Polymer Bulletin

https://doi.org/10.1007/s00289-019-02749-4

ORIGINAL PAPER

Cellulose‑supported Pd nanoparticles: effective

for the selective oxidation of glucose into gluconic acid

Xinxin Zhang1 · Haoyan Shi1 · Quan Chi1 · Xixi Liu1 · Lianqing Chen1

Received: 28 August 2018 / Revised: 18 March 2019 / Accepted: 19 March 2019

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Abstract
Cellulose-supported on Pd nanoparticles (Pd/cellulose) were successfully prepared
by chemical reduction technique and characterized by various experimental tools.
The Pd/cellulose catalyst was found to effectively promote the oxidation of glucose
into gluconic acid under mild conditions. The base played a crucial role in the oxi-
dation of glucose into gluconic acid. Glucose was fully converted at room tempera-
ture after 3 h by the use of stoichiometric amount of ­Na2CO3 to neutralize gluconic
acid, and gluconic acid was obtained in a high yield of 91.2%. The catalyst was
recovered from product and reused up to five times without significant loss in its
catalytic activity.

Keywords  Cellulose · Pd nanoparticles · Glucose · Gluconic acid · Oxidation

Introduction

In the recent years, much more emphasis has been shifted on the environment-
friendly and sustainable resources and processes [1, 2]. In this regard, the renew-
able biomass has been attracted growing attention to supply chemicals and fuels
for the world [3]. Many chemicals and fuels have been obtained from biomass via
different technologies [4, 5]. Among them, gluconic acid, which is the oxidation
product of glucose, is one of the value-added chemicals [6]. Gluconic acid has
been widely used in food, pharmaceutical, and light industries, and it can also
been used as a precursor for the synthesis of chemicals. Currently, gluconic acid
is industrially produced by biochemical oxidation of glucose (enzymatic oxida-
tion). However, the biochemical method still demonstrates some drawbacks such

* Quan Chi
chiquanscuec@163.com
* Lianqing Chen
lqchen@mail.scuec.edu.cn
1
Key Laboratory of Catalysis and Materials Sciences of the Ministry of Education, South-Central
University for Nationalities, Wuhan 430074, People’s Republic of China

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 Polymer Bulletin

as the low space–time slow, reaction rate, and the tedious separation procedure
of the products and enzymes [7]. Therefore, many other methods have also been
developed for the oxidation of glucose-based carbohydrates into gluconic acid,
such as chemical and electrochemical oxidation methods [8, 9].
Recently, much attention has been paid to the catalytic oxidation of glu-
cose into gluconic acid with molecular oxygen over heterogeneous catalysts
(Scheme  1). The heterogeneous catalysts were mainly focused on supported Pt,
Pd and Au nanoparticles [10–14]. In particular, metal oxides-supported Au cata-
lysts have been extensively studied for the oxidation of glucose into gluconic acid.
Some Au catalysts demonstrated high activity, high stability and high selectivity
toward the oxidation of glucose into gluconic acid. For instance, T ­ iO2-supported
Au catalyst was reported to be active for the aerobic oxidation of glucose, afford-
ing glucose with a yield up to 98% [15]. Nevertheless, these reported heterogene-
ous catalytic systems suffered some drawbacks such as the deactivation of the
catalytic activity and high molar ratio of the catalysts to substrate. Therefore, it is
still attractive to develop new catalytic methods for the oxidation of glucose into
gluconic acid.
Currently, metal oxides were mainly used as the supports for the immobiliza-
tion metal nanoparticles; however, they are not biodegradable, widely available
and economical. In this regard, the use of natural polymers as supports for the
immobilization of metal nanoparticles has been received a great interest in recent
years [16]. Several natural polymers such as gelatin [17], starch [18], chitosan
[19], bulk cellulose [20–22] and cellulose nanofibers [23] have been acted as sup-
ports for the immobilization of metal nanoparticles.
Among them, cellulose is the most abundant and easily available polymers
in nature, as it is the main component of the lignocelluloses in plants. Thus, it
can serve as a promising alternative to metal oxides for the immobilization of
metal nanoparticles because of the excellent properties as described as follows:
(1) chemical inertness in a wide pH range. (2) An oxygen-rich group in its struc-
ture that can be used to anchor metal nanoparticles. (3) Insolubility of cellulose
in water and in most of the organic solvents. Thus, cellulose has emerged as an
attractive support for the metal nanoparticles for many kinds of chemical reac-
tions [24, 25]. Herein, we reported the environmentally friendly approach to syn-
thesize Pd NPs, which were decorated on the cellulose fiber. The cellulose-sup-
ported Pd catalyst was used for the oxidation of glucose into gluconic acid under
mild conditions.

