Chemical Engineering Journal 262 (2015) 356–363

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Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

Fabrication of Pd/c-Al2O3 catalysts for hydrogenation

of 2-ethyl-9,10-anthraquinone assisted by plant-mediated
strategy
Huimei Chen a, Dengpo Huang b, Xiyao Su b, Jiale Huang b,⇑, Xiaolian Jing a, Mingming Du b,
Daohua Sun b, Lishan Jia b, Qingbiao Li a,b,c,⇑
a
Environmental Science Research Center, College of the Environment & Ecology, Xiamen University, Xiamen 361005, PR China
b
Department of Chemical and Biochemical Engineering, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, PR China
c
College of Chemistry & Life Science, Quanzhou Normal University, Quanzhou 362000, PR China

h i g h l i g h t s

 Green Pd/Al2O3 catalysts for 2-ethyl-9,10-anthraquinone hydrogenation were fabricated.

 The maximum H2O2 yield of 96.4% could be achieved at lower reaction temperature.
 The Pd/c-Al2O3 catalysts exhibited their excellent durability.

a r t i c l e i n f o a b s t r a c t

Article history: Pd/c-Al2O3 catalysts efficient for the liquid-phase hydrogenation of 2-ethyl-9,10-anthraquinone were
Received 27 May 2014 prepared via an adsorption–reduction method using Cacumen Platycladi extract as both reductive and
Received in revised form 6 September 2014 protective agent. The catalysts were characterized by N2 physisorption, X-ray diffraction, transmission
Accepted 30 September 2014
electron microscopy and X-ray photoelectron spectroscopy. The results showed that Pd nanoparticles
Available online 8 October 2014
(NPs) measuring <10 nm were uniformly distributed on c-Al2O3. Based on the catalyst with the Pd load-
ing of 0.5 wt.%, H2O2 yield of 85.6% could be achieved at the optimum reaction conditions (H2 flow rate
Keywords:
40 mL/min, working solution volume 10 mL, hydrogenation time 1.5 h and reaction temperature 40 °C).
Bioreduction
Pd/c-Al2O3
And the reaction temperature was lower than those in the previous reports. Additionally, the catalysts
Hydrogenation showed much better catalytic activities after pretreatment of the support by HCl, NaOH, Na2CO3 and Na2-
Anthraquinone SiO3 solutions. Particularly, after c-Al2O3 was pretreated with Na2SiO3 solution, the H2O2 yield could
reach 96.4% and the catalysts exhibited excellent durability while the degradation products were inhib-
ited to some extent. Furthermore, the Pd NPs thereof did not aggregate after reuse. Therefore, the cata-
lysts assisted by plant-mediated strategy may be promising for the industrial application.
Ó 2014 Elsevier B.V. All rights reserved.

1. Introduction and non-polar solvents [4,5]. As presented in Scheme 1, during

Hydrogen peroxide (H2O2) is an environmentally friendly
chemical that is widely used in many chemical processes [1]. Com-
mercially, H2O2 is produced by the anthraquinone auto-oxidation
process [2,3] in which 2-ethyl-9,10-anthraquinone (eAQ) is dis-
solved in an organic solvent system consisted of a mixture of polar
⇑ Corresponding authors at: Department of Chemical and Biochemical Engineering,
College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005,
PR China (Q. Li and J. Huang). Tel.: +86 592 2183088; fax: +86 592 2184822.
E-mail addresses: cola@xmu.edu.cn (J. Huang), kelqb@xmu.edu.cn (Q. Li).
the reaction, eAQ is first catalytically hydrogenated to produce
the corresponding 2-ethyl-9,10-anthrahydroquinone (eAQH2) and
2-ethyl-5,6,7,8-tetrahydro-9,10-anthrahydroquinone (H4eAQH2).
Then, the as-obtained eAQH2 and H4eAQH2 are oxidized by O2/air
to produce H2O2 and some other active anthraquinones (mixture
of the original eAQ and 2-ethyl-5,6,7,8-tetrahydro-9,10-anthraqui-
none (H4eAQ)) [1,2,6–8]. However, in cyclic hydrogenation/oxida-
tion operations, due to the consumption via the parallel reaction
pathway I and II (Scheme 1), the content of eAQH2 slowly
decreases and produces products termed as ‘‘degradation prod-
ucts’’ [9,10]. Among these, the reaction pathway I is a consecutive
process of aromatic ring saturation from eAQH2 to H4eAQH2 and

