Catalytic glycosylation of glucose with alkyl alcohols over sulfonated mesoporous carbons

Article abstract of DOI:10.1016/j.mcat.2019.02.016

Herein we investigated the catalytic performances of sulfonated mesoporous carbons in the glycosylation of carbohydrates with alkyl alcohols. Catalytic performances were compared to common solid acid catalysts previously reported for this reaction. Under optimized conditions, the targeted alkyl glycosides were obtained in 85% yield, together with a turn over frequency and a space time yield higher than those of the best heterogeneous catalysts reported so far in such reaction. Furthermore, the presence of mesoporous channels significantly lowered the deactivation rate of the catalyst in comparison to a non-porous sulfonated carbon.

Full text of DOI:10.1016/j.mcat.2019.02.016

MolecularCatalysis468(2019)125–129
Contents lists available at ScienceDirect
Molecular Catalysis
journal homepage: www.elsevier.com/locate/mcat
Catalytic glycosylation of glucose with alkyl alcohols over sulfonated
mesoporous carbons
Wahiba Ghezali Ramdania, Ayman Karama, Karine De Oliveira Vigiera, Sébastien Riob,
Anne Ponchelb,⁎, François Jérômea,⁎
a Institut de Chimie des Milieux et Matériaux de Poitiers, CNRS/Université de Poitiers, 1 rue Marcel Doré, ENSIP Bat B1, 86073, Poitiers, France
b Univ. Artois, CNRS, Centrale Lille, ENSCL, Univ. Lille, UMR 8181, Unité de Catalyse et de Chimie du Solide (UCCS), F-62300, Lens, France
A R T I C L E I N F O
A B S T R A C T
Keywords:
Biomass
Catalysis
Carbohydrates
Glycosylation
Mesoporous carbon
Herein we investigated the catalytic performances of sulfonated mesoporous carbons in the glycosylation of
carbohydrates with alkyl alcohols. Catalytic performances were compared to common solid acid catalysts pre-
viously reported for this reaction. Under optimized conditions, the targeted alkyl glycosides were obtained in
85% yield, together with a turn over frequency and a space time yield higher than those of the best hetero-
geneous catalysts reported so far in such reaction. Furthermore, the presence of mesoporous channels sig-
nificantly lowered the deactivation rate of the catalyst in comparison to a non-porous sulfonated carbon.
1. Introduction
options to decrease the production cost of AAG. In particular, the re-
placement of H2SO4 by robust, active and recyclable solid acid catalysts
With the exponential growth of the world population, and our
concerns about climate changing, the chemical industry needs to pro-
duce always more and better from resources that are declining or be-
coming less and less accessible. In this context, carbohydrates represent
a huge reservoir of renewable carbon from which a myriad of chemicals
can be theoretically produced [1–11]. The implementation of sugar-
based processes on a large scale is far from being an easy task and it
requires scientists to overcome scientific and technological bottlenecks.
For instance, carbohydrates tend to form tar-like materials, also com-
monly named humins, which not only decreases the overall selectivity
of the catalytic process but also leads to a severe deactivation of solid
catalysts [12–13]. As a consequence, the space time yield of sugar-
based processes are often too low to be competitive with petrochemical
processes, for which chemistry has developed very efficient technolo-
gies over more than 70 years.
The catalytic Fischer glycosylation of glucose with fatty alcohols is
one of the important sugar-based reactions deployed at an industrial
scale [14–21]. This reaction is catalyzed by sulfuric acid and yields
amphiphilic alkyl glycosides (AAG) that are valuable biosurfactants,
with current applications in the cosmetic and detergence industries.
The price of AAG is about 1.5–2 €/kg, which is still too high to compete
with fossil derived surfactants exhibiting similar performances. Opti-
mization of the catalytic Fisher glycosylation reaction is one of the
is a possible strategy. Beside the intrinsic catalytic performances of solid
acids, the absence of neutralization step at the end of the reaction and
the easiness in recovery/recycling of solid catalysts represent additional
advantages over H2SO4.
From the view point of catalysis, the direct glycosylation of un-
protected carbohydrates with fatty alcohols is a difficult reaction. In
particular, improving the catalyst activity is essential in order to assure
that the glycosylation rate of carbohydrates is higher than their thermal
degradation rate to humins, as above mentioned these tar-like materials
leading to a rapid deactivation of catalysts. In the field of hetero-
geneous catalysis, this reaction is even more complex to kinetically
control because carbohydrates and fatty alcohols are bulky substrates,
which restrict to some extent, their accessibility to the grafted or an-
chored catalytic sites, thus reducing the catalyst activity.
