Gold Catalysis and Photoactivation: A Fast and Selective Procedure for the Oxidation of Free Sugars

Article abstract of DOI:10.1021/acscatal.7b03394

A fast and efficient methodology for the selective oxidation of sugars into corresponding sodium aldonates is herein reported. Hydrogen peroxide was used as a cheap oxidant and electron scavenger, in the presence of only 0.003-0.006 mol % of gold in basic conditions. Three photocatalysts were studied, namely Au/Al₂O₃, Au/TiO₂, and Au/CeO₂, the latter being the most efficient (TOF > 750 000 h^-1) and perfectly selective. Only a 10 min exposition under standard incident sunlight irradiation (A.M.1.5G conditions, 100 mW/cm²) affords total conversion of glucose into the corresponding sodium gluconate. Demonstrating its versatility, this methodology was successfully applied to a variety of oligosaccharides leading to the corresponding aldonates in quantitative yield and high purity (>95%) without any purification step. The photocatalyst was recovered by simple filtration and reused 5 times leading to the same conversion and selectivity after 10 min of illumination.

Full text of DOI:10.1021/acscatal.7b03394

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Letter
Gold catalysis and photoactivation: a fast and
selective procedure for the oxidation of free sugars
Mehdi Omri, Frédéric Sauvage, Yan Busby, Matthieu Becuwe, Gwladys Pourceau, and Anne Wadouachi
ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.7b03394 • Publication Date (Web): 19 Jan 2018
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ACS Catalysis
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Gold catalysis and photoactivation: a fast and selective
procedure for the oxidation of free sugars
Mehdi Omri,1 Frédéric Sauvage,2 Yan Busby,3 Matthieu Becuwe,2 Gwladys Pourceau,*,1 and Anne
Wadouachi1
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1 Laboratoire de Glycochimie, des Antimicrobiens et des Agroressources (LG2A) UMR CNRS 7378 - Institut de Chi-
mie de Picardie FR 3085, Université de Picardie Jules Verne, 33 rue Saint Leu, FR-80039 Amiens Cedex, France.
2 Laboratoire de Réactivité et Chimie des Solides (LRCS), UMR CNRS 7314 - Institut de Chimie de Picardie FR 3085,
Université de Picardie Jules Verne, 33 rue Saint Leu, FR-80039 Amiens Cedex, France.
3 Laboratoire Interdisciplinaire de Spectroscopie Electronique (LISE), Namur Institute of Structured Matter (NISM),
University of Namur, 61 Rue de Bruxelles, 5000 Namur, Belgium.
KEYWORDS: carbohydrates, photocatalytic oxidation, gold catalysis, aldonates, oligosaccharides modification
ABSTRACT: A fast and efficient methodology for the selective oxidation of sugars into corresponding sodium aldonates is
herein reported. Hydrogen peroxide was used as a cheap oxidant and electron scavenger, in the presence of only 0.003-
0.006 mol % of gold in basic conditions. Three photocatalysts were studied, namely Au/Al2O3, Au/TiO2 and Au/CeO2, the
latter being the most efficient (TOF > 750 000 h-1) and perfectly selective. Only 10 minutes exposition under standard
incident sunlight irradiation (A.M.1.5G conditions - 100 mW/cm2) affords total conversion of glucose into the correspond-
ing sodium gluconate. Demonstrating its versatility, this methodology was successfully applied to a variety of oligosaccha-
rides leading to the corresponding aldonates in quantitative yield and high purity (>95%) without any purification step.
The photocatalyst was recovered by simple filtration and re-used 5 times leading to the same conversion and selectivity
after 10 min of illumination.
KEYWORDS: carbohydrates, photocatalytic oxidation, gold catalysis, aldonates, oligosaccharides modification
The use of sugars as renewable and abundant feedstock
and their eco-friendly conversion into chemicals are be-
coming increasingly attractive to synthesize high-value-
added products.1 Sugars are polyfunctional and serve as a
chemical platform to synthesize a wide variety of deriva-
tive compounds after chemical modifications.2 However,
the multi-step protocols and hazardous chemicals used
for these transformations penalize this chemistry to be
transposed to the industrial scale. Among the different
"glycotransformations", C1-oxidation is of particular inter-
est since it leads to aldonic acids or their salts, widely
used in cosmetics, pharmaceutical, food and paper indus-
tries.3 Conventional procedures gather several drawbacks
such as limited selectivity to aldonic acids, production of
degradation by-products owing to the weakness of the
interglycosidic bond, separation issues of the products, or
environmental toxicity. In this context, heterogeneous
photocatalytic transformation is considered as one of the
most promising sustainable and eco-friendly procedure.
