90
95
Temp. (
100
105
110
80
85
90
95
100
105
110
°C)
Temp. ( C)
°
Fig. 8. Effect of reaction temperature on D-glucose hydrogenation using 5Ru/AFPS catalyst (a) TOF, (b) yield and selectivity of D-sorbitol; D-glucose = 11.10 mmol, cata-
lyst = 0.1 g, water = 48 g, pH2 = 5.5 MPa, stirring rpm = 1000.
(3.5–6.0 MPa). The effect of the hydrogen pressure on conversion
and selectivity of D-glucose hydrogenation is presented in Fig. 9.
The reaction rate (in term of TOF) of D-glucose hydrogenation
was low at lower hydrogen pressure due to low concentration
of dissolved hydrogen. The initial TOF was found to increase lin-
early on increasing the partial pressure of hydrogen (Fig. 9a). At
1.0 MPa hydrogen pressure, the TOF for D-glucose was observed
117 h−1 that increased considerably up to 263 h−1 with an increase
of hydrogen pressure from 3.5 to 6.0 MPa. In parallel, the increase
of H2 pressure, the yield of D-sorbitol was increased from 42
to 73%. However, in all instances, high selectivity to D-sorbitol
was obtained and was slightly affected (97–98%). Generally,
the increase in the partial pressure of hydrogen increases the
dissociation of hydrogen on the metal center as a result the
concentration of hydrogen available for hydrogenation increases.
Hence, at higher partial pressure of hydrogen, the adsorption and
desorption of hydrogen on the metal surface is higher, which
increases the conversion of D-glucose and product formation in
less reaction time. Hoffer as well as Crezee et al. also observed
first order dependency with respected hydrogen pressure in D-
glucose hydrogenation using Raney Ni and Ru/C based catalysts
[26,34].
As mentioned above, the catalyst activity and selectivity of D-
glucose hydrogenation using 5Ru/AFPS catalyst were influenced
by temperature and H2 pressure. The effect of reaction time was
also studied for D-glucose hydrogenation under optimum reaction
conditions (100 ◦C and 5.5 MPa H2 pressure). The reaction profile
for conversion of D-glucose and selective formation of D-sorbitol
is presented with respect to time in Fig. 10. In 30 min, 48% con-
version of D-glucose was observed. The conversion of D-glucose
was reached 86% in 90 min then the reaction became sluggish.
The complete conversion of D-glucose was attained in 120 min.
The catalytic hydrogenation of D-glucose yielded mainly D-sorbitol.
Interestingly, the selectivity of D-sorbitol was maintained through-
out the reaction and was slightly affected. However, small amount
of D-mannitol and D-fructose were observed up to 2%. On further
increase of reaction time, the yield of was not changed significantly.
In order to determine heterogeneous character of 5Ru/AFPS catalyst
by leaching test, one reaction was performed in which hydrogena-
tion of D-glucose was stopped after 60 min at D-glucose conversion
of 69%. Then, the catalyst was removed by filtration and the reac-
tion was allowed to proceed at 100 ◦C and 5.5 MPa H2 pressure for
further 2 h without presence of Ru catalyst. No further conversion
of D-glucose into D-sorbitol was observed. Moreover, Ru could not
Yield SB (%)
Selec. SB (%)
280
100
80
60
40
20
0
240
(b)
(a)
200
160
120
80
3.5
4.0
4.5
5.0
5.5
6.0
3.5
4.0
4.5
5.0
5.5
6.0
Pressure (H2), MPa
Pressure (H2), MPa
Fig. 9. Influence of hydrogen pressure on D-glucose hydrogenation using 5Ru/AFPS catalyst (a) TOF, (b) yield and selectivity of D-sorbitol; D-glucose = 11.10 mmol, cata-
lyst = 0.1 g, water = 48 g, temp. = 100 ◦C, stirring rpm = 1000.