http://dx.doi.org/10.1016/j.cej.2014.09.117
1385-8947/Ó 2014 Elsevier B.V. All rights reserved.
 H. Chen et al. / Chemical Engineering Journal 262 (2015) 356–363
Scheme 1. Reaction routes for hydrogenation of eAQ.
2-ethyl-1,2,3,4,5,6,7,8-octahydro-9,10-anthrahydroquinone (H8-
eAQH2). And the reaction pathway II comprises the hydrogenolysis
reactions of C–O bonds from eAQH2, such as 2-ethyloxanthrone
(OXO-E), 2-ethylanthrone (eAN), 2-ethylanthracene (eANT) and
dianthrone, etc. [11–16]. It has been demonstrated that the selectiv-
ity of the desired reaction (i.e., hydrogenation of quinone to hydro-
quinone) should be above 99% in industrial practice [3]. This
clearly shows that the side reactions at the cost of active anthraqui-
nones must be strongly inhibited. However, even for the active Pd
catalysts prepared by chemical reduction methods (impregnation,
H2 reduction, etc.), the consumption of eAQH2 to produce degrada-
tion products is inevitable [9,10,17]. Thus, it is imperative to develop
an efficient and durable catalyst with high selectivity in the hydro-
genation of the carbonyl group rather than the aromatic ring.
Green plant-mediated biosynthesis of metal nanoparticles (NPs)
in which plant extract played dual roles as reductive and protective
agents has been regarded as an alternative to chemical methods in
the last decade [18–22]. Interestingly, the biosynthetic metal NPs over
proper supports exhibited high activity and stability toward some
reactions [23–31]. As far as biosynthetic Pd NPs were concerned,
few reports were devoted to their catalytic application. In our previ-
ous study, the biogenic Pd NPs by antioxidants in Gardenia jasminoides
Ellis as long lifetime nanocatalysts for p-nitrotoluene hydrogenation
was demonstrated. Very recently, biosynthesis of Pd NPs using Delo-
nix regia leaf extract and their catalytic applications to nitro-aromatics
hydrogenation were reported [32]. Herein, we aimed at expanding
the green plant-mediated strategy to highly active and stable Pd nan-
ocatalysts for the liquid-phase hydrogenation of eAQ. In this work, Pd/
c-Al2O3 catalysts were prepared via an adsorption-reduction method
with Cacumen Platycladi (CP) extract without calcination. In order to
optimize the catalytic performance, effect of reaction temperature,
hydrogenated time, working solution volume and H2 flow rate was
investigated. In particular, pretreatments of c-Al2O3 support with
HCl, NaOH, Na2CO3 and Na2SiO3 solutions on the catalytic perfor-
mance were also studied. The Pd/c-Al2O3 catalysts were characterized
by N2 physisorption (BET), X-ray diffraction (XRD), transmission elec-
tron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS).
And atomic absorption spectrophotometry (AAS) was used to mea-
sure the actual Pd loading of the catalyst.
2. Materials and methods
2.1. Materials and reagents
Palladium nitrate (AR), 2-octanol (AR) and xylol (AR) were
purchased from Sinopharm Chemical Reagent Co., Ltd., China.
357
Hydrogen peroxide (3 wt.%) was purchased from Beijing J&K Scien-
tific Co., Ltd., China. 2-ethylanthraquinone (99%) was bought from
Henan Hongye Chemical Co., Ltd., China. The Cacumen Platycladi
biomass and c-Al2O3 were purchased from Xiamen Jiuding Drug-
store and CNOOC Tianjin Chemical Research & Design Institute,
China, respectively.
2.2. Preparation of CP extract and measurement of main components
In order to obtain CP extract, the carefully weighted sundried
biomass, which was screened with a 50 mesh sieve, 1.0 g was
added to 100 mL deionized water in a conical flask of 250 mL