With these criteria in mind, microporous catalysts and gel-type re-
sins were previously reported. Two catalytic strategies can be dis-
tinguished in the current literature. The first option consists in syn-
thesizing AAG by the direct catalytic Fischer glycosylation of glucose
with fatty alcohols under biphasic conditions. In this case, zeolite H-
BEA (Si/Al = 25) [22], ZnFe2O4 supported on ZrO2 [23], H2SO4/SiO2
[24,25], polyvinyl bound tri- and disulfonate ethylamine chloride[26]
and Aquivion PFSA [27] have been previously investigated and good to
excellent yields were claimed. Cellulose, and even lignocellulosic
Abbreviations: AAG, amphiphilic alkyl glycosides; PFSA, perfluorinated sulfonic acid; TOF, turn over frequency; TON, turn over number
⁎ Corresponding authors.
E-mail addresses: anne.ponchel@univ-artois.fr (A. Ponchel), francois.jerome@univ-poitiers.fr (F. Jérôme).
https://doi.org/10.1016/j.mcat.2019.02.016
Received 3 December 2018; Received in revised form 14 February 2019; Accepted 15 February 2019
2468-8231/©2019PublishedbyElsevierB.V.

W.G. Ramdani, et al.
MolecularCatalysis468(2019)125–129
biomass, were also successfully employed as a source of glucose in the
synthesis of AAGs through glycosylation reaction [28]. In order to
overcome the low miscibility of carbohydrates with fatty alcohols, a
second strategy was explored in the literature. It consists in the trans-
glycosylation of pre-synthesized methyl- or butylglycosides with fatty
alcohols. Catalysts of the type Amberlyst-15, Nafion SAC-13, zeolite
ITQ-2, sulfonated carbons, sulfonated graphene oxides and hetero-
polyacids were typically used in such approach [28d,29]. Even though
the catalytic transglycosylation of methyl/butylglycosides with fatty
alcohols generally led to catalytic reactions with higher space time
yields than the direct glycosylation of glucose with fatty alcohols, it has
however the main drawback of requiring an extra synthetic step. One
should however mention that, in some cases, the glycosylation and
transglycosylation reactions were advantageously combined in a suc-
cessive way in a single reactor, thus avoiding intermediate purification
[28d].
In all these examples, the catalyst activity is depending on (i) the
strength of acid sites (Bronsted or Lewis) and (ii) the accessibility of
acid sites, which is often improved by the presence of micropores or by
the ability of catalysts to swell into the reaction media. The release of
water as a co-product and the formation of tar-like materials impact, to
a more or less extent, the long term stability of catalyst (catalyst coking,
surface hydrolysis, etc.). Whatever the catalytic routes (glycosylation vs
transglycosylation), good results were generally claimed in terms of
yield and selectivity but the stability, the recyclability and the space
time yields of these solid catalysts needs to be further improved to be
more competitive with H2SO4, the reference catalyst used at the in-
dustrial scale for such reaction [14].
In the field of heterogeneous catalysis applied to biomass, carbon-
based catalysts are attracting growing interest [30–39]. The improved
stability of carbon materials in the presence of water (common co-
product or solvent in carbohydrate chemistry), their ease of surface
functionalization, the possibility to tune their surface polarity and
prepare them at a nanoscale represent important features which were
previously taken as advantages in the catalytic conversion of carbohy-
drates [40–41]. From all these data, it occurred to us that sulfonated
mesoporous carbons could be promising catalysts for the direct cata-
lytic glycosylation of glucose with fatty alcohols, the presence of me-
sopores being expected to dramatically facilitate the diffusion of car-
bohydrates within the catalyst backbone while the carbonaceous
skeleton should confer to the catalyst a greater stability in the presence
of water than metal oxides for instance. As recently reviewed by
Doustkhah et al., sulfonated carbons have been used as solid acid cat-
alysts in a wide range of reactions such as acetalization, CeC bond
couplings, Fries and Beckman rearrangement, etc [42]. To the best of
our knowledge, the catalytic activity of sulfonated mesoporous carbons
has never been reported in the direct Fisher glycosylation of carbohy-
drates with fatty alcohols, although this family of catalyst gathers the
main criteria to be efficient in such reaction. Mesoporous carbons are
typically prepared by the so-called hard-templating synthesis. The
mesoporous carbons are thus the negative replica of an inorganic hard
template used as mold. Typically, cubically mesoporous MCM-48
aluminosilicate or mesoporous silica such as 3D cubic cage-like SBA-1
and 2D hexagonal SBA-15 were used as an inorganic template and af-
ford mesoporous carbons referred as CMK-1, CMK-2 and CMK-3, re-
spectively [43,44]. Then, these mesoporous carbons can be sulfonated
according to different strategies, including sultone, sulfuric acid, etc
[42].
