Catalytic application of biogenic platinum nanoparticles for the hydrogenation of cinnamaldehyde to cinnamyl alcohol

Article abstract of DOI:10.1080/15533174.2013.862813

Pt catalysts and Co doped Pt catalysts with TiO2 as the support were prepared by the sol immobilization method based on biological synthesis process, whereby Pt nanoparticles (PtNPs) were reduced from Na₂PtCl₄ using Cacumen Platycladi extract (CPE). The catalytic performance of the catalysts was studied using hydrogenation of cinnamaldehyde as the model reaction. For comparison, Co doped Pt/catalysts were also prepared by traditional impregnation method, TEM observation, and XRD measurement were carried out to characterize the catalysts. The effects of different Pt loadings and Co doping amounts were investigated. The results showed that the PtNPs could be well dispersed onto the TiO₂ support with narrow size distribution between 4 and 6 nm. 1.0% was observed as the optimal Pt loading amount in our experiments showing a cinnamaldehyde conversion of 73.3% with 68.8% selectivity to cinnamyl alcohol. A proper Co doping amount was also essential to the catalytic performance of the prepared Pt/catalysts as well as a favorable for the reaction process, 1.0% doping amount showed the best activity in which a 70.4% conversion and 88.3% selectivity was achieved. Recyclability tests carried out revealed that the 1.0 Co-1.0 Pt/TiO₂ catalysts possessed possessing good durability. In this work, Co-Pt/TiO₂ catalysts prepared by the sol immobilization method based on biological reduction process, showed better selectivity than that from traditional impregnation method.

Full text of DOI:10.1080/15533174.2013.862813

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Catalytic Application of Biogenic Platinum
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Cinnamaldehyde to Cinnamyl Alcohol
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b
b
Bingyun Zheng , Xiaolian Jing , Tareque Odoom-Wubah , Tao Kong , Huimei Chen , Daohua
b
b
b
Sun , Jiale Huang & Qingbiao Li
a
Environment & Biochemical Engineering School, Putian University, Putian, P. R. China
Department of Chemical and Biochemical Engineering, College of Chemistry and Chemical
b
Engineering, Xiamen University, Xiamen, P. R. China
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Qingbiao Li (2015) Catalytic Application of Biogenic Platinum Nanoparticles for the Hydrogenation of Cinnamaldehyde
to Cinnamyl Alcohol, Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 45:7, 967-973, DOI:
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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry (2015) 45, 967–973
Copyright © Taylor & Francis Group, LLC
ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2013.862813
Catalytic Application of Biogenic Platinum Nanoparticles for
the Hydrogenation of Cinnamaldehyde to Cinnamyl Alcohol
1
,2
2
2
2
2
BINGYUN ZHENG , XIAOLIAN JING , TAREQUE ODOOM-WUBAH , TAO KONG , HUIMEI CHEN ,
2
2
2
DAOHUA SUN , JIALE HUANG , and QINGBIAO LI
1
Environment & Biochemical Engineering School, Putian University, Putian, P. R. China
2
Department of Chemical and Biochemical Engineering, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen,
P. R. China
Received 16 April 2013; accepted 2 November 2013
Pt catalysts and Co doped Pt catalysts with TiO as the support were prepared by the sol immobilization method based on biological
2
synthesis process, whereby Pt nanoparticles (PtNPs) were reduced from Na PtCl using Cacumen Platycladi extract (CPE). The
2
4
catalytic performance of the catalysts was studied using hydrogenation of cinnamaldehyde as the model reaction. For comparison,
Co doped Pt/catalysts were also prepared by traditional impregnation method, TEM observation, and XRD measurement were
carried out to characterize the catalysts. The effects of different Pt loadings and Co doping amounts were investigated. The results
showed that the PtNPs could be well dispersed onto the TiO support with narrow size distribution between 4 and 6 nm. 1.0% was
2
observed as the optimal Pt loading amount in our experiments showing a cinnamaldehyde conversion of 73.3% with 68.8%
selectivity to cinnamyl alcohol. A proper Co doping amount was also essential to the catalytic performance of the prepared Pt/
catalysts as well as a favorable for the reaction process, 1.0% doping amount showed the best activity in which a 70.4% conversion
and 88.3% selectivity was achieved. Recyclability tests carried out revealed that the 1.0 Co–1.0 Pt/TiO2 catalysts possessed
possessing good durability. In this work, Co-Pt/TiO catalysts prepared by the sol immobilization method based on biological
2
reduction process, showed better selectivity than that from traditional impregnation method.
