Advanced Materials Research Vol.

412 (2012) pp 235-238

Online available since 2011/Nov/29 at www.scientific.net
© (2012) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.412.235

Nano-Au/C Catalysts for the Selective Oxidation of Glucose into

Gluconate

Zijing Li1,2,a, Dushu Huang1,2, Wei Liu1,2,b, Ruimin Xiao1,2, Jie Liu3,
Chun Xu1,2 , YanJiang1,2 and Lida Sun1,2
1
Science College, Honghe University, Mengzi 661100, P. R. China
2
Key Laboratory of Natural Pharmaceutical & Chemical Biology of Yunnan Province, Mengzi
661100, P. R. China
3
Assets Administration of Honghe University, Mengzi 661100, P. R. China
a
lizijing@gmail.com,b liuwei4728@126.com (Corresponding author)

Keywords: gold catalyst, liquid phase oxidation, glucose, gluconate

Abstract. Au/C catalyst used for the liquid phase selective oxidation of glucose to gluconate was
prepared by gold sol method that includes the preparation of metallic colloid by citrate reduction and
subsequent immersion by carbon support. The influence of gold particles of different size on the
activity of Au/C catalyst was studied. The results show that the catalyst with good dispersed spherical
gold particles has higher catalytic activity. After 16 runs, the conversion of glucose selective
oxidation can still achieve over 96% under mild reaction conditions.

Introduction
Recent years, the study and application of gold catalysis have attracted considerable attention from
scientists, because nanotechnology has transformed gold from a marginal into a very effective catalyst
with unique properties [1]. The field of the fundamental and applied research for gold catalyst mainly
focuses on pollution control, chemical processing and fuel cells etc.[2-6] For the liquid phase
oxidation reactions of polyols, the previous studies by Prati and co-workers [7-10] have shown that
carbon-supported gold catalyst exhibits very high catalytic activity and selectivity, because of less
sensitive to overoxidation and/or self-poisoning than platinum or palladium. As far as the preparation
of Au/C catalyst is concerned, gold sol method is a preferred tool. These authors used chemical
reduction method to prepare gold sol by sodium borohydride (NaBH4) as reducing agent and by PVA
or PVP as protective agent, and then immobilized it on active carbon at stirring vigorously, resulting
in a very effective catalyst with 7-8 nm gold particles in an average diameter. Using the Au/C catalyst,
the selective oxidation of glucose to gluconic acid was performed under mild conditions [10].
To obtain carbon-supported gold catalyst with high catalytic activity, the present paper focuses on
the study of the preparation and characterization, because the catalytic performances of gold catalysts
markedly depend on the preparation methods and conditions [11]. The size controlled colloidal gold
nanoparticles which used as precursors of gold catalysts were generated by glucose reduction [12],
subsequently were immobilized on active carbon. The size, shape and size distribution of Au nano-
particles in the colloidal solution and on activated carbon surface were characterized by transmission
electron microscopy (TEM). In order to evaluate the catalytic activity of resulting Au/C catalyst, we
also chose the liquid phase selective oxidation reaction of glucose to gluconic acid [10], because
gluconic acid and its salts are important products of fine chemical industry, for example, being used as
water-soluble cleansing agents, additives in food and beverages as well as medicine and so on.
The influence of gold nanoparticles with different size on the activity of Au/C catalyst was studied
in detail.

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236 Chinese Ceramics Communications II

Experimental
Reagents and apparatus. Tetrachloroauric acid (HAuCl4) was prepared from pure gold (99.99 %).
All chemical reagents used are of analytical-reagent grade. Double distilled water was used for all
preparations and catalytic experiments. All glassware was rigorously cleaned with chromic acid
solution and rinsed in turn with distilled water before use. The granularity of activated carbon was
approximately 160 µm, specific surface area is 1000 m2/g.
Size, shape and size distribution of gold nanoparticles in the solution and on catalyst surface were
characterized in a 250 mL conical flask. The solution was heated up to a boil, and 15 mL of 5 %
aqueous glucose was added while stirring vigorously, keeping boiling for 10-20 min. The mixture
solution underwented a series of color changes before finally turning wine red and cooling to room
temperature.
The colloidal solution obtained was immersed by active carbon support under condition of stirring
vigorously. The amount of support was calculated as having a final gold loading of 1 wt%. After about
2 h stirring, the carbon of supporting gold was filtered, and the filtrate became colorless. The resulting
catalyst was washed with hot water until the filtrate was chloride free (AgCl test), and was used in the
wet form.
Approximately 200 nanoparticles from each sample were observed using a transmission electron
microscopy, operating voltage at 200 kV, to measure particle sizes and size distribution.
Preparation of catalyst. Colloidal solution of glucose-reduced gold ions were prepared according
to Frens method [12]. 1 mL HAuCl4 aqueous solution (6.00 mg/mL) and 150 mL water were added to
a 250 mL conical flask. The solution was heated up to a boil, and 15 mL of 5 % aqueous citrate was
added while stirring vigorously, keeping boiling for 10-20 min. The mixture solution underwented a
series of color changes before finally turning wine red and cooling to room temperature.
Oxidation of glucose. The oxidation reactions of glucose were carried out in a thermostatted glass
reactor of 500 ml with a stirring rate of approximately 600 r/min. Glucose solution (10 wt%) was
added to the reactor in the presence of Au/C catalyst and oxidized by bubbling oxygen at atmospheric
pressure and controlling temperature 55 ~ 60°. Mass ratio of glucose to gold is 1000:1 and the mixture
solution pH was controlled within 8-9 through adding dropwisely a solution of 0.5 M NaOH in whole
the course of reaction. After adding small amount of NaOH solution, the pH of the mixture solution
slowly dropped to 8.2 and kept no change for 10min at least, indicating a complete oxidation reaction.
The content of gluconate in the reaction solution was determined by the spectrophotometric method,
calculating conversion of the catalytic oxidation of glucose.