OH OH OH OH O
O
Metal catalyst HO
HO
H + 1/2 O2 OH

OH OH OH OH

Glucose Gluconic acid

Scheme 1  Catalytic oxidation of glucose into gluconic acid over metal catalysts

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Experimental section

Materials

Glucose (99.5%), medical cotton, sulfuric acid ­(H2SO4, 98 wt%) and sodium
borohydride ­(NaBH4, 97%) were purchased from Sinopharm Chemical Reagent
Co., Ltd. (Shanghai, China). Sodium tetrachloropalladate(II) (98.0%) ­(Na2PdCl4)
and gluconic acid were purchased from Aladdin Chemicals Co. Ltd. (Beijing,
China). All the solvents were purchased from Sinopharm Chemical Reagent Co.,
Ltd. (Shanghai, China). All the chemicals were of analytical grade and used with-
out further purification. Ultrapure water was used for the catalyst preparation and
catalytic reactions.

Preparation of cellulose‑supported Pd nanoparticles

Cellulose nanocrystals (CNs) were prepared according to the known procedure as

reported by Kloser et al. [26]. Briefly, medical cotton (4 g) was added into 70 ml
of 64 wt% ­H2SO4 solution and the mixture was stirred vigorously at 45  °C for
45 min. Then, the mixture was kept at room temperature, and 700 ml of water was
added to stop the hydrolysis immediately. Then, the suspension was centrifuged
and washed with deionized water three times to remove all the soluble compo-
nents. Dialysis was performed to remove residual acid in the suspension, and the
result was monitored by checking the neutrality of the dialyzate. The suspension
was concentrated to a desired concentration and sonicated for 30  min at room
temperature.
In a typical experiment, cellulose (1.0 g) was dispersed in 20 mL of water with
the assist of ultrasonication for 1 h. Then, N
­ a2PdCl4 (30 mg) in ethanol was added
dropwise at room temperature. Then, the mixture was continually stirred at room
temperature for 6 h. After reaction, the mixture was filtrated, and the solid residue
was washed with large amount of water, and dried in a vacuum oven overnight at
60 °C.

Catalyst characterization

Transmission electron microscope (TEM) images were obtained using an FEI Tec-
nai ­G2-20 instrument at 300 kV. The sample powder was firstly dispersed in ethanol
and dropped onto copper grids for observation. X-ray powder diffraction (XRD) pat-
terns of samples were determined with a Bruker advanced D8 powder diffractometer
(Cu Kα). All XRD patterns were collected in the 2θ range of 10°–80° with a scan-
ning rate of 0.016°/s. X-ray photoelectron spectroscopy (XPS) was conducted on a
Thermo VG scientific ESCA MultiLab-2000 spectrometer with a monochromatized
Al Kα source (1486.6 eV) at constant analyzer pass energy of 25 eV. The binding
energy was estimated to be accurate within 0.2 eV. All binding energies (Bes) were

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corrected referencing to the C1 s (284.6 eV) peak of the contamination carbon as an

internal standard.

Catalytic oxidation of glucose into gluconic acid

Glucose (1 mmol, 180 mg) and ­Na2CO3 (0.5 mmol, 53 mg) were added to 10 mL
of water with a magnetic stirring to give a clean solution. Then, the Pd/cellulose
(40 mg) was added to the mixture, and the reaction was started at room temperature
by bubbling molecular oxygen (30 mL/min). After a reaction for a certain time, the
reaction was stopped. Then, the catalyst was removed by centrifugation, and the liq-
uid solution was analyzed by HPLC.