Keywords: biosynthesis, Pt, sol immobilization, cinnamaldehyde
Introduction
directed toward the intracellular or extracellular biosynthesis
of PtNPs using microorganisms under mild conditions with-
[
2–5]
Pt and its alloys are mainly used as excellent catalysts for oxi- out auxiliary capping agents.
However, subsequent proc-
dation and hydrogenation processes in the petrochemical essing of NPs via intracellular biosynthesis is generally
[
1]
industry. With the development of nanotechnology, Pt difficult, and microorganisms used for the extracellular bio-
[
6]
nanoparticles (PtNPs) have been demonstrated to exhibit synthesis of NPs must be extensively screened. Living
high catalytic activity, owing to their high surface area, mak- plants, plant extracts, and plant biomass are attracting more
ing synthesis of PtNPs for catalytic applications one of the attention as simple but effective alternative candidates for the
[
1]
highlights in related fields.
Consequently, well-defined extracellular biosynthesis of PtNPs. For example, Diospyros
[
7]
[8]
PtNPs of particular shapes and sizes have been synthesized kaki leaf extract, Cochlospermum gossypium extract, and
[
9]
through various methods. However, conventional physical honey have recently been used to prepare PtNPs. Interest-
and chemical methods are not only energy intensive, because ingly, biogenic PtNPs produced by using honey can be used
of stringent conditions, but also environmentally unfriendly, as catalysts for reacting aniline with 4-aminoantipyrine in an
due to the use of toxic solvents or additives. Compared with acidic aqueous medium.
conventional methods, biosynthetic methods based on micro- Cinnamyl alcohol is an important a,b-unsaturated alco-
[
9]
organisms or plants have been regarded as cost-effective and hol; it is a raw material and an intermediate with a wide
environmentally benign approaches for producing highly sta- range of applications in medicine, bactericide, fragrance,
[
10,11]
ble metal NPs in recent years. Some efforts have been cosmetics, and pesticides.
At present, cinnamyl alco-
hol is industrially produced in two ways: one approach
involves the saponification of storax oil and cinnamon oil,
among others, using hot NaOH solution, whereas the other
refers to the reduction of cinnamaldehyde by benzyl alco-
hol aluminum or aluminum isopropoxide. Both methods
are costly and environmentally unfriendly. However, an
approach to producing cinnamyl alcohol through selective
Address correspondence to Jiale Huang, Department of Chemi-
cal and Biochemical Engineering, College of Chemistry and
Chemical Engineering, Xiamen University, Xiamen 361005,
P. R. China. E-mail: cola@xmu.edu.cn
Color versions of one or more of the figures in the article can be
found online at www.tandfonline.com/lsrt.

9
68
Zheng et al.
hydrogenation of cinnamaldehyde can overcome these dis- Experimental
[
12,13]
advantages.
Nevertheless, in the cinnamaldehyde mol-
ecule, the CHO and CHC bonds of the acrolein group are Materials
[
14]
conjugated.
The former bond possesses higher bond
Sundried CP was purchased from Xiamen Jiuding Drugstore,
energy compared with the latter bond, resulting in poor
selectivity towards cinnamyl alcohol. Therefore, exploring
efficient catalysts for selective hydrogenation is crucial.
Currently, heterogeneous catalysts have received immense
attention because of their favorable characteristics, includ-
China. Sodium tetrachloroplatinate (Na PtCl ) and chloro-
2
4
platinic acid (H PtCl ) used as platinum precursor was sup-
2
6
plied by Aladdin Chemistry Co. Ltd., China. TiO and Co
2
.
(
NO ) 6H O were obtained from Sinopharm Chemical
3 2 2
Reagent Co. Ltd., China. H (ꢀ99.99%), N (ꢀ99.999%) and
[
10]
2
2
ing easy separability and recyclability.
heterogeneous catalysts (e.g., Pt/MCM-48, Pt/
and Pt/ZrO2 ) have been devel-
Some Pt-based
compressed air were provided by Fuzhou Xinhang Industrial
Gases Co. Ltd. (China).