In this communication, we thus investigate the catalytic perfor-
mances of various sulfonated mesoporous carbons in the direct glyco-
sylation of glucose with n-dodecanol. Sulfonated mesoporous carbons
were then benchmarked to previously reported solid acid catalysts, and
also from various carbohydrates and alkyl alcohols, to assess their po-
tential but also their limitations.
2. Experimental section
In a typical procedure, glucose (1.0 g, 5.5 mmol) was mixed with n-
dodecanol (10 g, 53 mmol) in a 50 mL round-bottom flask, equipped
with a magnetic stirring bar. Then, an acid catalyst (1.8 mol % of
-SO3H) was added and the solution was heated in an oil bath at 393 K
under vacuum (15 mmHg) for the desired reaction time. The reaction
was monitored by gas chromatography on a Varian 3900 instrument
equipped with
a flame ionization detector and an HT5 column
(30 m x 0.32 mm x 0.25 μm). Before analysis, AAGs were silylated as
described in the supporting information. After complete conversion of
glucose, the catalyst was filtered off ; and the excess n-dodecanol was
removed under vacuum. For recycling experiments, the solid acid cat-
alyst was recovered by filtration at the end of the reaction, washed with
ethanol, dried in an oven at 60 °C and then re-used as is without any
further purification. 1H and 13C NMR spectra of the as-obtained AAGs
are provided in Figures S13 and S14.
3. Results and discussion
Sulfonated mesoporous carbons were prepared through a nano-
casting method adapted from the procedures of Ryoo [43] and Wu [44].
Briefly, the experimental protocol involves (i) the preparation of a
mesoporous SBA-15 mold, (ii) the impregnation/infiltration of the sa-
crificial SBA-15 with an aqueous solution of sucrose containing sulfuric
acid, (iii) a thermo-polymerization reaction at 373 K and 433 K fol-
lowed by a pyrolysis under N2 at a controlled temperature and (iv) the
removal of the SBA-15 mold by treatment with 1 M NaOH in a mixture
H2O/ethanol (1/1). According to the temperature of pyrolysis, different
CMK-3 samples were obtained and referred as CMK-3-T, with T being
the pyrolysis temperature (723, 823, 923, 1073 and 1173 K). The as-
obtained CMK-3-T mesoporous carbons was then sulfonated by reaction
with ClSO3H/H2SO4 at 353 K for 20 h affording the CMK-3-T-SO3H
catalyst. To assess the utility of mesopores in the catalytic experiments,
an amorphous carbon, named AC-723-SO3H, was prepared in the same
way as CMK-3-723-SO3H, but without using SBA-15 as hard-template.
Detailed experimental procedures and full characterization have been
placed in the supporting information (Table S1 and figure S1-S10). The
textural properties determined by N2 adsorption-desorption and proton
Table 1
Characterization of carbon-based materials.
Catalyst
-SO3H (mmol/g)[a]
BET[b] (m2/g)
Pore diameter (nm)[c]
Pore volume (cm3/g)[d]
Mesopore volume (cm3/g)[c]
CMK-3-723-SO3H
CMK-3-823-SO3H
CMK-3-923-SO3H
CMK-3-1073-SO3H
CMK-3-1173-SO3H
AC-723-SO3H
0.64
0.38
0.06
0
0
0.54
618
800
790
777
983
110
3.9
3.6
3.8
3.7
3.7
> 50
0.38
0.68
0.64
0.75
0.74
–
0.18
0.48
0.51
0.72
0.70
–
[a] the –SO3H loading was determined by suspending sulfonated carbons in a KCl solution (exchange H3O+/K+) followed by a titration of released HCl with NaOH
(see SI for more details); [b] Specific surface area calculated from the Brunauer-Emmet-Teller equation in the P/P° range of 0.025-0.20; [c] calculated by the Barrett-
Joyner-Halenda method; [d] Total pore volume estimated at P/P° = 0.95.