Analytic methods

Glucose and gluconic acid in the reaction solution were analyzed by high-perfor-
mance liquid chromatography (HPLC). Glucose and gluconic acid were separated
by a Whatman Partisil10 SAX column (250 × 4.6 mm, 5 μm), and detected by R.I.
detector. The mobile phase was composed of an aqueous solution of 0.02 M ­H3PO4
and menthol with a volume ratio of (95:5) at the flow rate of 1.0  mL  min−1. The
column oven temperature was maintained at 30 °C. The content of glucose and glu-
conic acid in samples was obtained directly by interpolation from calibration curves.
Glucose conversion and gluconic acid yield are defined as follows:
Glucose conversion = moles of glucose used∕moles of starting glucose × 100%

Gluconic acid yield = moles of gluconic acid∕moles of starting glucose × 100%

Gluconic acid selectivity = moles of gluconic acid∕moles of reacted glucose × 100%

Recycling of the catalyst

After reaction, the Pd/cellulose catalyst was recovered via centrifugation and the
spent catalyst was washed with excessive water to remove ant-absorbed chemicals.
Then, it was dried in a vacuum over at 60 °C overnight. The spent catalyst was used
for the next run under the same reaction conditions.

Results and discussion

Catalyst characterization

The Pd/cellulose catalyst was firstly characterized by several techniques. Firstly,

the morphology of the Pd/cellulose catalyst was characterized by TEM technology.
As shown in Fig.  1, Pd nanoparticles were successfully decorated on the surface
of the cellulose. An average size of Pd nanoparticle was calculated to be 5.1  nm
by the measure of more than 200 particles of 20 photographs. In addition, the Pd

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25 5.1 nm

20

Frequency (%)
15

10

0
1 2 3 4 5 6 7 8 9 10 11 12
Size (nm)

Fig. 1  TEM images of Pd/cellulose catalyst and particle size distribution of Pd nanoparticles

nanoparticles were homogenously dispersed on the surface cellulose, indicating that

the hydroxyl groups in cellulose have a strong interaction with the Pd nanoparticles
due to the strong electron donating ability. However, some aggregation of Pd nano-
particles was also observed.
The Pd/cellulose catalyst was further characterized by XRD technology. It is
reported that the major diffraction peak with 2θ ranging between 22° and 23° is the
characteristic XRD peak of cellulose. In addition, two weak peaks with 2θ value
at 16.5 and 34.5° were also assigned to the characteristic XRD peaks of cellulose
[27, 28]. As shown in Fig. 2, a strong peak with the 2θ value center at 22.2° and a
weak peak with 2θ value center at 34.7° were clearly observed. Thus, it clearly indi-
cated that the presence of the crystalline structure of the cellulose constituent was
maintained in the sample when medical cotton (4 g) was treated with 64 wt% ­H2SO4
solution. It seems that catalytic acid hydrolysis did not disrupt the whole structure
of the cellulosic matrix. Besides the XRD peaks for cellulose, three well-defined
peaks were also present in the Pd/cellulose catalyst. The peaks with the 2θ values at

Fig. 2  XRD patterns of the Pd/

cellulose catalyst
Intensity (a. u.)

