Preparation of a magnetic mesoporous Fe3O4-Pd@TiO2 photocatalyst for the efficient selective reduction of aromatic cyanides

Article abstract of DOI:10.1039/c8nj06508j

Herein, a hierarchical magnetic mesoporous microsphere was successfully prepared as a photocatalyst via a simple and reproducible route. Typically, Pd nanoparticles (NPs) were evenly dispersed on the surface of a magnetic Fe₃O₄ microsphere and then coated with a porous anatase-TiO₂ shell to form Fe₃O₄-Pd@TiO₂. The core-shell structure could efficiently suppress the conglomeration of Pd NPs during the calcination process at high temperatures as well as the shedding of Pd during the catalytic reaction process in the liquid phase. The as-prepared photocatalyst was characterized by TEM, XRD, XPS, VSM, and N₂ adsorption-desorption. Fe₃O₄-Pd@TiO₂ exhibits high photocatalytic activity for the selective reduction of aromatic cyanides to aromatic primary amines in an acidic aqueous solution. Moreover, this magnetic photocatalyst could be easily recovered from the reaction mixture by an external magnet and reused five times without significant reduction in its activity. The superior photocatalytic efficiency of the proposed photocatalyst may be attributed to its high charge separation efficiency and charge transfer rate, which are caused by the Schottky junction and large interface area. The results indicate that the strategy of coating the active noble metal sites with a mesoporous semiconductor shell has a significant potential for application in metal-semiconductor-based photocatalytic reactions.

Full text of DOI:10.1039/c8nj06508j

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Jason B. Benedict et al.
The role of atropisomers on the photo-reactivity and fatigue of
diarylethene-based metal–organic frameworks
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Preparation of magnetic mesoporous Fe3O4-Pd@TiO2
photocatalyst for efficient selective reduction of aromatic cyanide
Ziming Zhaoa, Yu long*a, Sha Luoa, Wei Wua and Jiantai Ma*a
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
A hierarchical magnetic mesoporous microsphere has been successfully prepared as photocatalyst with a simple and
reproducible route. Pd nanoparticles (NPs) are evenly dispersed on the surface of magnetic Fe3O4 microsphere, then being
coated by porous anatase-TiO2 shell to form Fe3O4-Pd@TiO2. The core-shell structure can efficiently suppress the
conglomeration of Pd NPs in the process of calcining at high temperature, as well as the shedding of Pd during the catalytic
reaction process in the liquid phase. The as-prepared photocatalyst was characterized by TEM, XRD, XPS, VSM, and N2
adsorption-desorption. Fe3O4-Pd@TiO2 exhibits a high photocatalytic activity for the selective reduction of aromatic
cyanide to aromatic primary amines in acidic aqueous. Moreover, this magnetic photocatalyst can be easily recovered by
an external magnet from the reaction mixture and reused five times without significant reduction in activity. The superior
photocatalytic efficiency may be attributed to high charge separation efficiency and charge transfer rate, which are caused
by schottky junction and large interface area. The results display that the strategy of coating active noble metal sites with
mesoporous semiconductor shell has a great potential in metal-semiconductor based photocatalytic reaction.
www.rsc.org/
Particularly, TiO2 has been considered as the promising
photocatalyst due to its unique advantages, such as stable, non-
Introduction
toxic, low cost, and recyclable.16-18 It is widely accepted that both
brookite- and rutile-type TiO2 exhibit lower photocatalytic activity
than anatase-type TiO2.19-21 Therefore, attention is mainly paid to
anatase-type TiO2. Because of its wide bandgap, anatase-TiO2 can
be motivated by UV light, whose wave length is just under 387nm,
to generate catalytic activity. However, reduction potentials of
many organic compounds are higher than the reduction potential of
electrons (-0.26 eV) in anatase TiO2 conduction band.22 Fortunately,
loading a proper metal to form schottky junction is an effective
method to reduce the reaction activation energy,23-25 in this case,
the reduction potential of the organic compound is not limited by
the reduction potential of electrons in TiO2 conduction band. For
example, the reduction (H+/H2) can be catalyzed by the Pd-loaded
Aromatic primary amines are considered to be the important
compounds as intermediates of organic chemicals and fine
chemicals.1-4 Nowadays, the demand for primary amines increases
with increasing development of these chemical products. Thus, the
efficient and fast transformation of cyano group into amino group
by catalytic hydrogenation has become an important research focus.
