China Petroleum Processing and Petrochemical Technology

Catalyst Research

2013, Vol. 15, No. 2, pp 24-30

June 30, 2013

Research on Catalytic Properties of Palladium Catalyst

Prepared by Biological Reduction Method
Zhang Feng; Fu Jiquan
(School of Materials Science and Engineering, Beijing Institute of Fashion Technology, Beijing 100029)
Abstract: This paper relates to highly dispersed supported Pd/MWCNTs and Pd/-Al2O3 catalysts prepared by biological
reduction method. The physico-chemical properties and the difference in catalytic activity of Pd catalysts prepared by biological reduction method and chemical method, respectively, were investigated using XRD, TEM and specific surface characterization methods. The catalytic properties of catalysts were studied through activity evaluation means. The test results
showed that the catalysts prepared by biological method were characteristic of small Pd nanoparticle size, good dispersion
and low agglomeration, while possessing a high activity and stability in styrene hydrogenation reaction in comparison with
catalysts prepared via the chemical method.
Key words: Pd/MWCNTs; Pd/- Al2O3; biological reduction; ginkgo leaf; Pd nanoparticles

1Introduction
Catalyst with precision metal nanoparticles deposited on
a support plays a dominant role in the field of oil refining, petrochemical industry and environmental protection
thanks to its superior catalytic activity and selectivity.
The traditional methods for preparing precious metal
nanoparticles include physical method and chemical
method. The catalyst preparation process using the physical method is simple, but the requirement on equipment
is high and the production cost is expensive; the chemical
method is flexible and diversified, but it should be realized with chemical reagents, which will bring about some
environmental pollution problems. The biological reduction method for preparing precious metal nanoparticles is
becoming a research focus in the field of nanometer scale
technology along with the increasingly active research on
greenization technology for preparation of materials [1].
Upon using biological method to prepare precious metal
nanoparticles, there is no need to add additional chemical reagents, and pollution is reduced along with a full
utilization of rich biological resources and biomass as
the reducing agent[2-4]. Huang, et al.[5] prepared gold and

(CNTs) having good chemical stability and high specific

surface area are the excellent support for active catalytic
component[6-7]. The researchers have developed CNTs as
the catalyst support that has been used in hydrogenation,
dehydrogenation, and oxidation reactions[8-9]. The research
on catalyst prepared by biological reduction method using carbon nanotubes as the support has not been reported
previously.
This study prepared a series of catalysts using ginkgo leaf
extract as a reducing agent, with MWCNTs (multi-walled
carbon nanotubes) and -Al2O3 serving as the support.
The catalysts were characterized through XRD, TEM and
specific surface area measurements, and the performance
of catalysts was investigated through styrene hydrogenation to produce ethylbenzene for activity evaluation purposes.

2Experimental
2.1Preparation of extract
Five gram of ginkgo leaf powder was added to a conical
flask filled with 250 mL of deionized water. The conical
flask was oscillated for 12 h at 60 . Insoluble biomass

silver nanoparticles through reduction using camphor

Recieved date: 2013-01-31; Accepted date: 2013-03-30.

leaf extract, and the addition of chemical reagent was not

Corresponding Author: Professor Fu Jiquan, Telephone: +86-

needed during the preparation process. Carbon nanotubes

10-64288291; E-mail: fujq010@sina.com.

24

Zhang Feng, et al. Research on Catalytic Properties of Palladium Catalyst Prepared by Biological Reduction Method

was removed by centrifugation after being cooled down.

The obtained supernatant liquid was the ginkgo leaf extract at a concentration of 20 g/L, which was then stored

surface measuring instrument made by the Beijing Jingweigaobo Science and Technology Development Center,
with a P/P0 in the range of 0.050.95.

in refrigerator at 4 prior to use.

2.4Evaluation of catalyst activity

2.2Preparation of catalyst

The reaction of styrene hydrogenation to form ethylbenzene was used as the probe reaction for evaluating the
catalyst activity. The main reaction proceeds according to
Formula (1), and this reaction only generates ethylbenzene under this condition, with the catalytic selectivity
reaching 100%. 0.1 g of catalyst (with a particle size of
60-100 mesh) was weighed and added to the continuous
micro-reactor device. H2 flow was controlled at a rate of
80 ml/min, and the space velocity on catalyst was 20 h-1,
with anhydrous ethanol used as solvent at a volume ratio
of 1:1. The reaction temperature was 120 , and sampling was performed at regular intervals. The composition
of reaction products was analyzed by a GC-7890 gas
chromatography system (made by the Beijing Tianmei
Instrument Company), equipped with a HJ-1 capillary
column measuring 0.25 mm25 m and a FID detector,
with the temperature in column equating to 100 , in the
sample room200 , and in the detection room200 .
The content of each component was calculated by means
of the area normalization method.