Although many efforts were devoted to design semicon-
ducting (SC) materials exhibiting a high photocatalytic
yield and selective charge transfer processes under visible
light exposure rather than the lower UV flux of photons,
the most promising photocatalyst materials developed so
far are suffering from low oxidative selectivity and re-
stricted spectral absorption into the UV owing to a too
large bandgap value.4-6 This is for instance the case of the
benchmark anatase TiO2 semi-conductor for which its
3.20 eV bandgap value restricts the light absorp-
tion/conversion below 410 nm, thus representing at best
only 5 % of the total solar spectrum. Among other ap-
proaches such as aliovalent doping, the use of SC-
supported metal nanoparticles, especially gold or silver,
was rapidly highlighted as an efficient approach to ad-
dress this issue by extending the spectral absorption to
the visible region thanks to localized surface plasmon
resonance (LSPR) effect. In addition, it also affords to
prolong electron/hole charge separation in the metal
owing to the interfacial metal/SC Schottky barrier assist-
ing the electron injection into the conduction band of the
SC.7-12 Some studies on the selective photo-oxidation of
organic compounds such as thiol into disulfide,13 aliphatic
alcohol into carbonyl derivative14 or aminobenzyl alcohol
into aminobenzaldehyde15 were recently reported in the
presence of catalyst Au/MOx (MOx: metal oxide).13-17 On
the other hand, only a few studies aimed at selectively
photo-oxidizing carbohydrates using TiO2, Ag/TiO2 or
Cr/TiO2 with limited success.18-21 Indeed, the results sys-
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tematically report a low conversion yield and a lack of
Page 2 of 6
values reported in the literature for oxidation using at-
mospheric air (7-16% in most cases).18-21 Surprisingly,
Au/TiO2 exhibited the lower photocatalytic activity in
terms of both conversion and selectivity, albeit still supe-
rior than values reported in the literature: 78% of glucose
were transformed into corresponding sodium gluconate
with a selectivity of ~85% in 30 minutes. Au/Al2O3 enables
evaluating the intrinsic photo-catalytic properties of gold
itself since the 4.4 eV bandgap value of Al2O3 prevents any
electron injection from Au to Al2O3 and any direct
bandgap excitation. Although one would have expected
this catalyst lagging far behind, light absorption by gold
ensures a quantitative conversion into pure sodium glu-
conate with a selectivity greater than 95% in 30 minutes.
Supporting gold to nanocrystalline CeO2 accelerates sig-
nificantly glucose oxidation without penalizing the selec-
tivity (Fig. 1). Quantitative conversion to the gluconate
was obtained in only 10 minutes of illumination. A turn-
over frequency (TOF) of 752 380 h-1 was calculated for this
photocatalyst after 5 min of irradiation (i.e. at 79% con-
version).
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selectivity to the corresponding gluconic acid, leading to
smaller chain monosaccharides and partial- and over-
oxidized byproducts. Interestingly, Zhou et al. reported
very recently the aerobic oxidation of two monosaccha-
rides (glucose and xylose) at micromolar scale in 4 hours
at 30°C under high light power (300 mW/cm2) into the
corresponding acids with good selectivity by using
Au/TiO2 photocatalyst (3.8 mol %).22
9
In this work, we report on a simple and an efficient
procedure affording a fast and selective photoelectro-
chemical reaction leading to pure sodium mono- and
oligo-aldonates in less than 10 minutes of incident light
exposure under standard photovoltaic A.M.1.5G condi-
tions (100 mW/cm2) at room temperature (Scheme 1).
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Au/MOx
1.1 eq H2O2
1 eq NaOH
OH
OH OH
ONa
R
O
HO
O
HO
ν
h
O
OH
O
HO
OH
R
R= H, mono- or oligo-saccharides
Scheme 1. Photocatalyzed oxidation of saccharides into
corresponding aldonates.
100
80
60
40
20
0
In this study, three different photocatalysts are investi-
gated: Au/TiO2 and Au/CeO2 for which hot electrons from
gold excited state can be injected into the related conduc-
tion band of the SC, and Au/Al2O3 for which the excessive
value of the bandgap (≈ 4.4 eV) prevents any interfacial
charge transfer to proceed.23 The photocatalysts were
prepared by a deposition−precipitation method and char-
acterized by transmission electron microscopy (TEM),
flame spectrometry (AAS) and X-ray diffraction (XRD).24
The gold nanoparticles have a size of around 2-3 nm with
good monodispersity (Fig. S1). Gold loading of each cata-
lyst is between 0.4-0.7 wt % (Table S1) and no change of
crystallinity of the SC support was noticed subsequently
to gold deposition (Fig. S2). Gold nanoparticles show a
broad plasmonic absorption band at ca. 550 nm as meas-
ured in UV-visible absorption spectroscopy in reflectance
mode (Fig. S3). The XPS analysis on SC supported gold
nanoparticles shows that gold is mainly found in the me-
tallic state (Au0 represent 85% of the peak area in
Au/CeO2 while Au+I oxidation state 15%, Fig. S4).