[
15]
[
16]
[17]
[18]
CNTs,
Pt/TiO2,
oped for the selective hydrogenation of cinnamaldehyde.
Among them, Pt/TiO has been reported to exhibit excel-
2
Preparation of CP Extract
lent catalytic activity because of the strong interaction
[
17]
between Pt and TiO with high reducibility.
Moreover,
2
The biomass of CP for reduction was milled, and the powder
was screened with a 20-mesh sieve. 3 g of the CP powder was
then dispersed in 90 mL of deionized water in a 200 mL bea-
ker and boiled for 5 min. Thereafter, the resulting broth was
cooled down to room temperature and filtered to obtain the
filtrate, which was subsequently adjusted to 100 mL by add-
its catalytic activity can be enhanced by doping a small
amount of a transition metal (e.g., Co) due to the electron-
[
19]
deficient species of transition metals.
However, Pt cata-
lysts using biosynthesized PtNPs in selective hydrogenation
have not been reported hitherto.
In this work, Pt sols (or PtNPs) were biosynthesized by
reducing aqueous Na PtCl with Cacumen Platycladi extract
ing deionized water. The resulting CPE was refrigerated at
ꢀ
2
4
6
C for the biosynthesis of PtNPs within seven days after
(
CPE) as the reducing agent. The effects of Pt loading and Co
preparation.
doping on the TiO support and the catalytic performance of
2
the Pt/TiO and Co–Pt/TiO catalysts prepared through sol
immobilization were studied. Transmission electron micros-
2
2
PtNPs Sol
copy (TEM) and X-ray diffraction (XRD) were used to char- The Pt sol was prepared by the biosynthetic method using
acterize the Pt catalysts. To the best of our knowledge, this is biomass extract of CP. The typical synthesis process of the
the first report on the fabrication of biogenic Pt nanocatalysts PtNPs sol is shown in Scheme 1a. First, an aqueous solution
for selective hydrogenation of cinnamaldehyde that high- with 7 mL CPE and 3 mL deionized water was heated at
ꢀ
lights the potential catalytic application of PtNPs through 90 C in an oil bath under continuous stirring for 10 min.
biosynthesis.
Then 0.096 mL aqueous Na PtCl solution (52.24 mM) was
2 4
Sch. 1. (a) Synthesis of PtNPs. (b) Preparation of Pt and Co-Pt catalysts. (c) Hydrogenation of cinnamaldehyde.

Catalytic Application of Biogenic Platinum Nanoparticles
969
ꢀ
suddenly added to the flask with continuous stirring at 90 C Results and Discussion
for 24 h.
XRD Characterization
Pt Catalysts
The XRD patterns of the TiO support and calcined Pt/TiO
2
2
Scheme 1b illustrates the typical preparation process for Pt/ catalysts are shown in Figure 1. Anatase crystal structure of
TiO catalysts through sol- immobilization using the above TiO remained in the XRD pattern of calcined Pt/TiO cata-
2
2
2
biogenic PtNPs sol. An appropriate amount of HCl was used lysts. Samples with higher Pt loadings (1% and 2%) showed
ꢀ
ꢀ
to adjust the pH of the PtNPs sol to 2 and 0.4 g TiO was diffraction peaks at approximately 38.9 and 45.7 corre-
2
added to the Pt sols under vigorous stirring. After 1 h, the sponding to the Pt species with a face-centered cubic structure.
solid was collected by filtration and washed with deionized And no obvious Pt was detected on the catalysts with lower Pt
ꢀ
water. The obtained solid was subsequently dried at 50 C in loadings (0.5 and 1%), indicating Pt species were highly dis-
ꢀ
vacuum for 4 h and then calcinated at 500 C for 4 h.
persed on the support. As shown in Figure 2, the XRD pat-
Besides, traditional impregnation method was also used to terns of Co-Pt/TiO catalysts showed just little difference
2
prepare Pt/TiO catalysts for comparison: 0.4 g TiO was compared with Pt/TiO , which means that Co doping has no
2
2
2
suspended in a desired amount of H PtCl solution, followed significant effect on the structure of the Pt/TiO catalysts.