10 20 30 40 50 60 70 80
2

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40.1°, 46.7°, and 67.8° were assigned to the metallic Pd planes of (1 1 1), (2 0 0), (2
2 0), respectively, according to JCPDS No.65-6174 [29]. The average particle size of
the as-prepared Pd nanoparticles (d) was estimated to be 5 nm by using the Scher-
rer equation [30] after background subtraction from Pd (1 1 1) peak at 2θ of 40.1°,
which was consistent with TEM result.
Finally, the as-prepared Pd/cellulose catalyst was characterized by XPS technol-
ogy. As shown in the survey scan spectrum of Fig.  3a, there are only three peaks
with the binding energy at 285.7, 532.7, and 339.3 eV observed for the Pd/cellulose
catalyst, which were assigned to C 1s, O 1s, and Pd 3d binding energy, respectively.
Thus, it can be concluded that the Pd/cellulose catalyst consisted of Pd, C, and O
without any other impurities. The O peak with strong intensity indicated that cellu-
lose surface was enriched with hydroxyl group, which were used to immobilize the
Pd nanoparticles. The high-resolution XPS spectrum of Pd 3d is shown in Fig. 3b.
Two peaks with binding energies of 335.4 and 340.6 eV were assigned to Pd ­3d5/2
and Pd ­3d3/2, respectively, and the two peaks were the characteristic peaks of metal-
lic Pd [31].

Fig. 3  XPS spectra of the Pd/ (a) O1s

cellulose catalyst. a Survey scan
of Pd/cellulose catalyst; b Pd
3d region in the Pd/cellulose
catalyst
Intensity (a.u.)

C 1s

Pd 3d

1000 800 600 400 200 0

Binding Energy (eV)

(b)
Pd 3d5/2

Pd 3d3/2
Intensity (a.u.)

333 336 339 342 345 348

Binding Energy (eV)

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Catalytic oxidation of glucose over Pd/cellulose catalyst with different kinds

of bases

The as-prepared Pd/cellulose catalyst was evaluated by the oxidation of glucose

into gluconic acid. For the oxidation reaction, an appropriate base is generally
very important. Therefore, different kinds of bases were used for the oxidation of
glucose into gluconic acid including organic base and inorganic base. The amount
of base was used to neutralize the theoretic amount of the produced gluconic acid.
The representative organic base (pyridine) was also ineffective to promote the
oxidation of glucose into gluconic acid by Pd/cellulose catalyst (Table  1, Entry
1). Two reasons should be explained in this phenomenon. On the one hand, the
basicity of pyridine is low. On the other hand, it has a strong coordination ability
with metal nanoparticles to block the active sites. The highest glucose conver-
sion was obtained by the use of NaOH as the additive, but the selectivity of glu-
cose was only 63.4% (Table  1, Entry 2). High glucose conversion and gluconic
acid selectivity were achieved by the use of both ­Na2CO3 and ­NaHCO3 (Table 1,
Entries 3 and 4). The different results obtained by the use of NaOH, ­Na2CO3, and
­NaHCO3 should be caused by basicity of the reaction solution. The initial pH of
the reaction solution with NaOH was 13, while those for ­Na2CO3 and ­NaHCO3
were less than 9. It is reported that glucose started to decompose in a strong alka-
line solution at pH above 11 [31]. Therefore, there were much more side reactions
for the glucose oxidation by the use of NaOH as additive. In addition, the use of
Mg(OH)2 as the additive also gives a high selectivity, but at a low glucose con-
version (Table 1, Entry 5). The reason should be that Mg(OH)2 is heterogeneous
that cannot effectively contact with substrate. Thus, ­Na2CO3 and ­NaHCO3 should
be the best base for the oxidation of glucose into gluconic acid over Pd/cellu-
lose catalyst without pH control. A control experiment was also performed in the
absence of the catalyst, and no oxidation product was produced.

Table 1  The effect of base on the oxidation of glucose into gluconic acid over Pd/cellulose catalyst
Entry Base Base amount Glucose Gluconic acid Gluconic acid
(mg) ­conversiona (%) ­yielda (%) ­selectivitya
(%)

1 Pyridine 85 0 0 0
2 NaOH 40 100 63.4 63.4
3 Na2CO3 53 76.6 69.6 90.9
4 NaHCO3 100 83.7 76.8 91.7
5 Mg(OH)2 58 23.9 22.6 94.5

Reaction conditions: Pd/cellulose (50  mg), a setting amount of base and glucose (180  mg) was added
into 10 ml of water. The reaction was started at room temperature with oxygen flow rate of 30 ml/min
a
 Calculated according to the HPLC results