capacity. The mixture was thereafter shaken (150 rpm, 2 h) at
30 °C and filtrated to get filtrate, i.e. the CP extract. The extract
was reserved in a refrigerator (4 °C) for further experiments. The
reducing sugar, flavonoid, polysaccharides and protein contents
before and after the reaction were measured by the same methods
in our previous study [33].
2.3. Preparation of Pd/c-Al2O3 catalysts
The original support c-Al2O3 was calcined at 500 °C prior to its
use. Then c-Al2O3 was soaked in 0.5 M HCl, 0.5 M NaOH, 0.05 M
Na2CO3 or 0.007 M Na2SiO3 solution under stirring for 2 h, respec-
tively. Next, the slurry was filtered, washed and dried to obtain
pretreated c-Al2O3 for further experiments. In a typical preparation
of Pd/c-Al2O3 catalyst, an adsorption–reduction method in which
Pd(NO3)2 adsorbed onto c-Al2O3 support was reduced with the
CP extract was adopted. Firstly, 0.5 g support was immersed in
aqueous Pd(NO3)2 (30 mL, 0.78 mM) for 0.5 h. Then, 30 mL of CP
extract was added to the solution under stirring. After 1 h, the
slurry was filtered, and the solid (0.5 wt.% Pd/c-Al2O3 catalysts)
was washed thoroughly with distilled water, dried in vacuum oven
at 50 °C overnight (without calcination) and their catalytic activity
for hydrogenation of 2-eAQ was then tested. The actual Pd loading
of the catalyst was analyzed by AAS (Pgeneral, China) by dissolving
the catalyst in aqua regia for 24 h.
2.4. Characterizations of Pd/c-Al2O3 catalysts
N2 physisorption isotherms were recorded on a porosimetry
analyzer (Micromeritics TriStar 3000) at 77 K. Before measure-
ments, Pd/c-Al2O3 samples were outgassed at 300 °C for 3 h. The
TEM observation was performed on a Tecnai F30 microscope at
300 keV with a high-angle annular dark field detector (HAADF).
The average size and size distribution of Pd NPs were measured
358 H. Chen et al. / Chemical Engineering Journal 262 (2015) 356–363
on the basis of TEM images by the previous method [33]. Powder
X-ray diffraction (XRD) patterns were performed on an X’pert
PRO diffractionmeter at 40 kV and a current of 30 mA with Cu-
Ka radiation (k = 1.5418 Å). X-ray photoelectron spectroscopy
(XPS) was performed on a Quantum 2000 spectrometer, and the
Al-Ka line was used as the excitation source.
2.5. Hydrogenation of 2-ethylanthraquinone and analytical procedure
Firstly, the catalytic activity for hydrogenation of 2-eAQ was
tested in agitated glass reactor at 40 °C using xylene and 2-octanol
(volume ratio 1:1) as mixing solvent, with constant eAQ concentra-
tion 20 g/L, H2 flow rate 30 mL/min, catalyst 0.1 g. Subsequently,
about the solution volume 3 mL was oxidized by oxygen (flow rate:
40 mL/min) for about 15 min in the other glass reactor without agi-
tation. By observing the color of the solution, one can determine
whether the oxidization was complete or not. In the previous stud-
ies, the hydrogen peroxide amount in the aqueous extract was
determined by titration with standard potassium permanganate
solution [1,6,8,11,13–15,34,35]. However, this method caused a
large error in our system because some biological components
might be extracted and oxidized by potassium permanganate. Thus,
in this work, H2O2 amount in the aqueous extract was analyzed by
HPLC using a chromatograph (Agilent, USA) with an UV detector
(200 nm), column 25 cm long, C18 fraction dp = 5 lm, and mixing
eluent composed of 80% acetonitrile and 20% ultrapure water. The
retention time of standard hydrogen peroxide was about 2.43 min,
and the peak of hydrogen peroxide was well identified.