0
10
20
30
Time (min)
100
80
60
40
20
0
The photocatalysts performance was evaluated in water
for the oxidation of glucose using a catalytic charge of
0.003-0.006 mol % of gold (i.e. a substrate/gold ratio
between 15 000 and 30 000), 1.1 eq of hydrogen peroxide as
an electron scavenger and 1 eq of sodium hydroxide. After
filtration of the catalyst, the resulting reaction media was
freeze-dried and analyzed by NMR and HPLC to evaluate
both conversion and selectivity into sodium gluconate
(Fig. S5-S6). Otherwise, EDX analysis of lyophilized media
did not evidence any dissolution of the photocatalyst (Fig.
S7). As shown in figure 1, whatever the photocatalyst,
moderate to high conversion yields (between 30 and 79%)
into gluconate were already achieved in only 5 minutes of
illumination (Fig. S8). This is significantly higher than the
5
10
20
30
Time (min)
Figure 1. Top: Conversion of glucose vs time using
Au/Al2O3 (green line), Au/TiO2 (red line) or Au/CeO2
(blue line) catalysts; bottom: Selectivity toward sodium
gluconate using Au/Al2O3 (green bar), Au/TiO2 (red bar)
or Au/CeO2 (blue bar) catalysts
Although the bandgap value of TiO2 and CeO2 are rela-
tively comparable, the differences between TiO2 and
CeO2-supported gold photocatalysts can be explained by
three factors: 10,14,25 (i) LSPR effect is stronger for Au/CeO2
than for Au/TiO2; this enables a better light capture by
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ACS Catalysis
the gold nanoparticles (ii) the conduction band position
air as oxidant for the oxidation of carbohydrates.7,8 This
discrepancy may stem from the shorter reaction time (<
30 minutes) and the lower amount of gold lying between
0.003-0.006 mol % in our study, whereas several hours in
presence of 1000 times more catalyst were reported in
literature.22 Although more investigations are underway
by electron spin resonance and transient absorption and
emission spectroscopies to better insight on the nature of
the intermediate species which are formed at Au/SC sur-
face responsible for the sugar oxidation, for which the
results will be reported elsewhere, we argue that in our
case H2O2 plays the role of electron scavenger after gold
has injected electron into the conduction band of the SC.
This electron scavenging affords enhancing the charge
separation lifetime in agreement with previous observa-
tions in the literature to avoid unwished fast radiative
recombination processes.28-29 This electron transfer leads
to ·OH oxidant radicals and HO- formation.30 Interesting-
ly, it is well-established that 1 mole of hydrogen peroxide
can be reformed after reaction of 2 moles of ·OH.31 This is
fully consistent with our results showing that 75 % of
glucose is converted with only 0.5 eq of H2O2 (entry 12).
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of CeO2 is more oxidizing than TiO2 counterpart and the
Schottky barrier is lower for CeO2 (0.8 eV) than in TiO2
(1.09 eV), thus one could anticipate that gold excited
states should inject faster in CeO2 than in TiO2 which for
this latter already takes place in less than 240 fs (more
efficient charge separation) and (iii) a strong quenching of
CeO2 luminescence has been observed under UV excita-
tion (375 nm) when supporting Au NPs suggesting either
a reduction of recombination rate or also electron injec-
tion into the metal gold, thus offering more separated
carriers to onset the photo-oxidation process. In addition,
the oxygen vacancies at the CeO2 surface help to achieve
a better gold dispersion at the surface of the semi-
conductor as well as to enhance the stability of gold na-
noparticles. The lower selectivity of TiO2-based photo-
catalysts has been previously pointed out.22 It has been
endowed to the formation of strong oxidizing radicals
formed from the direct hole transfer from the O 2p orbit-
als of TiO2 under UV irradiation. A very recent work
showed that glucose can be converted into formate using
nano-TiO2 in basic conditions as a result from the for-
mation of two types of strongly oxidative radicals ·OH (E°
= +2.38 V vs. NHE) and O2·- (+1,72 V vs. NHE) when in
presence of hydroxyl ions.26
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Table 1. Influence of some parameters on the conver-
sion of glucose and on the selectivity towards glu-
conic acid
Several blank tests were carried out to better highlight
the role of the photocatalyst (Table 1). Firstly, a reaction
without any photocatalyst was performed under A.M.1.5G
illumination showing no reaction as one would have ex-
pected (entry 1). Secondly, the properties of the semi-
conducting materials alone (without gold nanoparticles)
were evaluated according to the same reaction conditions
(entries 2-4). In all cases, whatever the nature of the met-
al oxide, glucose remained unchanged, thus confirming
that gold-free semi-conductors are not photocatalysts
under A.M.1.5G white light, proving the photochemical
stability of these latter together with stressing the need to
combine synergistically the SC with the Au NPs to achieve
an efficient and selective photon-induced oxidation reac-
tion. This gives evidence that OH. formed subsequently to
hole transfer from the SC valence band cannot oxidize the
glucose in our conditions, therefore is not an intermedi-
ate involved in the glucose to gluconate conversion, at
least under AM1.5G conditions. Finally, similar reactions
were performed in darkness. In this case, whatever the
catalyst, glucose remained unchanged (entries 7, 10, 16)
confirming that glucose is chemically stable in our
conditions and underlying that the oxidation reaction
involves photon-induced charge transfer processes.