A series of palladium catalysts supported on MWCNTs

(including MWCNTs-0, Pd/MWCNTs-C, and Pd/
MWCNTs-B) and on -Al2O3 (including -Al2O3-0, Pd/
-Al2O3-C, Pd/-Al2O3-B) were prepared respectively.
Herein, 0 denotes the pure support (the pure support was
prepared in order to study the influence of the said support
on catalytic activity), C denotes the chemical method, and
B denotes the biological method. A required concentration
of palladium nitrate solution was prepared. An excess of
palladium solution was used to impregnate multi-walled
carbon nanotubes and -Al2O3 was used as the support for
6 h, followed by drying for 12 h at 60 . Pd/MWCNTs-C
catalyst and Pd/-Al2O3-C catalyst were prepared by the
chemical method. A certain amount of palladium nitrate
solution was mixed with the same amount of ginkgo leaf
extract. The excessive amount of the solution was used to
impregnate multi-walled carbon nanotubes and -Al2O3
for 12 h. Thus, the Pd/MWCNTs-B catalyst and Pd/
-Al2O3 -B catalyst were prepared by the biological method after being dried for 24 h at 60 . A series of catalysts

(1)

using -Al2O3 as the support were calcined respectively

for 2 h at 500 , and were then reduced in the hydrogen
flow.

2.3Characterization of catalysts
The crystalline structure of catalysts was analyzed using

3Results and Discussion

3.1Characterization of catalysts

a D8 Advance high-power X-ray diffractometer with a ro-

3.1.1XRD study

tating target (made by the Bruker company), operating at

Six prepared catalysts were characterized by XRD method in order to investigate whether the palladium loading
could affect the structure of catalyst support and the crystalline structure of palladium on the catalyst.
Figure 1 depicts XRD patterns of a series of catalysts supported on MWCNTs, and Figure 2 shows XRD patterns
of a series of catalysts supported on -Al2O3. It can be
seen from the spectral line of MWCNTs-0 shown in Figure 1 that the diffraction peaks of crystal planes (002) and
(101) in carbon nanotubes appear at 2=25.87 and 42.7,
respectively, while other peaks are not obvious. The dif-

a tube voltage of 40 kV, a tube current of 250 mA, a scan

step size of 0.02/step, and a scan range of 1090. The
morphology of catalysts was observed using a JOELs
JEM2100 transmission electron microscope. The highresolution TEM images were obtained by a high magnification transmission electron microscope (JEM2100) at an
accelerating voltage of 200 kV after dipping the ultra-thin
carbon film in reaction solution followed by drying. Specific surface area and pore volume of each catalyst were
measured by utilizing a pore distribution and specific

25

China Petroleum Processing and Petrochemical Technology

Figure 1XRD patterns of MWCNT and Pd/MWCNTs

catalyst samples

2013,15(2):24-30

It can also be learned from XRD patterns that there was

a diffraction peak of Pd0 phase at 33.04, indicating that
a part of Pd0 species was also deposited on the surface
of MWCNTs. The reason was that the grain size of Pd0
supported on the surface of MWCNTs was small, and it
could be oxidized easily by the oxygen in air. So it could
be reduced first in hydrogen stream before the commencement of catalytic reaction in the presence of Pd/MWCNTs
catalyst.
It can be seen from the XRD patterns of Pd/Al2O3-C
and Pd/Al2O3-B presented in Figure 2 that the supported Pd samples show characteristics diffraction peaks of
crystal planes (111), (200) and (220) of Pd species at 2
of 39.67, 46.0 and 67.02, respectively. This suggests
that palladium species also existed in the form of single
element on the surface of Al2O3 support.