2
6
2
ꢀ
by drying at 100 C. The remaining paste was then calcinated
in air at 500 C for 3 h and subsequently reduced in flowing
ꢀ
ꢀ
TEM Results
hydrogen at 500 C for 1 h.
For the preparation of Co–Pt/TiO catalysts, in addition
to all the steps in the preparation of Pt/TiO2 catalysts,
2
TEM images of the Pt catalysts obtained based on bioreduc-
tion are shown in Figure 3. The PtNPs were well dispersed
0
.355 mL aqueous Co(NO ) (19.1 mM) was mixed with the
3 2
on the TiO support and had a narrow size distribution of 4–
2
Pt/TiO composites before the calcinations procedures.
2
6 nm. Compared with the PtNPs measuring 2.4 § 0.8 nm
The as prepared Pt catalysts were denoted as x Pt/TiO2
freshly biosynthesized before immobilization, those of the 1.0
and y Co-x Pt/TiO , where x and y stands for the calculated
2
Pt/TiO catalyst were larger (5.1 § 2.7 nm; Figure 3b) due
2
weight percentage of Pt and Co in the catalyst, respectively.
to aggregation under calcination. Moreover, based on the
TEM images, the histogram inserts show that PtNPs over
TiO with particle sizes of 4.7 § 2.5, 5.1 § 2.7, 5.3 § 2.7, and
2
Characterization
5
.4 § 2.6 nm corresponds to 0.5%, 1.0%, 1.5%, and 2.0% Pt
loading respectively, indicating that increasing the loading
process leads to larger PtNPs. TEM images of Co -Pt/TiO2
catalysts are shown in Figure 4. After doped with different
amount of Co, it was found that the higher the Co doping
amount was, the smaller the mean particle size of the PtNPs
became. Hence, it can be concluded that Co doping could
prevent the aggregation of PtNPs under calcination.
XRD
The XRD patterns of Pt catalysts were collected using an
X’Pert Pro X-ray Diffractometer (PANalytical BV, the Neth-
erlands) with CuKa radiation.
TEM
Specimens for TEM were prepared by placing a drop of etha-
nol suspension of Pt catalysts on carbon-coated copper grids
and the tests were carried out using a Tecnai F30 microscope.
In addition, the size distribution and average size of the
PtNPs were estimated by the same method as that in our pre-
Catalytic Activity
Effects of Pt Loading
Figure 5 shows the effects of different Pt loadings on the cat-
alytic performance. As shown, pure TiO support exhibited
[
20]
vious work.
2
Evaluation of Pt Catalysts
2
.0Pt/TiO2
The catalytic performance of the Pt catalysts for the
hydrogenation of cinnamaldehyde was tested in a stainless
steel reactor (500 mL) at 60 C by dispersing 0.3 g of cata-
ꢀ
1.5Pt/TiO2
lyst samples into 100 mL of alcoholic medium containing
1
.0Pt/TiO2
2
.5% cinnamaldehyde at 3 MPa. Reactants and hydro-
genation products, such as cinnamyl alcohol, 3-phenylpro-
panal, and 3-phenylpropanol, among others, as illustrated
0.5Pt/TiO
2
[
21]
in Scheme 1c,
were analyzed using a gas chromatogra-
pher equipped with a SE-30 capillary column and a flame
ionization detector. In addition, the reactants and all
products were identified based on corresponding standard
samples, and a normalization calibration method was
TiO2
30
40
50
60
70
80
90
o
2
Theta/
employed to quantify the consumption of cinnamaldehyde Fig. 1. XRD pattern of the TiO support and the catalysts pre-
2
and the selectivity of the products.
pared by bio-method with different Pt loadings.

9
70
Zheng et al.
over TiO could be efficient catalysts for the hydrogenation
2
of cinnamaldehyde to cinnamyl alcohol. Nevertheless, further
increasing the Pt loading to 2.0% resulted in just a slight
increase in the conversion of cinnamaldehyde, whereas that
of the selectivity to cinnamyl alcohol slightly decreased.