The yield of total hydrogenated anthraquinones was deter-
mined by the following equations:
Y H2 O2 =% ¼ nðH2 O2 Þ =n0ðH2 O2 Þ  100% ¼ nðH2 O2 Þ =n0ðeAQ Þ  100%
Average yield ¼ n0ðH2 O2 Þ  Y H2 O2  M H2 O2 =ðmPd  hÞ
where n0ðH2 O2 Þ and nðH2 O2 Þ are the initial and the obtained mole of
H2O2, respectively. MH2 O2 and mPd represent the H2O2 molar mass
(34 g/mol) and the Pd (g) mass in the catalyst, respectively. The con-
centrations of both eAQ and H4eAQ were determined with a gas
chromatograph (GC 9160, Shanghai Ouhua, China) equipped with
FID detector in conditions: column FFAP, 0.53 mm  50 m 
0.4 lm, isothermal run 245 °C, which were analyzed by internal
standard method. Dibutyl phthalate was chosen as an internal stan-
dard substance. The sum of n(eAQ) and nðH4 eAQ Þ was smaller than the
initial content of n0(eAQ). And the percentage of degradation prod-
ucts (ND) over n0(eAQ) could be calculated according to the law of
mass conservation:
ND ¼ 1  nðeAQ Þ =n0ðeAQ Þ  nðH4 eAQ Þ =n0ðeAQ Þ
Fig. 1. (a) Nitrogen adsorption/desorption isotherms and (b) the corresponding pore size distributions of c-Al2O3 before and after pretreatments.
Table 1
Structural properties of c-Al2O3 before and after pretreatments.
Sample SBET/m2 g1 VP/cm3 g1 DP/nm
Al2O3 208 0.35 3.3
Al2O3–HCl 245 0.35 2.8
Al2O3–NaOH 230 0.33 2.9
Al2O3–Na2CO3 237 0.32 2.7
Al2O3–Na2SiO3 227 0.32 2.8
That is, when the sum of n(eAQ)/n0(eAQ) and nðH4 eAQ Þ /n0(eAQ) was
much closer to 1, the content of degradation products was much
less.
3. Results and discussion
3.1. Characterization of c-Al2O3 and the bioreduced Pd/c-Al2O3
catalysts
Nitrogen physisorption was used to evaluate pore structure
parameters of c-Al2O3 before and after pretreatments, including
specific area (SBET), pore volume (VP) and pore diameter (DP).
Fig. 1a and b shows the N2 adsorption/desorption isotherms and
pore size distributions, respectively. As shown, all the samples fol-
lowed Langmuir type IV isotherms, revealing that they were typi-
cal mesoporous materials. The pore size distribution (Fig. 1b)
showed a shoulder peak of pore size at about 2.9 nm after pretreat-
ment, indicating some small mesopores were created. In addition,
pore structure parameters in Table 1 indicated that the SBET slightly
increased while DP decreased after pretreatment.
ð1Þ As far as the preparation of Pd/c-Al2O3 catalysts, Pd(II) ions
were firstly adsorbed on the c-Al2O3 support, then CP extract
ð2Þ was introduced into reduce Pd(II) ions. In order to clarify the mech-
anism of bio-reduction, the contents of flavonoids, polysaccharides,
reducing sugars and proteins in the extract before and after the
reaction were measured. Fig. S1 (Supporting Information) shows
that all the contents of the flavonoids and reducing sugars (actually
included in saccharides) decreased largely, especially the content
of flavonoids. Hence, these flavonoids and reducing sugars in the
extract were responsible for the reduction of Pd(II). The morphol-
ogy of Pd/c-Al2O3 catalysts with theoretical Pd loading of
0.5 wt.% was obtained by HAADF-STEM in Fig. 2a, in which bright
spots (Orange box) represented the Pd NPs within size range of
4–10 nm. Even after 8-run reuse, Pd NPs were still well distributed
over the support and did not aggregate (Fig. 2b). According to the
AAS results, the actual Pd loading was 0.41 wt.%, which was
ð3Þ slightly lower than the theoretical one. XPS technique was further
used to determine the electronic state of Pd, and the spectra of Pd
 H. Chen et al. / Chemical Engineering Journal 262 (2015) 356–363 359