Indeed, no glucose decomposition in presence of hydro-
gen peroxide is herein observed (entries 1-4, 7, 10, 16, Ta-
ble 1), by contrast to what has been experienced by
Comotti et al. using various mixture between glucose and
hydrogen peroxide at pH = 9.5 without catalyst and in
darkness.27 The role of hydrogen peroxide is crucial: even
in presence of gold catalyst (entries 6, 9, 13), neither oxi-
dation nor degradation of glucose was observed if hydro-
gen peroxide was not added. This is in contrast to several
works in the literature reporting the use of atmospheric
neq
neq
Conversion Selectivity
Catalyst
H2O2 NaOH
(%)
(%)
1
2
-
1.1
1.1
1.1
1.1
1.1
0
1
1
0
-
-
TiO2
Al2O3
CeO2
0
3
1
0
-
4
1
0
-
5
1
49
0
<81
-
6
1
Au/TiO2
b
7
1.1b
1.1
0
1b
0b
69
0
-
8
1
>95
-
9
1
Au/Al2O3
b
10
11
12
13
14
15
16
1.1b
1.1
0.5
0
1b
0b
>99
75
0
-
1
>95
>95
-
1
1
Au/CeO2
1.1
1.1a
1.1b
0.5
0a
1b
63
29a
0b
>95
>95a
b
-
Reaction conditions: glucose 250 mg, catalyst 2.5 mg,
water 5 mL, light power 100 mW/cm2 (A.M.1.5G), 10 min. [a]
reaction time extended to 1 hr, [b] reaction performed in
darkness.
On the other hand, when reducing the quantity of
NaOH to 0.5 eq, the conversion yield decreased to 63 % in
10 min and to 29 % only without any base after 1 hour
(entries 14-15). We hypothesized that the base plays three
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roles: (i) free of base, the surface of the gold catalyst can
Page 4 of 6
mono- to oligosaccharides (degree of polymerisation (DP)
from 1 to 6) leading to the corresponding mono to hexa-
aldonates with excellent conversion and selectivity (Table
3, Fig. S9-S10). Interestingly, by contrast to the micro-
wave-assisted procedure recently described,24 NaOH can
be used as a base even for oligosaccharides without deg-
radation and/or hydrolysis of the interglycosidic bond,
probably thanks to the mild conditions (room tempera-
ture and short reaction time). Moreover, this photo-
electrochemical reaction is not substrate-dependent:
lactose, maltose or cellobiose (entries 2-4), which exhibits
different types of glycosidic linkage (α or β) and of glyco-
sidic residues (glucose or galactose) reacted quantitatively
in 10 minutes with a selectivity greater than 95 %.This
methodology was also successfully applied to higher DP
oligosaccharides such as maltotriose and maltohexose
(entries 5-6) demonstrating its versatility. This appealing
result underlines once again the advantage of photochem-
istry against, for instance, microwave-assisted procedure
in terms of substrate-dependency. We thus demonstrate
systematically fast, quantitative conversion yield and
excellent selectivity regardless of the type of sugar, lead-
ing to pure aldonates without any means of purification
step.