3.1.2TEM study

Figure 2XRD patterns of -Al2O3 and Pd/- Al2O3

catalyst samples

fraction peak of crystal plane (002) is wide, and its diffraction peak is high, suggesting that the degree of longrange order of nanostructure is poor. This may be caused
by superposition of diffraction peaks of impurities such
as amorphous carbon and graphite particles. It is known
that the carbon nanotubes-supported Pd still retains the
characteristics diffraction peaks of crystal planes (002)
and (101) in carbon nanotubes and their diffraction peak
intensity is relatively weak upon comparing the spectral
lines of MWCNTs-0, Pd/MWCNTs-C and Pd/MWCNTsB presented in Figure 1. These results indicated that the
structure of carbon nanotubes was not destroyed, and
could serve as excellent support of palladium. It can be
learned from Figure 1 that Pd/MWCNTs-B has characteristics diffraction peaks of crystal planes (111), (200),
(220) and (311) of Pd at 2 of 40.06, 46.59, 68.13 and
82.11, respectively upon comparing XRD patterns of Pd/
MWCNTs-C and Pd/MWCNTs-B. This has revealed that
ginkgo leaf extract could reduce Pd2+ ions to Pd0 species,
which were then deposited on the MWCNTs support. So
ginkgo leaf extract is a good reducing agent for Pd2+ ions.

26

XRD characterization confirmed that the palladium loading did not affect the structure of support, and palladium
existed in the form of single element. TEM characterization was carried out in order to further study the surface
morphology of the catalyst as well as the concentration
and particle size of palladium particles.
Figure 3 shows HRTEM images of Pd/MWCNTs catalysts. It can be seen from Figure 3 that the MWCNTs
supported Pd species retain a good tubular morphology.

Figure 3HRTEM images of Pd/MWCNTs catalysts

Zhang Feng, et al. Research on Catalytic Properties of Palladium Catalyst Prepared by Biological Reduction Method

We can see from the HRTEM images by comparing Pd/

MWCNTs-C and Pd/MWCNTs-B that Pd nanoparticles
are supported on the inner wall of MWCNTs in the Pd/
MWCNTs-C catalyst. However, the distribution of Pd
nanoparticles is more uniform, and the Pd nanoparticles
are supported on the outer and inner walls in the Pd/
MWCNTs-B catalyst prepared by the biological reduction method. It can be concluded that Pd nanoparticles
had obvious lattice fringes as demonstrated by the highresolution lattice image of the Pd/MWCNTs-B catalyst.
Thus, the formation of crystalline Pd was verified, which
was consistent with the XRD characterization results.
The particle size distribution of Pd nanoparticles existing
in the form of single element in Pd/MWCNTs-B and Pd/
MWCNTs-C catalysts was calculated, with the results
shown in Figure 5. We can see that when the particle size
is small, the range of particle size distribution is narrow,
and the average size of Pd particles is about 4 nm in the
Pd/MWCNTs-B catalyst. We also can see that when the
particle size is big, the range of particle size distribution
is broader, and the average size of Pd particles is about
14.8 nm in the Pd/MWCNTs-C catalyst.
Figure 4 shows HRTEM images of Pd/-Al2O3 catalyst.
It can be seen from Figure 4 that -Al2O3-supported Pd
retains a good morphology. By comparing TEM images
of Pd/-Al2O3-C and Pd/-Al2O3-B we can know that pal-

Figure 4HRTEM images of Pd/- Al2O3 catalysts

Figure 5Particle size distribution for supported Pd

nanoparticles Frequency

ladium nanoparticles supported on the surface of -Al2O3

can agglomerate to certain extent to form larger particles
than that prepared by the biological method. However,
palladium particle distribution in Pd/-Al2O3-B catalyst
prepared by the biological reduction method is more uniform and the particle is finer. This phenomenon may be
attributed to the existence of biomass which makes the
distribution of active components of catalyst more uniform during its preparation by the biological method, and
Pd species exist in the form of single element in a reduced
state. Thus, the agglomeration of active components was
effectively avoided during the process of calcination.
It should be noted that Pd supported on -Al2O3 at first
existed in an ionic form, then turned to be single elemental Pd after calcination and reduction that took place in
chemical immersion method. However, Pd was reduced
directly on the support upon being treated by the biological reduction method. The two preparation methods were
different in nature. It can be concluded that the supported
Pd nanoparticles had obvious lattice fringes upon analyz

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China Petroleum Processing and Petrochemical Technology

ing the high-resolution lattice images of Pd nanoparticles

obtained by the biological reduction method. This outcome confirmed the existence of crystalline Pd, which
was consistent with the XRD characterization results.

3.1.3Specific surface area

The specific surface area and pore volume of two series
of catalysts were characterized, and the results are listed
in Table 1.
Table 1BET surface area measurements
No.