2
.0Co-2.0Pt/TiO2
1
.0Co-2.0Pt/TiO2
.0Co-1.0Pt/TiO2
Effects of Co Doping
Figure 6 illustrates the effect of Co doping on the conver-
sion of cinnamaldehyde and selectivity to cinnamyl alco-
hol. In order to invegate the effect of Co doping on Pt/
1
0
.5Co-1.0Pt/TiO2
TiO catalysts, the Pt loading was fixed at 1% with the Co
2
doping increased from 0.5% to 2% and the same reaction
conditions as those described in the legend to Figure 5,
were used to evaluate the activity of the Co doping cata-
30
40
50
60
70
80
90
o
2
Theta/
Fig. 2. XRD pattern of some catalysts with Co doping prepared lysts. As shown in Figure 6, although the selectivity to cin-
by bio-method.
namyl alcohol increased from 38.5% to 63.6% compared
with pure TiO support, the 1.0 Co/TiO catalyst without
2
2
Pt loading exhibited a very low conversion (<20%). As for
very low conversion rates for cinnamaldehyde (about 10%). the Co-Pt/ TiO2 catalysts, increasing the Co doping
After the biosynthesized PtNPs were immobilized onto the amount, resulted in a minimal increase in the selectivity
TiO support, the selectivity to cinnamyl alcohol obviously toward cinnamyl alcohol that is from 67.2% to 76.7%.
2
increased significantly to above 60%. With the increasing of When the Co doping was 0.5%, the conversion of cinna-
the Pt loadings, from 0.5% to 1.0%, a great improvement in maldehyde was even lower than that without Co in Fig-
the conversion of cinnamaldehyde was observed from 19.6% ure 5. On the contrary, increasing the Co doping to 1.0%,
to 66.8%. As for the 1.0 Pt/TiO catalysts, the rates of con- the conversion was greatly improved reaching a maximum
2
version and selectivity were calculated as 66.8% and 73.2%, of 88.3%. The conversion increased slightly when the Co
respectively, indicating that the biogenic PtNPs supported doping was upped to1.5% in comparison with the 1.0% Co
Fig. 3. TEM images of the biosynthesized catalysts: (a) TiO , (b) 0.5 Pt/TiO , (c) 1.0 Pt/TiO , (d) 1.5 Pt/TiO , (e) 2.0 Pt/TiO , and
2
2
2
2
2
(f) HR-TEM of PtNPs on the catalysts.

Catalytic Application of Biogenic Platinum Nanoparticles
971
Fig. 4. TEM images of the biosynthesized catalysts: (a) 0.5 Co-1.0 Pt/TiO , (b) 1.0 Co-1.0 Pt/TiO , (c) 1.5 Co-1.0 Pt/TiO , and (d)
2
2
2
2
.0 Co-1.0 Pt/TiO , respectively.
2
catalysts. However, when the Co doping amount was Durability of the Pt Catalysts
increased to 2.0% a dramatic decrease in the conversion
Durability is a very important criterion for catalysts to be
considered for practical application. Recyclability tests
were conducted to assess the durability of the 1.0 Co–1.0
[
22]
was observed. Englisch et al.
suggested that a stronger
interaction exists between Co and Pt because of micropola-
rization due to the electronic effects of Co. Therefore, the
stronger interaction could polarize C D O more easily,
making the hydrogenation of C D O easier and thereby
enhancing the selectivity to cinnamyl alcohol. However,
for the phenomenon of diminished conversion of cinnamal-
dehyde with higher Co doping, we speculated that the
excess cobalt (nCo:nPt D 3.3) might have covered the PtNPs
Pt/TiO catalysts. The catalysts after reaction were recov-
2
ered by centrifugation, washed with ethanol several times
to remove the binding substances on the catalysts, dried
without further calcination, and then reused under the
same reaction conditions. As shown in Figure 7, the con-
version of cinnamaldehyde was kept at above 80% after
three cycles with a steady selectivity to cinnamyl alcohol
almost unchanged. The conversion of cinnamaldehyde
and selectivity toward cinnamyl alcohol after the fifth
cycle, were 79.2% and 67.3%, respectively, indicating that
loaded on the TiO , thus slowing down the reaction rate,
2
leading to the conversion of cinnamaldehyde simulta-
neously showing a downward trend.

9
72
Zheng et al.