126

W.G. Ramdani, et al.
MolecularCatalysis468(2019)125–129
exchange capacities determined by treatment with a KCl solution
(H3O+/K+ exchange and titration of released HCl) of all prepared
sulfonated carbons are summarized in Table 1.
glucopyranoside form.
The turn over frequency (TOF) and the turn over number (TON) of
CMK-3-723-SO3H were 110 h−1 and 50, respectively (Table 2, entry 2).
Although high pyrolysis temperatures (> 823 K) generated CMK-3-
T materials with a well-defined mesoporous structure, it was however
not beneficial for the subsequent introduction of sulfonic acid groups in
a sufficient amount for catalytic applications (Table 1). As a general
trend, the higher the pyrolysis temperature, the lower the –SO3H
loading, and the higher the mesopority. This result is consistent with
previous reports and with our FT-IR, TEM, XRD and N2 adsorption in-
vestigations presented in the supporting information. This is actually
attributed to a progressive disappearance of sites favorable for the
subsequent functionalization of the CMK-3 surface with -SO3H groups
at high pyrolysis temperature due to a more complete carbonization of
the precursor forming large carbon sheets which generated, in return, a
higher mesoporosity [45]. Hence, for a catalytic application, a com-
promise has to be made between the amount of –SO3H groups and the
mesoporosity of the carbon support. Well-ordered carbons are indeed
attractive but they bear a negligible amount of –SO3H which means that
high amount of catalyst should be used in this case, which is, in our
views, not realistic for the present application. In this context, only two
CMK-3-T-SO3H materials (with T = 723 K and 823 K) have been se-
lected for catalytic experiments.
In catalytic trials, 1 g of glucose was mixed with 10 g of n-dodecanol
and heated at 120 °C under vacuum (15 mmHg) in the presence of
1.8 mol% of -SO3H sites grafted either on CMK-3-T (T = 723 and 823)
or on AC-723. The reaction was monitored by gas chromatography,
allowing the conversion, yields and selectivity to be determined with an
experimental error of 5%. Results are summarized in Table 2. A ty-
pical kinetic profile of the reaction is provided in the Figure S11.
Because non-sulfonated CMK-3-T materials (with T = 723 K and
823 K) bear (only) weak acid sites (−COOH groups), these materials
were tested first as control catalysts. Over CMK-3-723, in the above
described experimental conditions, 86% of glucose was converted after
3 h of reaction, but no formation of AAGs was observed. Only tar-like
materials were produced in this case (Table 2, entry 1). Reversely, over
CMK-3-723-SO3H, glucose was completely converted after 3 h of reac-
tion but AAGs were obtained with 85% yield, confirming that strong
acid sites are required for the glycosylation of glucose with n-dodecanol
(Table 2, entry 2). Other products formed were dodecylpolyglucosides
resulting from the slight oligomerization of glucose on n-dodecanol. As
determined by gas chromatography, produced AAGs were formed as a
mixture of dodecyl glucopyranoside and dodecyl glucofuranoside in a
ratio pyranoside/furanoside of 20. Both forms existed also as two
anomers (α and β). The α/β ratio was 2 for the major dodecyl
Under these conditions, the space time yield reached 48 kg.m-3. h−1
,
which is in line with industrial values of the field. Extrapolation of these
results to a reactor of 10 m3, running 8 000 h per year (typical size of
reactor in this field of chemistry), suggests a theoretical production
capacity of 3 840 tons per year and per reactor. It is worth noting that
CMK-3-823-SO3H afforded similar results, although it was necessary to
use a larger amount of catalyst to keep the -SO3H mol% identical in
both trials (Table 2, entry 3).
To benchmark CMK-3-723-SO3H, the catalytic performances were
further compared under the same conditions to a series of solid acid
catalysts previously published in the literature. SBA-SO3H did not yield
AAGs due to its rapid deactivation caused by the stoichiometric release
of water (surface hydrolysis and/or -SO3H solvation with water, as
previously observed [46]), leading to the major thermal degradation of
glucose to humins. (Table 2, entry 5). Amberlyst-15, often used in acid-
catalyzed reactions, was unfortunately not stable at 120 °C and it was
also quickly degraded in our experimental conditions, leading again to
the major formation of tar-like materials (10% AAG yield at 60% of
conversion of glucose, Table 2, entry 6). In contrast, H-BEA zeolite af-
forded AAGs in 59% yield but with a very low space time yield of
2 kg.m−3. h-1 (Table 2, entry 7), which may be rationalized by the
presence of acid sites with a lower acid strength than –SO3H groups.