Fig. 2. STEM images of 0.5 wt.% Pd catalysts on the support pretreated by Na2SiO3 solution (a) before reaction and (b) after 8-run reuse.

Fig. 3. (a) XPS spectra of Pd 3d regions recorded on support adsorbed Pd(NO3)2 (a0 ), bioreduced catalyst with 0.5 wt.% Pd loading (b0 ) before reaction and (c0 ) after reaction, (b)
Powder XRD patterns of catalysts with 0.5 wt.% Pd loading on pure c-Al2O3 and various pretreated supports.

3d region are presented in Fig. 3a. It was evident that a doublet of
the Pd 3d peak consists of the 3d5/2 and 3d3/2 peaks. When
Pd(NO3)2 was adsorbed by the support at the beginning, the bind-
ing energy of Pd 3d5/2 peak was around 336.5 eV (a0 ), indicating
that Pd(II) had not yet been reduced. The shift of the Pd 3d5/2 peak
to a lower position at 335.6 eV (b0 ) indicated that Pd(II) ions were
reduced to elemental Pd [36,37], and the position of the peak little
changed after the recycling test. Different from the 3d5/2 peak, the
3d3/2 peak possessed higher binding energy, i.e. 340.85 eV. Fig. 3b
shows XRD patterns of the support before and after pretreatment.
All the supports presented predominant peaks (2h = 36.2°, 45.4°,
66.5°) of the c-Al2O3, while the Bragg reflections of Pd were not
distinct because of alumina diffractions.
3.2. Catalytic activity studies
3.2.1. Effect of reaction temperature
The hydrogenation of eAQ was carried out in a 3-phase system.
And the rate of mass-transport process was associated with the
reaction parameters (reaction temperature, hydrogenated time,
working solution volume and H2 flow rate). First, as this reaction
was exothermic, the temperature had a significant effect on the
eAQ conversion. The H2O2 yield and the evolution of eAQ and
H4eAQ as a function of reaction temperature in the range of 30–
70 °C are plotted in Fig. 4a and b, respectively. As shown, the max-
imum H2O2 yield of 85.6% and average H2O2 yield of 32.9 g H2 O2 /
(gPd h) were attained at 40 °C, respectively, while the eAQ conver-
sion was 90%. If the temperature increased, the H2O2 yield did not
increase further while the percentage of degradation products ND
increased (Fig. 4b). Thus, the optimal reaction temperature was
40 °C, which was lower than those in the previous studies
[6,38,39].
3.2.2. Effect of hydrogenated time
With the reaction time going on, a consecutive process of aro-
matic ring saturation eAQH2 ! H4 eAQH2 ! H8 eAQH2 or hydrog-
enolysis reactions of C-O bonds to generate degradation products
occurred [11]. Fig. 5 illustrates the effect of hydrogenation time
on the H2O2 yield and the active anthraquinone content. When
the hydrogenation time was 1.5 h, the H2O2 yield reached the high-
est value of 85.6%. Nevertheless, as the reaction time proceeded,
the average yield decreased accordingly. When the hydrogenation
time was just 0.5 h, the quite high average yield of 95.8 g H2 O2 /
(gPd h) was achieved. However, the H2O2 yield was only 83.2%.
Accordingly, ND increased with the hydrogenation time going on.
3.2.3. Effect of working solution volume
Comparative experiments were also conducted to study the
effect of working solution volume on the H2O2 yield and the active
anthraquinone content. As shown in Fig. 6, when the working solu-
tion volume was 10 mL, the highest catalytic activity was achieved.
By contrast, when it was much lower than 10 mL, deep hydrogena-
tion as well as generation of degradation products were resulted
because of much less eAQ and effective intermediate, given the
same H2 flow rate. In this case, ND was about 10%. On the other
hand, when the working solution volume was larger than 10 mL,
ND became much lower, while the H2O2 yields were less as well.
According to equation (2), n0ðH2 O2 Þ were much higher when the
360 H. Chen et al. / Chemical Engineering Journal 262 (2015) 356–363