5,
6
According to the previous reports, there are some major
methods for the preparation of aromatic primary amines from
aromatic cyanide. For instance, suitable support supported metals,
such as nickel, palladium, cobalt, copper, and ruthenium, were
applied for catalytic reduction of nitriles to amines,7-11 whereas it is
difficult to withstand a tough reaction condition. Due to these
reactions require high temperature and high pressure, the
operation is not convenient. Simultaneously, it is difficult to
produce primary amines selectively by traditional hydrogenation of
corresponding nitriles. Therefore, handy operation and milder
conditions are favored.
27
TiO2,26, whereas it is impossible to reduce H+ using bare TiO2.
Therefore, metal-loaded TiO2 has
a great potential both in
photocatalytic organic reaction, such as Pt-TiO2 photocatalytic
degradation of formaldehyde in air,28 Ag-TiO2 photocatalytic
synthesis of benzimidazole.29 In 2013, Kazuya et al. firstly found that
benzonitrile could be reduced to benzylamine by palladium-loaded
TiO2 photocatalyst, contributed to its impressively high
photocatalytic activity.30 Although the photocatalyst is a robust
method for the selective reduction of aromatic cyanide to aromatic
primary amines, some shortcomings are found. For instance, the
active components may be lost in the reaction process, making the
catalyst unstable in the reaction. Furthermore, the photocatalyst
cannot be reused, leading to high catalysts cost and waste of
precious metals. To solve these problems, the corresponding
improving methods were raised in this work.
A photocatalytic reaction benefits from a room temperature and
atmospheric pressure. Photocatalysis has excellent properties of
moderate reaction condition, high selectivity and activity, thus
many researchers have paid great attention for a long time.12-15
a. State Key Laboratory of Applied Organic Chemistry (SKLAOC), The Key Laboratory of
Catalytic Engineering of Gansu Province, College of Chemistry and Chemical
Engineering, Lanzhou University, Lanzhou, Gansu, 730000, P. R. China
E-mail: majiantai@lzu.edu.cn；longyu@lzu.edu.cn
Electronic Supplementary Information (ESI) available: [details of any supplementary
information available should be included here]. See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
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Synthesis of Fe3O4-Pd@TiO2 microsphere
It is commonly known that morphology plays an important role in
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DOI: 10.1039/C8NJ06508J
heterogeneous catalyst.31-35 The morphology of catalyst has
important influence on the activity and selectivity of catalytic
reaction. Specifically, because of the large surface area and uniform
To obtain a mesoporous titanium dioxides shell grown on the
Fe3O4-Pd composite. Firstly, 100mg as-made Fe3O4-Pd was
dispersed in chromatographic grade ethanol (50 mL) with an
ultrasonic treatment for 1 h. Second, the concentrated ammonia
solution (0.35 mL, 28 wt%) was added into the solution with
vigorous stirring. Then, the mixture solution of tetrabutyl titanate
(0.7 mL) and chromatographic grade ethanol (6 mL) were slowly
dropped for 7min with strong stirring at 45 °C for 24h. Finally, with
the help of a magnet, the products were washed with deionized
water and ethanol for three times and dried in a vacuum at room
temperature overnight.
pore size, the mesoporous material becomes the hot topic of
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research in catalysis.36,
The pore structure might improve the
specific surface area and expose more active sites of catalyst, thus
enhancing the catalytic activity. In addition, Fe3O4 is particularly
promising as a superparamagnetism material, which has been used
as support in green chemical sciences and biomedical sciences.38-41
The preparation of shell coated magnetic Fe3O4 microspheres has
been widely developed, in order to make it easily be modified such
as grafting organic groups and stablely immobilizing metal NPs.42-44
Based on the above, in this work, Fe3O4@TiO2(anatase)-Pd and
Fe3O4-Pd@TiO2(anatase) are synthesized for comparison of catalytic
activity in the reduction of aromatic cyanide with different
structural catalyst. As expected, Fe3O4-Pd@TiO2(anatase) displays
outstanding photocatalytic activity towards the selective reduction
of aromatic cyanides to aromatic primary amines at room
temperature, including a high conversion rate of aromatic cyanide,
yield and selectivity of aromatic primary amines. Furthermore, this
photocatalyst can be easily retrieved by an outer magnet from the
reaction system and there is no significant decrease in activity after
being reused for five times.