Sample

S, m2/g

Vp, cm3/g

MWCNTs-0

139.16

0.63

Pd/MWCNTs-C

165.47

0.55

Pd/MWCNTs-B

169.55

0.49

Al2O3-0

102.42

0.32

Pd/Al2O3-C

91.99

0.67

Pd/Al2O3-B

149.66

0.46

It can be seen from Table 1 that the specific surface of

catalyst samples varies to different extent ranging from
139.16 m2/g for support itself to 165.47 m2/g for catalyst
prepared by the chemical method and 169.55 m2/g for
catalyst prepared by the biological method due to the
use of different methods for supporting palladium with
MWCNTs. The reason is that the carbon nanotube is characteristic of a tubular structure. The overall specific surface of catalyst increases due to large specific surface area
of the palladium particles that are deposited on inner and
outer walls of the nanotubes. The specific surface area
of catalyst prepared by the biological method was larger
than that of catalyst prepared by the chemical method (as
evidenced by comparison between Pd/MWCNTs-C and
Pd/MWCNTs-B). The reason may be that Pd particles
prepared by the biological method were larger in dimension, and were deposited on the inner and outer walls in
a reduced state, leading to larger specific surface area.
The pore volume of palladium catalyst with MWCNTs
functioning as the support was smaller. This is because Pd
particles supported on MWCNTs were embedded inside
the carbon nanotubes, resulting in the blocking of a part
of carbon nanotubes. Some carbon nanotubes were hollow, leading to the reduction of effective pore volume.
This finding was consistent with the results shown by

28

2013,15(2):24-30

TEM measurements.
For catalysts supported on -Al2O3, the specific surface
area of Pd/-Al2O3-C prepared by the chemical method
was 91.99 m2/g, which was lower than 102.42 m2/g for
the -Al 2O 3-0 support. However, the specific surface
area of Pd/-Al2O3-B prepared by the biological method
was 149.66 m2/g, which was greater than the -alumina
support. This is probably because palladium particles
prepared by the chemical method agglomerated on the
surface of -Al2O3 during the process of calcination, and
the particle size was greater, which blocked a part of the
carbon nanotubes. The palladium nanoparticles supported
on the surface were mainly in the form of single element
on the Pd/-Al2O3-B catalyst, and its particle size was
small, which would not cause the blocking of nanotubes.
The protective effect of biomass could be better utilized,
so agglomeration would not easily take place during
calcination. Due to large specific surface area of small
particles, the overall specific surface area of the catalyst
increased. The increase of pore volume was probably due
to the acid etching effect of palladium nitrate solution
(with a pH value of 1.0) on the surface of support during the process of impregnation, leading to an increased
pore volume[10]. The pore volume of Pd/-Al2O3-B was
smaller compared with Pd/-Al2O3-C due to the buffering
effect of biomass, which could weaken the acid etching
effect during the process of catalyst preparation by the
biological method.

3.2Evaluation of catalyst activity

The conversion of styrene during catalytic hydrogenation
reaction on Pd/-Al2O3-C and Pd/-Al2O3-B catalysts is
shown in Figure 6.

Figure 6Effect of reaction time on conversion of styrene

Pd/-Al2O3-B; Pd/-Al2O3-C

Zhang Feng, et al. Research on Catalytic Properties of Palladium Catalyst Prepared by Biological Reduction Method

It can be seen from Figure 6 that two catalysts have a

high activity and stability in catalytic hydrogenation reaction of styrene. The activity of each catalyst is still high
even after continuous reaction for 20 h. The catalytic performance of catalyst prepared by the biological method
is better. The space velocity on styrene hydrogenation
catalyst was increased from 20 h-1 to 200 h-1 in order to
evaluate the catalytic activity of various catalysts. The
activities of 6 catalyst samples were evaluated, and the results are shown in Figure 7. It can be seen from Figure 7
that the catalytic activity of catalysts varies significantly.
The catalytic activity of MWCNTs-0 and Pd/-Al2O3-0
comprising pure support is close to zero, indicating that
pure support materials MWCNTs and -Al2O3 have no
catalytic activity.