Interestingly, in terms of catalytic properties, CMK-3-723-SO3H was
found as performant as Aquivion PFSA PW 98, one of the best solid
catalysts reported so far for this reaction (Table 2, entry 4) [27,28].
However, at the end of the reaction, the CMK-3-723-SO3H has a much
lower settling time than Aquivion PFSA, this later being swelled in a
very large extent in alkyl alcohol. As a consequence, the recycling
procedure of CMK-3-723-SO3H was technically much simpler than that
of Aquivion PFSA. Recyclability of CMK-3-723-SO3H is discussed later
in the manuscript. Interestingly, the CMK-3-723-SO3H catalyst has a
TOF in a similar range to that of H2SO4 (Table 1, entry 8). Although the
space time yield was lower than the one obtained with H2SO4, it is
noteworthy that the maximum yield of AAG was higher with CMK-3-
723-SO3H (85%) than with H2SO4 (74%) (Table 1, entries 2 and 8).
CMK-3-723-SO3H was next compared to AC-723-SO3H in order to
highlight the importance of mesopores in the catalyst performances.
Under identical conditions, AC-723-SO3H was nearly not active
achieving a very low yield in AAGs of 8% after 3 h of reaction (Table 1,
entry 9). Analysis of the used AC-723-SO3H revealed a drastic decrease
in the BET surface from 110 to only 3 m2/g, suggesting the deposition of
tar-like materials on the surface of AC-723-SO3H. In contrast, CMK-3-
Table 2
Optimal results in the catalytic glycosylation of glucose with n-dodecanol at 120 °C[a]
.
[b]
[e]
Entry
Catalyst
Time (min)
180
180
180
180
600
540
720
90
Conv. (%)
86
100
100
98
75
60
100
90
37
TOF (h−1
nd[f]
110
94
105
6
8.8
–
118
nd
)
TON[c]
–
50
45
53
0
6
–
120
4
Yield (%)[d]
–
Space Time Yield (kg. m−3. h-1
)
–
48
45
50
0
2
7
86
4
1
2
3
4
5
6
7
8
9
CMK-3-723[e]
CMK-3-723-SO3H
CMK-3-823-SO3H
Aquivion PW98
SBA-SO3H
85
82
98
0
10
59
74
8
Amberlyst-15
[g]
H-BEA
H2SO4
AC-723-SO3H
180
[a] 120 °C, 1.8 mol % of –SO3H, n-dodecanol/glucose mass ratio = 10; [b] determined at a conversion of glucose lower than 20%; [c] determined at the maximum
yield in AAGs; [d] other product are dodecyclpolyglycosides and polydextrose; [e] it corresponds to the mass of product converted per volume of solution and per
unit of time (determined from the AAG yield); [f] not determined, only tar-like materials were formed; [g] 15 wt% (Si/Al = 25).
127

W.G. Ramdani, et al.
MolecularCatalysis468(2019)125–129
reaction still proceeded well, achieving an AAG yield of 70% (Table 3,
entry 2). Regarding carbohydrates, the substitution of glucose by
mannose or galactose in the catalytic glycosylation reaction with n-
dodecanol was found feasible over CMK-3-723-SO3H, but afforded
AAGs with a lower yield of 50% and 30%, respectively, indicating that
the reaction conditions initially defined for glucose are not the opti-
mized ones for mannose and galactose (Table 3, entries 3, 4). These
carbohydrates are indeed known to be more sensitive to the reaction
temperature (thermal degradation) than glucose. In this context, the
same reaction was conducted from mannose at 100 °C instead of 120 °C,
affording the corresponding AAGs with 95% yield (Table 3, entry 5).