Fig. 4. Correlations of (a) the H2O2 yield and (b) the active anthraquinone content with reaction temperature, respectively. (Conditions: 0.5 wt.% Pd/c-Al2O3 catalysts 0.1 g,
hydrogenated time 1.5 h, working solution volume 10 mL, H2 flow rate 30 mL/min.)

Fig. 5. Correlations of (a) the H2O2 yield and (b) the active anthraquinone content with hydrogenation time, respectively. (Conditions: 0.5 wt.% Pd/c-Al2O3 catalysts 0.1 g,
temperature 40 °C, working solution volume 10 mL, H2 flow rate 30 mL/min.)

Fig. 6. Correlations of (a) the H2O2 yield and (b) the active anthraquinone content with working solution volume, respectively. (Conditions: 0.5 wt.% Pd/c-Al2O3 catalysts
0.1 g, hydrogenated time 1.5 h, temperature 40 °C, H2 flow rate 30 mL/min.)

working solution volume was larger than 10 mL, leading to higher
average yield though the corresponding yields were lower. How-
ever, the concentration of catalysts was changed and simulta-
neously the gas–liquid surface was also changed by changing the
volume of working solution. Thus, the mass-transport effect might
be complicated and remains unclear. Therefore, it was necessary to
control the working solution volume when the H2 flow rate was
constant.
3.2.4. Effect of H2 flow rate
It should be mentioned that the hydrogenation of quinone to
hydroquinone is very easy and commonly limited by mass transfer
of H2 [6,12,40]. Thus, in this work, the hydrogenation experiments
were carried out above stoichiometric line (Fig. S2). Then the
amount of H2, that is, the H2 flow rate had some effect on the
H2O2 yield and the active anthraquinone content, given the same
reaction time (1.5 h). It can be seen from Fig. 7 that the H2O2 yield
increased slightly with increasing the flow rate of hydrogen gas at
the beginning. When the H2 flow rate exceeded 30 mL/min, the
H2O2 yield, however, began to decrease. At the same time, ND
started to increase. According to a previous report, hydrogen was
firstly adsorbed onto the Pd and subsequently reacted with eAQ
[9]. If H2 flow rate was large enough, more H2 flowed out of the
liquid phase prior to its dissociation on Pd surface and did not par-
ticipate in the reaction, thus leading to the decrease in yield and
increase in ND. Thus it was quite significant to maintain the H2 flow
 H. Chen et al. / Chemical Engineering Journal 262 (2015) 356–363 361

Fig. 7. Correlations of (a) the H2O2 yield and (b) the active anthraquinone content with H2 flow rate, respectively. (Conditions: 0.5 wt.% Pd/c-Al2O3 catalysts 0.1 g,
hydrogenated time 1.5 h, working solution volume 10 mL, temperature 40 °C.)