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The effect of base amount on the oxidation of glucose over Pd/cellulose catalyst

Secondly, the oxidation of glucose was carried out with different amounts of
­Na2CO3 at room temperature over Pd/cellulose catalyst, and the results are shown
in Table 2. It can be seen that no oxidation products were observed in the absence
of ­Na2CO3 (Table  2, Entry 1), indicating that the base played a crucial role in
the oxidation of glucose into gluconic acid. It is reported that the major role of
base is that it can neutralize the oxidation product of gluconic acid to give the
product in the form of salt. Gluconic acid has a strong affinity to the metal nano-
particles, and thus, the deposition of gluconic acid on the surface of Pd/cellulose
catalyst will cause the catalyst deactivation. As shown in Table 2, an appropriate
amount of N ­ a2CO3 was necessary to get a high glucose oxidation rate and glu-
conic acid selectivity. Glucose conversion and gluconic acid yield increased with
an increase in the amount of ­Na2CO3. As discussed above, the base of ­Na2CO3
was mainly used to neutralize the product gluconic acid, and the gluconic acid
absorbing on the surface of the Pd/C catalyst will cause the catalyst deactiva-
tion. Therefore, much more amount of ­Na2CO3 accelerated the release of glu-
conic acid from the catalytic surface into the reaction solution. Thus, a higher
reaction rate was observed for glucose oxidation with a higher amount of ­Na2CO3
from 26.5 to 53 mg (Table 2, Entries 2 and 3). Furthering increasing the amount
of ­Na2CO3 from 106 mg to 212 mg, glucose conversion continuously increased,
while gluconic acid yield slowly decreased. The reason should be that much more
side reactions occurred when the amount of N ­ a2CO3 was beyond 106  mg. It is
reported that glucose was not very stable under high pH conditions. For example,
glucose can isomerize into fructose or degrade into lactic acid, formic acid, and
acetic acid under alkaline conditions [31]. Therefore, much more side reactions
were present when too much amount of ­Na2CO3 was used.

Table 2  Effect of amount of Entry Na2CO3 Glucose Gluconic acid Glucose

­Na2CO3 over Pd/cellulose amount (mg) ­conversiona ­yielda (%) ­selectivitya
catalyst at room temperature (%) (%)

1 0 0 0 0
2 26.5 17.7 16.6 93.7
3 53 36.2 33.1 91.4
4 106 45.8 30.6 66.8
5 159 56.7 26.3 46.4
6 212 68.4 21.2 31.0

Reaction conditions: Pd/cellulose (50 mg), a setting amount of base

and glucose (180 mg) was added into 10 ml of water. The reaction
was started at room temperature with oxygen flow rate of 30 ml/min
for 30 min
a
 Calculated according to the HPLC results

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Time course of glucose oxidation into gluconic acid

Figure  4 shows the time course of glucose oxidation over Pd/cellulose catalyst at
optimized condition. It can be seen that the Pd/cellulose was very active toward
the oxidation of glucose at room temperature. Glucose conversion of 36.2% was
achieved in a short reaction time of 15 min. Prolonging the reaction time, the glu-
cose conversion and gluconic acid yield gradually increased. Full conversion of glu-
cose was reached after 3 h at room temperature, and gluconic acid was obtained in
a yield of 91.2%. Interestingly, the gluconic acid yield remained stable even after
further prolonging the reaction time to 4 h, which indicated that the oxidation prod-
uct gluconic acid was stable under our reaction conditions. Thus, a high selectiv-
ity of gluconic acid can be achieved and little by-product would be produced under
our reaction conditions. The sharper slope of the curves of glucose conversion and
gluconic acid yield in the initial reaction stage than that in the latter reaction stage
should be due to the higher glucose concentration in the initial reaction stage.