4. Conclusion
Here, we investigated the catalytic performances, in terms of yield,
selectivity, space time yield and recyclability, of CMK-3-723-SO3H and
CMK-3-823-SO3H in the Fischer glycosylation of carbohydrates with
alkyl alcohols. We were pleased to see that CMK-3-723-SO3H exhibits
catalytic performances superior to the commonly used solid acid cata-
lysts. The presence of mesoporous channels resulted in a high catalyst
activity. As a consequence, the catalytic glycosylation rate of carbo-
hydrates with alkyl alcohols was greatly improved, to the detriment of
the thermal degradation of carbohydrate which remained drastically
limited in this case, thus preventing the CMK-3-723-SO3H catalyst from
deactivation and allowing its recycling for at least 8 consecutive cata-
lytic cycles. In contrast to Aquivion PFSA, one of the best solid catalyst
reported so far for this reaction, CMK-3-723-SO3H has the advantage of
being much more easily recovered at the end of the reaction, the re-
covery of Aquivion PFSA being hampered by its very important swel-
ling leading to a rapid filter clogging. With CMK-3-723-SO3H, AAGs
were obtained with 85–95% yield while the space time yields of the
glycosylation reaction remained in line with those expected at an in-
dustrial scale in this field of research. Being able to prepare mesoporous
carbons with a high mesoporosity and high –SO3H loading represents,
in our views, an important perspective to this work to prepare even
more performant catalysts.
Fig. 1. Catalytic recycling of CMK-3-723-SO3H (120 °C, 1.8 mol % of –SO3H, n-
dodecanol/glucose mass ratio = 10; between each cycle, CMK-3-723-SO3H was
washed with ethanol).
Table 3
Transposition of the catalytic process to different alkyl alcohols and sugars[a]
.
Entry
Sugar
Alkyl alcohol
Time (min)
Conv. (%)
AAG yield (%)
1
Glucose
Glucose
Mannose
Galactose
Mannose
n-hexadecanol
methanol
n-dodecanol
n-dodecanol
n-dodecanol
180
180
60
60
120
100
100
100
66
89
70
50
30
95
2[b]
3
4
5[c]
100
[a] 120 °C, 1.8 mol % of -SO3H (CMK-3-723-SO3H), n-alkyl alcohol/glucose
mass ratio = 10; [b] reaction was performed at reflux of methanol; [c] 100 °C.
723-SO3H was successfully recycled at least 8 times with only a slight
decrease of the AAGs yield from 85% to 80% (i.e. within the experi-
mental error) which unambiguously demonstrated the usefulness of
mesopores as regards accessibility of -SO3H to the reactants and re-
sistance to deactivation (Fig. 1).
The used CMK-3-723-SO3H (after 1 catalytic cycle) was analyzed by
FT-IR and the presence -SO3H sites was still clearly visible with typical
bands between 1000 and 1400 cm−1, as shown in Figure S12. The
determination of the H3O+ exchange capacity showed a slight decrease
of the -SO3H loading from 0.64 to 0.52 mmol/g which may be explained
by (1) a -SO3H leaching or (2) a deposition of tar-like materials on the
CMK-3-723-SO3H surface (i.e. dilution of –SO3H). By means of ICP
analysis, no trace of sulfur was found into the solution suggesting that
the slight decrease in the amount of -SO3H sites was presumably due to
the partial deposition of tar-like material on the CMK-3-723-SO3H
surface. Note that the total inhibition of tar-like materials is nearly
impossible to achieve in such reaction and a deactivation of the catalyst
will certainly occur in the long term. For instance, the BET surface
dropped from 618 to 130 m2/g after 8 cycles. However, in contrast to
non-mesoporous catalysts, the presence of mesopores seems limiting
the deposition of tar-like materials.
To further confirm the absence of -SO3H leaching, a hot filtration
test was performed. To this end, the CMK-3-723-SO3H catalyst was
filtered after 20% conversion and the solution was kept heating at
120 °C. No formation of AAGs was observed after removal of the CMK-
3-723-SO3H catalyst, thus confirming that, in our case, the catalytic
reaction was truly of heterogeneous nature.
The scope of CMK-3-723-SO3H was next generalized to other alkyl
alcohol and carbohydrate derivatives (Table 3). Replacing n-dodecanol
by n-hexadecanol had no effect on the catalytic performances of CMK-3-
723-SO3H and AAGs were obtained in 89% yield after 180 min of re-
action (Table 3, entry 1). This is an important result since it has been
shown that increasing the chain length of AAGs improved their foaming
properties and lowered their toxicity, in particular irritability for eyes
[47]. From short chain alkyl alcohols such as methanol for instance, the
Author contributions
The manuscript was written through contributions of all authors. All
authors have given approval to the final version of the manuscript.
Acknowledgment
Authors are grateful to the CNRS, the University of Poitiers and the
region Nouvelle Aquitaine for the financial supports. The FR CNRS
INCREASE 3707 and the chaire TECHNOGREEN are also strongly ac-
knowledged.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.mcat.2019.02.016.