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be poisoned by the gluconic acid produced (ii) mineral
bases inhibit the strong oxidative species generated under
UV light (hydroxyl radicals and singlet oxygen), and pro-
mote visible-light-induced oxidation as recently pointed
out by Zhou et al.22 and (iii) in addition to the locally
produced OH- from hydrogen peroxide reduction, the
base accelerates the hydration of aldehyde into geminal
diol, which adsorbs to the Au/SC surface to form a metal
alkoxide, and facilitates the β-hydride elimination by hole
transfer from gold excited state leading to the formation
of the corresponding carboxylate.32-33
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The photocatalyst was retrieved and re-used 5 times
and led to the same excellent conversion (>99%) and
selectivity (>95%) after 10 min of irradiation. Post-ageing
characterization by means of TEM and AAS showed no
structural, chemical and textural transformation of the
photocatalyst upon cycling (Table 2, Fig. S1, Table S1). No
further oxidation of gold was also evidenced by XPS (Fig.
S4). This stresses its high robustness in the different
media herein investigated. Nevertheless, a decrease in the
TOF value was observed: a TOF of 466 000 h-1, still higher
than those reported in literature, was calculated for the
sixth run after 5 min of irradiation (Fig. S8).
In conclusion, a mild, very fast and versatile method to
selectively produce aldonates from mono and oligosac-
charides derived from biomass was successfully devel-
oped. This reaction is performed in water, using a cheap
and green oxidant and involving a very few quantities of a
reusable catalyst. The photocatalytic results herein re-
ported were gathered using a class A calibrated standard
A.M.1.5G light source (P = 100 mW/cm2) typically used for
photovoltaic characterization; ie. a procedure reproduci-
ble and realistic with respect to the end-application. The-
se first results call for further development of novel oligo-
aldonate derivatives in large and green scale for their
utilization as detergents, pharmaceuticals or cosmetics to
replace petroleum-based chemicals.
Table 2. Characteristics of Au/CeO2 after 5 runs
Catalyst
initial
Mean sizea (nm)
2.9 ± 0.7
Gold contentb (%)
0.50 ± 0.01
after 5 runs
3.2 ± 0.6
0.49± 0.01
[a] Mean size was determined by TEM, [b] gold content
was determined by AAS
Such excellent results can be obtained also at 3g-scale
keeping same conversion yield and selectivity into sodium
gluconate.
Finally, the optimized conditions (Table 1, entry 11)
were successfully applied to a variety of saccharides from
Table 3. Photocatalyzed oxidation of various substrates.
Sugar
Product
Conv. (%)
>99
Select.(%)
>95
OH
OH
D
-Glucose
ONa
OH
HO
1
O
OH
OH
O
HO
HO
OH
OH
OH
D
-Maltose
ONa
O
O
HO
HO
HO
HO
OH
O
2
>99
>95
O
OH
HO
HO
OH
HO
OH
O
O
HO
HO
OH
OH
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ACS Catalysis
ONa
O
OH
HO
HO
D
-Lactose
1
O
2
3
4
5
6
7
8
9
O
HO
OH
3
OH
>99
>99
>95
>95
HO
OH
OH
O
O
OH
O
HO
HO
OH
HO
HO
OH
ONa
O
OH
D
-Cellobiose
HO
O
HO
HO
O
4
OH
OH
OH
OH
O
HO
O
OH
HO
HO
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O
HO
OH
HO
OH
OH
O
D
-Maltotriose
HO
HO
OH
OH
O
ONa
O
HO
OH
HO
5
OH
O
>99
>95
H
O
O
HO
O
OH
OH
HO
2
O
O
HO
OH
OH
OH
HO
OH
O
HO
HO
OH
OH
O
D
-Maltohexose
O
OH
HO
OH
O
O
HO
OH
OH
O
OH
O
OH
6
>99
>95
HO
OH
O
H
O
ONa
O
O
HO
O
HO
OH
HO
HO
5
OH
O
O
O
HO
OH
OH
OH
OH
HO
Reaction conditions: sugar 250 mg, Au catalyst 2.5 mg, NaOH 1 eq, H2O2 1.1 eq, water 5 mL, hν (standard A.M.1.5G conditions),
min. Conversion rates (conv.) and selectivity (selec.) were determined by NMR
10
(3) Hustede, H.; Haberstroh, H. J.; Schinzig, E. in Ullmann's
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ASSOCIATED CONTENT
Supporting Information. This material is available free of
charge via the Internet at http://pubs.acs.org.
Experimental details, materials, methods, comparison exper-
iments, catalysts and crude characterization.
AUTHOR INFORMATION
Corresponding Author
* E-mail: gwladys.pourceau@u-picardie.fr
Notes
The authors declare no competing financial interest
ACKNOWLEDGMENT
M. O., M. B., G. P. and A. W wish to thank the Conseil
Régional de Picardie for its financial support. F.S. wish to
thank the french national research agency ANR for
funding Photo2batt project.
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