Please cite this article in press as: A.A. Dabbawala, et al., Selective hydrogenation of D-glucose using amine functionalized nanoporous
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Fig. 10. Reaction profile for conversion of D-glucose and formation of D-sorbitol (a), catalyst re-use experiments (b); D-glucose = 11.10 mmol, catalyst = 0.1 g, water = 48 g,
temp. = 100 ◦C, pH2 = 5.5 MPa, stirring rpm = 1000.
be detected in reaction solution by ICP analysis. This indicated that
Ru was not leached from catalyst and the catalytic action of Ru/AFPS
catalyst was heterogeneous type.
the liquid phase. The newly generated active H can convert another
molecule of D-glucose and hydrogenation cycle can go on.
The reusability of the 5Ru/AFPS catalyst for D-glucose hydro-
genation was also studied under the optimized reaction conditions
and the results are presented in Fig. 10b. For catalyst reusability
tests, the catalyst was filtered from the reaction mixture after
reaction, washed thoroughly with water and dried. The recovered
catalyst was used for next hydrogenation run under similar reac-
tion conditions. No significant loss in D-glucose conversion and
D-sorbitol selectivity were observed up to five cycles (Fig. 10b). This
suggested the catalyst is reusable up to five cycles under employed
reaction conditions as Ru was not leached into reaction mixture.
Moreover, the recycled catalyst was characterized by FTIR and TEM
to study structural and morphological change in catalyst (Fig. 11).
The FTIR spectra of used catalysts almost similar to fresh catalyst,
however, some additional small peaks were observed which may
be due to the adsorption of substrate or/and product molecules.
From TEM images of fresh and re-used catalyst (after five run), it
could be seen that the morphology of the catalyst was not changed
considerably. The little aggregation of Ru nanoparticles could be
observed which might be responsible for slight decrease in catalyst
The hydrogenation of D-glucose to D-sorbitol using AFPS sup-
ported Ru catalyst is three phase (gas–liquid–solid) catalytic
reaction. It is realized that Ru loaded on mesoporous polymeric
support could adsorb H2 with higher quantity than metal itself
by hydrogen spillover [43]. In this view, the progress of D-glucose
hydrogenation can possibly be explained by pathways of H2 dif-
fusion, generation of activated H (H-Ru) and reaction of D-glucose
with activated H on catalyst surface. The possible mechanism is also
outlined for D-glucose hydrogenation using Ru/AFPS catalyst and is
presented in Scheme 3. In hydrogenation of D-glucose to D-sorbitol,
the hydrogen is spread first from air to liquid and is dissolved in the
gas–liquid interface. The dissolved hydrogen in liquid phase is then
spillover on the catalyst surface where activated H is generated by
the active metal (Ru) centers of the catalyst. The carbonyl group
in D-glucose reacts with the activated H and Ru to produce cyclic
transition structure. The hydrogen transfer is then occurred and
further addition of H2 produces active H and product D-sorbitol.
The product D-sorbitol desorbs from the catalyst and diffuses into
D-Glucose
OH
HO
HO
OH
H
H
H
D-Sorbitol
+
HO
OH
HO
O
OH
HO
OH
OH
HO
HO
OH
HO
HO
H
H
OH
H
O
H
H transfer
H
H
H
H
OH
H
O
O
H
H
H
H
O
H
H
H
O
H
H
Ru
Ru
Ru
Ru
Ru
Ru
Ru@AFPS
Ru@AFPS
Ru@AFPS
Scheme 3. Proposed reaction mechanism for D-glucose hydrogenation to D-sorbitol using 5Ru/AFPS catalyst.
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Fig. 11. FTIR spectra (a) and TEM image of used catalyst after fifth run.
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Please cite this article in press as: A.A. Dabbawala, et al., Selective hydrogenation of D-glucose using amine functionalized nanoporous
polymer supported Ru nanoparticles based catalyst, Catal. Today (2015), http://dx.doi.org/10.1016/j.cattod.2015.09.045