Effect of catalyst loading on the oxidation of glucose into gluconic acid

The effect of the catalyst loading on the oxidation of glucose was also investigated,
and the results are shown in Fig. 5. Reactions were carried out at room temperature
for 30 min. It can be seen that the reaction rate of glucose conversion was linear to
the catalyst loading. The more the catalyst loading was, the higher the reaction rate
was. An increase in the reaction rate with the increase in the catalyst loading should
be due to the fact that much more catalytic sites were presented with much more
catalyst loading. As the glucose oxidation reaction, the absorption of glucose onto
surface of the catalyst was the rate-determining step for the oxidation of glucose;
therefore, the reaction rate increased with the increase in the catalyst loading. In
addition, it was noted that the selectivity of gluconic acid was almost the same with
different amounts of the Pd/cellulose catalyst. Thus, it indicated that the selectivity
of gluconic acid should be tightly connected with other parameters such as the kind
of the catalyst and the base.

Fig. 4  Time course of glucose

oxidation over Pd/cellulose 100
catalyst at room temperature.
Reaction conditions: Pd/cel- 80
lulose (50 mg), N
­ a2CO3 (53 mg)
Percentage (%)

and glucose (180 mg) were 60 Glucose

added into 10 ml of water. The Gluconic acid
reaction was started at room 40
temperature with oxygen flow
rate of 30 ml/min
20

0 50 100 150 200 250

Time (min)

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Fig. 5  The effect of catalyst 60

loading on the oxidation of Glucose conversion
glucose. Reaction conditions: a 50 Gluconic acid
setting amount of Pd/cellulose
catalyst, ­Na2CO3 (53 mg), and

Percentage (%)
40
glucose (180 mg) were added
into 10 ml of water. The reaction
was started at room temperature 30
for 30 min with oxygen flow rate
of 30 ml/min 20

10

0
10 20 30 40 50 60
Catalyst amount (mg)

Catalyst recycling experiments

Finally, the reusability experiment of the Pd/cellulose catalyst was investigated.

Reaction condition for this study was carried out for 3  h at room temperature
with 40  mg of the catalyst and 0.5 equiv N ­ a2CO3. After reaction, the catalyst
was recovered via centrifugation and the spent catalyst was washed with lots
of water. After drying, the spent catalyst was used for the next cycle under the
same reaction conditions. As shown in Fig.  6, no significant change in conver-
sion and selectivity to gluconic acid was observed up to five runs. Therefore, the
catalyst can be recycled without any significant loss in activity under the reaction
conditions.

Fig. 6  Reusability of the Pd/cel- 100

lulose catalyst for the oxidation
of glucose into gluconic acid.
80
Gluconic acid yield (%)

Reaction conditions: Pd/cel-

lulose catalyst (40 mg), ­Na2CO3
(53 mg), and glucose (180 mg) 60
were added into 10 ml of water.
The reaction was started at room
temperature for 3 h with oxygen 40
flow rate of 30 ml/min

20

0
1 2 3 4 5
Run (No.)

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Conclusion

In summary, a green and effective method was developed for the oxidation of glu-
cose into gluconic acid. The green biopolymer cellulose from cotton was used as a
support to stabilize Pd nanoparticles, and the resulting Pd/cellulose was found to
be an effective heterogeneous catalyst for the oxidation of glucose under mild con-
ditions. Different reaction parameters have been investigated, and it was found the
kind of the base and the amount of base showed a great effect on the oxidation of
glucose into gluconic acid. N ­ a2CO3 with the stoichiometric ratio produced high glu-
cose conversion and gluconic acid selectivity. High glucose conversion of 100% and
gluconic acid selectivity of 91.2% were obtained after 3 h at room temperature. In
addition, the catalyst could be easily recovered via centrifugation and showed no
loss of its catalytic activity during the five runs. The attractive features of cellulose
as support and a high catalytic activity of cellulose-supported Pd catalyst in glucose
oxidation would extend the scope of cellulose as a catalyst support for other kinds of
chemical reactions.

Acknowledgements  The Project was supported by Special Fund for Basic Scientific Research of Central
Colleges, South-Central University for Nationalities (YCZW15100).

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