rate in the 3-phase system of hydrogenation of eAQ. By contrast, of Pd loading on the Na2SiO3-pretreated support was further stud-
the ring hydrogenation and C–O hydrogenolysis, are slower reac- ied. As shown in Fig. 9a, the H2O2 yield significantly increased with
tions so that the mass transfer of H2 had not so much important theoretical Pd loading increasing from 0.1 to 0.5 wt.%. If further
[12]. increasing the Pd loading, the yield did not increase significantly
but decreased slightly. According to the TEM images in Fig. 9b
and c, when Pd loading was as low as 0.3 wt.%, Pd NPs were too
3.2.5. Effect of pretreatment of the support
small to observe, even with HADDF-STEM. However, when Pd load-
The pretreatments on c-Al2O3 also influenced the catalytic
ing reached 1.6 wt.%, well dispersed Pd NPs on the support were
activity of the catalysts. In previous work, Drelinkiewicz et al.
observed with the bright field TEM, and the size was much larger
had done a lot of work on the pre-impregnation of alumina with
compared with the Pd NPs in the case of 0.5 wt.% Pd loading, as
Na2SiO3 [11,35], while we focused on catalytic activities of our
seen in Fig. 2. When Pd loading was below 0.5 wt.%, internal sur-
green catalysts with various pretreatments. Compared with the
face of catalyst (Pd NPs may be located inside the channel of sup-
unpretreated support, the catalysts using c-Al2O3 pretreated with
port according to Table 1) was inefficiently utilized in the main
HCl, NaOH, Na2CO3 and Na2SiO3 solutions, showed much better
reaction eAQ to eAQH2, thus leading to lower H2O2 yield. Neverthe-
catalytic activities, as shown in Fig. 8a. Especially, the Na2SiO3-pre-
less, when Pd loading was over 0.5 wt.%, larger size of Pd NPs was
treated catalyst achieved the highest H2O2 yield of 96.4%, a little bit
obtained, giving rise to less H2O2 yield. According to the active
higher than that of NaOH-pretreated catalyst, which was about
anthraquinone content, ND was much higher than ND of 0.5 wt.%
10% higher than that achieved with the unpretreated catalyst. It
Pd loading (data not shown). This may be due to deep hydrogena-
was reported that acid-base sites of the catalyst, which can act as
tion or hydrogenolysis reactions if much higher Pd loading was
adsorption sites for eAQ molecules, played an important role in
adopted. Therefore, the main reaction strongly depended on the
the hydrogenation of eAQ [9]. Drelinkiewicz et al. reported the role
Pd particle sizes, which was consistent with the previous report
of alkali modifiers was associated with stronger interactions
[35].
between the catalyst and quinone reagents, and degradation prod-
ucts are remarkably inhibited. The acidic sites of the support acted
as adsorption sites for the aromatic compound, and once these
3.2.7. Durability of the Pd/c-Al2O3 catalysts and the comparison with
adsorbed species were activated, they can react with hydrogen
other Pd catalysts
spilt from the Pd metal [9]. On the other hand, the formation of
In order to assess the durability of the bioreduced Pd catalyst,
degradation products was strongly inhibited on these pretreated
recycle tests were conducted using the Na2SiO3-pretreated cata-
catalysts, as shown in Fig. 8b.
lyst. The catalyst was washed with ethanol after reaction, then
dried and reused for the next reaction under the same condition.
3.2.6. Effect of Pd loading As shown in Fig. 10a, the H2O2 yield remained stable during eight
As discussed above, the maximum H2O2 yield was obtained if cycles, and the content of degradation products did not increase
the catalyst support was pretreated with Na2SiO3. Thus, the effect significantly (Fig. 10b), indicating that bioreduced Pd catalyst

Fig. 8. Effect of pretreatment of the support on (a) the H2O2 yield and (b) the active anthraquinone content, respectively. (Conditions: 0.5 wt.% Pd/c-Al2O3 catalysts 0.1 g,
hydrogenated time 1.5 h, working solution volume 10 mL, H2 flow rate 30 mL/min and temperature 40 °C.)
362 H. Chen et al. / Chemical Engineering Journal 262 (2015) 356–363