References
[1] A. Corma, S. Iborra, A. Velty, Chem. Rev. 107 (2007) 2411–2502.
[2] P.L. Dhepe, A. Fukuoka, ChemSusChem 1 (2008) 969–975.
[3] R. Rinaldi, F. Schüth, Energy Environ. Sci. 2 (2009) 610–626.
[4] M.J. Climent, A. Corma, S. Iborra, Green Chem. 13 (2011) 520–540.
[5] S. Van de Vyver, J. Geboers, P.A. Jacobs, B.F. Sels, ChemCatChem 3 (2011) 82–94.
[6] C.-H. Zhou, X. Xia, C.-X. Lin, D.-S. Tong, J. Beltramini, Chem. Soc. Rev. 40 (2011)
5588–5617.
[7] P. Gallezot, Chem. Soc. Rev. 41 (2012) 1538–1558.
[8] J. Luterbacher, D.M. Alonso, J. Dumesic, Green Chem. 16 (2014) 4816–4838.
[9] M. Yabushita, H. Kobayashi, A. Fukuoka, Appl. Catal. B: Environ. 145 (2014) 1–9.
[10] J. Wang, J. Xi, Y. Wang, Green Chem. 17 (2015) 737–751.
[11] I. Delidovich, P.J.C. Hausoul, L. Deng, R. Pfützenreuter, M. Rose, R. Palkovits,
128

W.G. Ramdani, et al.
MolecularCatalysis468(2019)125–129
Chem. Rev. 116 (2016) 1540–1599.
Green Chem. 12 (2010) 1790–1795;
[12] J.-P. Lange, Angew. Chem. Int. Ed. 54 (2015) 13186–13197.
[13] J.-P. Lange, Catal. Sci. Technol. 6 (2016) 4759–4767.
[14] F. Jérôme, S. Marinkovic, B. Estrine, ChemSusChem 9 (2018) 1395–1409.
[15] D. Balzer, H. Lüders, In Nonionic Surfactants: Alkyl Polyglucosides 91 Marcel
Dekker, New York and Basel, Switzerland, 2000, p. 19.
[16] W. von Rybinski, K. Hill, Angew. Chem. Int. Ed. 37 (1998) 1328–1345.
[17] F. Martel, B. Estrine, R. Plantier-Royon, N. Hoffmann, C. Portella, Top. Curr. Chem.
294 (2010) 79–115.
(i) A.V. Puga, A. Corma, Chem. Select 2 (2017) 2495–2498.
[29] N. Villandier, A. Corma, ChemSusChem 4 (2011) 508–513.
[30] D. Song, S. BoLu, Y. Guo, J. Leng, Appl. Catal. B 179 (2015) 445–457.
[31] J. Wang, Z. Zhang, S. Jin, X. Shen, Fuel 192 (2017) 102–107.
[32] D. Yamaguchi, K. Watanabe, S. Fukumi, Sci. Rep. 6 (2016) 20327.
[33] W. Yin, Z. Tang, R.H. Venderbosch, Z. Zhang, C. Cannilla, G. Bonura, F. Frusteri,
H.J. Heeres, ACS Catal. 6 (2016) 4411–4422.
[34] H. Kobayashi, T. Komanoya, K. Hara, A. Fukuoka, ChemSusChem. 3 (2010)
[18] A. Ismail, S. Soultani, M.J. Ghoul, Biotechnol. 69 (1999) 135–143.
[19] A. Ismail, S. Soultani, M.J. Ghoul, Biotechnol. 69 (1999) 145–149.
[20] J.Y. Li, Y.J. Liu, G. Zheng, Y. Sun, Y.N. Hao, T. Fu, Adv. Mater. Res. 550-553 (2012)
75–79.
440–443.
[35] F. Liu, Q. Liu, J. Xu, L. Li, Y.-T. Cui, R. Lang, L. Li, Y. Su, S. Miao, H. Sun, B. Qiao,
A. Wang, F. Jerome, T. Zhang, Green Chem. (2018), https://doi.org/10.1039/
C8GC00039E.
[21] K. Böge, L.F. Tietze, Fett/ Lipid 100 (S) (1998) 36–41.
[22] M.A. Camblor, A. Corma, S. Iborra, S. Miquel, J. Primo, S. Valencia, J. Catal. 172
(1997) 76–84.