these two catalysts identified at the beginning of reaction

was resulted from the hydrogen reduction of catalysts. Pd/
MWCNTs-B catalyst began to show a much higher activity than that of Pd/MWCNTs-C catalyst in 2.5 h after the
start of run. The reason is that the dispersion of palladium
particles prepared by the biological reduction method was
better, resulting in a uniform distribution of palladium on
the inner and outer walls of carbon nanotubes with high
stability. However, the stability of Pd/MWCNTs-C catalyst prepared by the chemical method was lower, which
was consistent with the results obtained from TEM characterization. The activity of two catalysts all decreased
due to the loss of active component with the extension
of reaction time. Although the activity of both of them
decreased, the activity of Pd/MWCNTs-B was slightly
higher than that of Pd/MWCNTs-C after 2.5 h of reaction.
In general, the activity of catalysts prepared by the biological method was higher than that of catalysts prepared
by the chemical method.
The activity of Pd/-Al2O3-B catalyst prepared by the biological method was even higher than that of Pd/- Al2O3C catalyst prepared by the chemical method as indicated
by the two curves of catalysts using -Al2O3 as the support.

Figure 7Effect of different catalysts on conversion of styrene

4Conclusions

MWCNTs-0; Pd/MWCNTs-C; Pd/MWCNTs-B;

Pd/-Al2O3-0; Pd/-Al2O3-C;

Pd/ -Al2O3-B

Upon comparing Pd/MWCNTs-C, Pd/MWCNTs-B and

Pd/-Al2O3-C and Pd/-Al2O3-B catalysts, it can be learned
that the catalytic activity of catalyst using MWCNTs as
the support was higher than that of catalyst using -Al2O3
as the support, which might be probably attributed to the
nanometer effect of carbon nanotubes. The structure of
carbon nanotube itself provides a larger specific surface
area, which significantly increases the support area and
contributes to the uniform distribution of active component of catalyst. This view has already been demonstrated
from previous characterizations. Therefore, the catalysts
using MWCNTs as the support have a higher activity
based on the same amount of catalyst support.
The results showed that Pd/MWCNTs-C and Pd/
MWCNTs-B catalysts all had a higher activity with carbon nanotubes serving as the support. The high activity of

1) MWCNTs containing no functional groups can be used

as a good support for palladium catalyst. The MWCNTsupported catalyst had a higher activity compared with
traditional Al2O3-supported catalyst, and had revealed
considerable development potential.
2) The biological reduction method using ginkgo leaf
extract can directly reduce Pd2+ ions to Pd0 species. The
biological method has the advantages of good dispersion,
small particle size of active component and low agglomeration of Pd particles.
3) Palladium catalysts prepared by the biological reduction method had higher activity and better stability than
that of catalysts prepared by the chemical method under
the reaction system adopted by this study.

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Massive Production of Zeolite Catalyst for Phenol/Acetone Production

On March 20, 2013 the Petrochemical Research Institute
of Jilin Petrochemical Company (JPC) had for the first
time successfully manufactured one m3 of the MCM-49
zeolite, symbolizing its capability to produce in commercial scale the MCM-49 zeolite. This catalyst is expected
to be applied on JPCs 125 kt/a phenol/acetone unit,
which can bring about an incremental economic benefit
amounting to 15 million RMB a year.
Currently JPC adopts the zeolite Y to manufacture isopropanol on the phenol/acetone unit. Since high benzene/
olefin ratio and high temperature are required for conducting the isopropanol alkylation reaction, there are a lot of
disadvantages such as large volume of circulating materials in the system, high energy consumption for product
separation, low production efficiency, and excessive byproducts. The catalyst needs to be flushed periodically
with hot benzene for regeneration, which would result in
high safety hazards and extended non-productive duration.
Application of the MCM-49 zeolite can reduce the benzene/olefin ratio and reaction temperature during the
alkylation reaction along with decreased raw materials

30

and energy consumption. Furthermore, this catalyst does

not need benzene flushing and can extend its service life
to 36 years, thus avoiding safety hazards arising from
flushing of zeolite by hot benzene, reducing catalyst replacement frequency, and extending production cycle to
raise the techno-economic level of cumene production to
a higher rung.
It is told that this research institute has performed optimization tests in commercial scale at the side cut of production unit after implementing two 1500-hour stability tests
running at a temperature of 130 , a propylene space velocity of 1.0 h-1, a benzene/olefin ratio of 6, and a recycle
ratio of 8 and 6, respectively. This unit has been operating
for 5000 h to achieve a propylene conversion of 100%.
Upon using a composite catalyst consisting of mainly
the HMCM-49 zeolite for transalkylation of polyisopropylbenzenes with benzene at a temperature of
190 the conversion of di-isopropylbenzene and tri-isopropylabenzene reached 58.3% and 50.3%, respectively,
which would command a domestic leading position with
all indicators reaching or exceeding those of imported
catalysts.