Research On Catalytic Properties of Palladium Catalyst Prepared by Biological Reduction Method
Research On Catalytic Properties of Palladium Catalyst Prepared by Biological Reduction Method
Research On Catalytic Properties of Palladium Catalyst Prepared by Biological Reduction Method
Catalyst Research
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
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
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Zhang Feng, et al. Research on Catalytic Properties of Palladium Catalyst Prepared by Biological Reduction Method
surface measuring instrument made by the Beijing Jingweigaobo Science and Technology Development Center,
with a P/P0 in the range of 0.050.95.
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.
(1)
2.3Characterization of catalysts
The crystalline structure of catalysts was analyzed using
3.1.1XRD study
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-
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2013,15(2):24-30
3.1.2TEM study
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.
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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.
Zhang Feng, et al. Research on Catalytic Properties of Palladium Catalyst Prepared by Biological Reduction Method
27
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
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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.
Zhang Feng, et al. Research on Catalytic Properties of Palladium Catalyst Prepared by Biological Reduction Method
4Conclusions
Pd/ -Al2O3-B
References
[1] Klefenz H. Nanobiotechnology: From molecules to
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2013,15(2):24-30
nanoparticles on carbon nanotubes in supercritical carbon
dioxide[J]. Chem Commun, 2003(5): 642-643
10(3): 718-722
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