Fig. 9. (a) Effect of Pd loading of c-Al2O3–Na2SiO3 support on the H2O2 yield and TEM images of Pd/c-Al2O3–Na2SiO3 with Pd loading of (b) 0.3 wt.% and (c) 1.6 wt.%,
respectively. (Conditions: Pd/c-Al2O3–Na2SiO3 catalysts 0.1 g, hydrogenated time 1.5 h, working solution volume 10 mL, H2 flow rate 30 mL/min and temperature 40 °C.) The
insert histogram in (c) indicates the corresponding size distribution.

Fig. 10. The catalytic performance of recycling bioreduced Pd catalysts: (a) the H2O2 yield and (b) the active anthraquinone content, respectively. (Conditions: 0.5 wt.% Pd/c-
Al2O3–Na2SiO3 catalysts 0.1 g, hydrogenated time 1.5 h, working solution 10 mL, H2 flow rate 40 mL/min and temperature 40 °C.)

showed high catalytic stability. In addition, even after 8-run reuse,
the Pd NPs almost retained stable on the support, as illustrated by
the TEM image in Fig. 2b. According to the AAS result, little Pd suf-
fered leaching during the reaction and the actual Pd loading remain
0.40 wt.% after 8-run reuse. For comparison, the catalytic activity of
Pd/c-Al2O3 catalyst prepared by H2 reduction was also studied.
However, the results showed that the H2O2 yield was only about
50%. Therefore, the bioreduced Pd/c-Al2O3 catalyst herein exhib-
ited much better catalytic performance. Furthermore, comparisons
of the catalytic performance between the bioreduced Pd/c-Al2O3
catalyst and other Pd catalysts reported in literatures were also
carried out [3,6]. Zhang et al. reported a Pd/Al2O3/cordierite could
obtain average yield of 15.16 g H2 O2 /(gPd h) [6], while Chen listed
APC-Q-1 spherical Pd catalyst could get more than 66.67 g H2 O2 /
(gPd h) compared with a commercial Pd catalyst could achieve
more than 45.83 g H2 O2 /(gPd h) [3]. Obviously, the catalytic perfor-
mance of the bioreduced Pd catalysts was comparable to other
Pd catalysts. Moreover, when the hydrogenation time was only
0.5 h for one-way reaction, the average yield of 101.3 g H2 O2 /(gPd h)
could be achieved, and the H2O2 yield was 80.3%.
4. Conclusion
In summary, the uncalcined Pd/c-Al2O3 catalysts for the liquid-
phase hydrogenation of 2-ethyl-9,10-anthraquinone were pre-
pared via an adsorption–reduction method using Cacumen Platycla-
di extract. Based on the catalyst with the Pd loading of 0.5 wt.%, the
optimum reaction conditions were reaction temperature 40 °C
(lower than those in the literature), hydrogenated time 1.5 h,
working solution 10 mL and H2 flow rate 40 mL/min. In particular,
if the supports were pretreated with HCl, NaOH, Na2CO3 and Na2-
SiO3 solutions, the H2O2 yield could increase by about 5–10%.
And the best H2O2 yield of 96.4% could be achieved when the sup-
port was pretreated with Na2SiO3 solution, and even after 8-run
reuse, the catalysts exhibited remarkable durability and the con-
tent of side products did not increase significantly. Also, Pd NPs
on the support were stable and did not aggregate after reuse.
Therefore, in terms of these advantages, the catalysts assisted by
plant-mediated strategy may be promising for future industrial
application.
Acknowledgements
This work was supported by the Natural Science Foundation of
China (21036004 and 21106117) and Research Fund for the Doctoral
Program of Higher Education of China (20110121120018). The
authors are grateful to Dr. Xianxue Li for his helpful discussion.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.cej.2014.09.117.
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