Fig. 5. Catalytic performance of the Pt catalysts. Reaction condi- Fig. 8. Catalytic performance of the Co–Pt catalysts prepared by
tions: cinnamaldehyde, 2.5 mL; ethanol, 97.5 mL; catalyst, impregnation method.
ꢀ
0
.3 g; reaction temperature, 60 C; reaction pressure, 3 MPa;
reaction time, 3 h.
the 1.0 Co–1.0 Pt/TiO catalysts possessed high durabil-
2
ity. These results have characterized promising catalysts
for the selective hydrogenation of cinnamaldehyde based
on biosynthesized PtNPs.
Comparison of the Biosynthesis-Assisted Catalysts with
Traditional Catalysts Prepared by Impregnation
Figure 8 shows the catalytic performance of the catalyst
prepared by traditional impregnation method. The differ-
ent amount of Co had just little influence on the selectiv-
ity, but had a significant impact on the conversion to the
desired product, which is similar to the bio-synthesized
sample. It is worth noting that with the same amount of
Co doping and Pt loading, the catalysts with Co doping
of 0.5% prepared by traditional impregnation method
showed much lower conversion than that by the bio-
method. The selectivity to cinnamyl alcohol of Co-Pt/
TiO2 prepared by traditional impregnation method was
obviously lower than that by the bio-method.
Fig. 6. Catalytic performance of the Co–Pt/TiO catalysts.
2
Conclusions
A sol immobilization method based on the biosynthesis of
Pt sols with CPE was used to prepare Pt/TiO and Co-
2
Pt/TiO catalysts for the selective hydrogenation of cinna-
2
maldehyde. Co-Pt/TiO2 catalysts were also prepared by
traditional impregnation method for comparison with the
biosynthesized sample. This study investigated the cata-
lytic application of Pt catalysts for the hydrogenation of
cinnamaldehyde to cinnamyl alcohol based on the biosyn-
thesis of Pt sols with CPE. The biogenic PtNPs supported
on TiO could be efficient catalysts for the hydrogenation
2
of cinnamaldehyde to cinnamyl alcohol. The 1.0 Co–1.0
Pt/TiO catalysts, showed significant conversion rates of
2
Fig. 7. Catalytic performance of recyclable bioreduction cata- cinnamaldehyde and selectivity towards cinnamyl alcohol
lysts under the following conditions: cinnamaldehyde/catalyst 88.3% and 70.4%, respectively. Proper amounts of Co
ꢀ
ratio, 2.5 mL:0.3 g; reaction temperature, 60 C; reaction pres- doping enhanced the catalytic performance, with the cata-
sure, 3 MPa; reaction time, 3 h.
lysts prepared by biomediated method showing higher

Catalytic Application of Biogenic Platinum Nanoparticles
973
selectivity to cinnamyl alcohol than the catalysts prepared
by impregnation method. In summary, the results of this
study have demonstrated the efficiency of biosynthetic
PtNPs as competitive catalysts for selective hydrogenation
of cinnamaldehyde.
honey solutions and their catalytic applications. Colloids Surf. A–
Physicochem. Eng. Aspects 2011, 384, 733–738.
0. Merlo, A. B.; Machado, B. F.; Vetere V.; Faria J. L.; Casella M. L.
PtSn/SiO(2) catalysts prepared by surface controlled reactions for
the selective hydrogenation of cinnamaldehyde. Appl. Catal. A–
Gen. 2010, 383, 43–49.
1. Jimenez, S.; Lopez, J. A.; Ciriano M. A.; Tejel C.; Martinez A.;
Sanchez-Delgado R. A. Selective hydrogenation of cinnamalde-
hyde and other alpha,beta-unsaturated substrates catalyzed by rho-
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1
1
Funding
3
202.
This work was supported by the Research Fund for the
Doctoral Program of Higher Education of China
1
1
2. Hammoudeh, A.; Mahmoud, S. Selective hydrogenation of cinna-
maldehyde over Pd/SiO2 catalysts: selectivity promotion by alloyed
Sn. J. Mol. Catal. A–Chem. 2003, 203, 231–239.
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hydrogenation of cinnamaldehyde to hydrocinnamaldehyde. Appl.
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(
20110121120018) and the Start-up Foundation for Scien-
tific Research Team Innovation of Putian University.
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