[36] Y. Zhang, A. Wang, T. Zhang, Chem. Commun. 46 (2010) 862–864.
[37] R. Ramakrishnan, T. Sivakumar, D. Arulselvan, K. Sakthivel, E. Elangovan,
K. Kathiravan, Appl. Catal. A Gen. 545 (2017) 33–43.
[23] N.S. Chaubal, V.Y. Joshi, M.R.J. Sawant, J. Mol. Cat. A Chem. 267 (2007) 157–164.
[24] Y. Wu, J.G. Yu, X.F. Ma, J.S. Zhang, Chin. Chem. Lett. 18 (2007) 1173–1175.
[25] I.A. Amin, M.A. Yarm, N.I.N. Yusoff, M.Z. Yusoff, A. Ayatillah, Adv. Mater. Res. 620
(2013) 446–452.
[26] A.A. Chaugule, A.R. Jadhav, H. Kim, RSC Adv. 5 (2015) 104715.
[27] A. Karam, K. De Oliveira Vigier, S. Marinkovic, B. Estrine, C. Oldani, F. Jérôme, ACS
Catal. 7 (2017) 2990–2997.
[38] F. Liu, K. Huang, A. Zheng, F.-S. Xiao, S. Dai, ACS Catal. 8 (2018) 372–391.
[39] (a) R. Zhong, Y. Liao, L. Peng, R.I. Iacobescu, Y. Pontikes, R. Shu, L. Ma, B.F. Sels,
ACS Sustainable Chem. Eng 6 (2018) 7859–7870;
(b) D.S. Sheng Su, S. Perathoner, G. Centi, Chem. Rev. 113 (2013) 5782–5816.
[40] R. Zhong, F. Yu, W. Schutyser, Y. Liao, F. de Clippel, L. Peng, B.F. Sels, Appl. Catal.
B Environ. 206 (2017) 74–88.
[41] R. Zhong, B.F. Sels, Appl. Catal. B Environ. 236 (2018) 518–545.
[42] E. Doustkhah, J. Lin, S. Rostamnia, C. Len, R. Luque, X. Luo, Y. Bando, K.C.‐W. Wu,
J. Kim, Y. Yamauchi, Y. Ide, Chem. Eur. J. (2018) in press https://doi-org.inc.bib.
cnrs.fr/10.1002/chem.201802183.
[28] (a) A. Karam, K. De Oliveira Vigier, S. Marinkovic, B. Estrine, C. Oldani, F. Jérôme,
ChemSusChem 10 (2017) 3604–3610;
(b) W. Deng, M. Liu, Q. Zhang, X. Tan, Y. Wang, Chem. Commun. (Camb.) 46
(2010) 2668–2670;
[43] S. Jun, S.H. Joo, R. Ryoo, M. Kruk, M. Jaroniec, Z. Liu, T. Ohsuna, O. Terasaki, J.
Am. Chem. Soc. 122 (2000) 10712–10713.
[44] R. Xing, Y. Liu, Y. Wang, L. Chen, H. Wu, Y. Jiang, M. He, P. Wu, Microporous
Mesoporous Mater. 105 (2007) 41–48.
(c) W. Deng, M. Liu, Q. Zhang, X. Tan, Y. Wang, Catal. Today 164 (2011) 461–466;
(d) M.J. Climent, A. Corma, S. Iborra, S. Martinez-Silvestre, ChemSusChem 9
(2016) 3492–3502;
(e) W. Deng, M. Liu, Q. Zhang, X. Tan, Y. Wang, Catal. Today 164 (2011) 461–466;
(f) S. Dora, T. Bhaskar, R. Singh, D.V. Naik, D.K. Adhikari, Biores. Technol. 120
(2012) 318–321;
(g) N. Villandier, A. Corma, Chem. Commun 46 (2010) 4408–4410;
(h) I.A. Ignatyev, P.G.N. Mertens, C. Van Doorslaer, K. Binnemans, D.E. de Vos,
[45] M. Zhang, A. Sun, Y. Meng, L. Wang, H. Jiang, G. Li, Microporous Mesoporous
Mater. 204 (2015) 210–217.
[46] A. Karam, J.-C. Alonso, T. Gerganova, P. Ferreira, N. Bion, J. Barrault, F. Jerome,
Chem. Commun. 45 (2009) 7000–7002.
[47] A. Mehling, M. Kleber, H. Hensen, Food Chem. Toxicol. 45 (2007) 747–758.
129