Results and Discussion

Preparation and TEM characterization of gold catalyst. In the chemical preparation of gold
nanoparticles, the most widely studied reagent is glucose which acts as both reducing agent as well as
stabilizer. By varying the glucose to gold ion ratio, it is possible to prepare monodispersed colloidal
particles with different size. In general, the minimum average diameter prepared gold particles is 12
nm by this method. In our work, the mass ratio of glucose to gold ion was controlled at 40:1 and80:1,
good dispersed spherical gold particles with a mean diameter of 10 and 15 nm were obtained,
respectively.
After the colloidal gold solutions were immersed with active carbon, respectively, the catalysts of
different gold size were obtained. The average diameter of gold nanoparticles characterized with
TEM on carbon surface is10.0 and 15.0 nm, respectively. TEM images of gold nanoparticles prepared
at the mass ratio of 40:1 were shown in Fig. 1 and Fig. 2 before and after the immersion. Obviously,
after gold colloid was immobilized on active carbon, the size and dispersity of particles were no
distinct change.
Effect of size and protective agent on the activity. For liquid phase selective oxidation of diols,
it has been proved that the Au/C catalyst with gold particles of 7 ~ 8 nm in a mean diameter has higher
catalytic activity [13].
 Advanced Materials Research Vol. 412 237

Fig. 1 TEM images of gold nanoparticles Fig. 2 TEM images of Au/C

100

80
Conversion/%

60

40
10.0 nm
20 15.0 nm

00 10 20 30 40 50 60
Reaction time/min
Fig. 3 Dependence of the conversion of glucoseon the sizes of gold nanoparticles

In the present paper, the effect of gold particle size on the activity of the Au/C catalyst was further
studied. Fig. 3 indicated the dependency of the conversion for oxidation of glucose to gluconate on
gold particle sizes, using above three gold catalysts. It is clear that the catalytic activity depends
strongly on the size of gold nanoparticles and decreases with increasing nanoparticle size for a certain
activated carbon support. A high reactive conversion of glucose oxidation can be achieved with the
catalyst of 10.0nm gold particles.
Selective oxidation of glucose. The oxidation of glucose was carried out by the 2.3 procedures,
using same Au/C catalyst with gold particles of 10 nm in diameter. The results showed that after 14
runs, the conversion of glucose to gluconate still achieves over 96% and the selectivity is higher than
98%. The dissimilarity in the course of recycling test is that the complete oxidation of glucose can
finish within 45 min in the front three runs; subsequently, the reactive time required gradually
increased with an increase of number runs and the complete reactive time is 120min for sixteenth
runs. This indicated that activity of the catalyst slowly decreased.

Conclusion
Recent research confirms that carbon supported gold catalyst is very effective for the liquid selective
oxidation of glucose. In the present study, we obtained the following conclusions.
(1) The Au/C catalyst used for the oxidation of glucose to gluconate can be produced by gold sol
method that includes the preparation of colloidal gold nanoparticles by citrate reduction and
subsequent immersion by carbon support.
(2) The Au/C catalyst with good dispersed gold nanoparticles of 10 nm in an average diameter has
high activity for the liquid phase oxidation of glucose.
238 Chinese Ceramics Communications II

Acknowledgment
This work was supported by the Public Welfare Scientific Research Project of the People's Republic
of China(NO.200810998),XSS of Honghe University(NO.XSS08011), Special projects of Honghe
University research institutes(NO. 10JGZ101) ,The Organic Chemistry key discipline construction of
Yunnan Province and Key Laboratory of Natural Pharmaceutical & Chemical Biology of Yunnan
Province.

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Chinese Ceramics Communications II
10.4028/www.scientific.net/AMR.412

Nano-Au/C Catalysts for the Selective Oxidation of Glucose into Gluconate

10.4028/www.scientific.net/AMR.412.235

DOI References
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