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Synthesis of Fe3O4@TiO2 microsphere
Fe3O4@TiO2 was prepared according to previous step. In brief,
100mg Fe3O4 was dispersed in chromatographic grade ethanol
solution under an ultrasonic treatment. The concentrated ammonia
solution was added into the solution with vigorous stirring. Then,
the mixture solution of tetrabutyl titanate and chromatographic
grade ethanol were slowly dropped with strong stirring at 45 °C for
24h. The products were washed with deionized water and ethanol
for three times and dried in a vacuum at room temperature
overnight.
Calcination process
Experimental
Fe3O4-Pd@TiO2(anatase) and Fe3O4@TiO2(anatase) were
prepared by calcining the amorphous Fe3O4-Pd@TiO2 and
Fe3O4@TiO2 with the protection of nitrogen gas at 500 °C for 2h.47
In addition, Fe3O4-Pd@TiO2(rutile) was prepared by calcining the
amorphous Fe3O4-Pd@TiO2 at 900 °C for 2h.
Materials
Iron (III) chloride hydrate, sodium acetate, ethylene glycol,
palladium chloride, sodium citrate, sodium borohydride, ethanol,
ammonia, and tetrabutyl titanate (TBOT) were purchased from
Sinopharm Chemical Reagent Co., Ltd. Benzonitrile, Oxalic acid were
purchased from Sigma-Aldrich, and all used as received without
further purification. Water was deionized with the Barnstead E-Pure
system.
Synthesis of Fe3O4@TiO2(anatase)-Pd composite
100 mg as-prepared Fe3O4@TiO2(anatase) microspheres were
dispersed in a 50 mL methanol solution (containing 10mL of
0.01mol/L palladium chloride aqueous solution) under an ultrasonic
treatment for 0.5h. Then, the solution was photoiradation with a
400W mercury high pressure lamp under magnetic stirring for 2h.
Synthesis of Fe3O4 microsphere
Fe3O4 microsphere was prepared via a hydrothermal process
according to our previous work.45, 46 First, FeCl3·6H2O (9 g), sodium
acetate (13 g), sodium citrate (7 g), and ethylene glycol (200mL)
were mixed with fiercely stirring for 5 h. Second, the mixture was
transferred to a hydrothermal synthesis reactor and heated at 200
°C for 12 h. Third, by an external magnet, the products were
obtained and washed three times with deionized water and ethanol
for three times, and dried in a vacuum drying oven for 10 h at 60℃.
Characterization
These core-shell microspheres were characterized by inductively
transmission electron microscope (TEM), scanning electron
microscope (SEM), powder X-ray diffraction (XRD), X-ray
photoelectron spectroscopy (XPS), vibrating sample magnetometry
(VSM), and Energy Dispersive X-Ray Spectroscopy (EDX). The
Brunauer-Emmett-Teller (BET) surface area and the pore size
distribution were analyzed by measuring the N2 adsorption
isotherms at 77 K using a TriStar 3020 system (Micrometrics). XRD
data were analyzed on a Rigaku D/max-2400 diffractometer with
Cu-Ka radiation as the X-ray source in the 2θ range of 20–80˚. The
transmission electron microscopy was used to observe the size and
morphology of core-shell microspheres with Tecnai G2 F30. The
scanning electron microscope was used to observe the morphology
of microspheres with MIRA 3 XMU. The magnetic measurement
Synthesis of Fe3O4-Pd composite
100 mg of as-prepared Fe3O4 microsphere was dispersed in
ethanol (50 mL) with an ultrasonic treatment for 1 h. Then, 10mL of
palladium chloride aqueous solution (0.01mol/L) was added under
strong stirring for 1 h. Then, NaBH4 solution (50 mL, 0.02 M) was
added into the above mixture solution drop by drop under fiercely
stirring for 5 h. After the reaction, the product was collected by an
external magnet. Finally, the products were washed three times
with ethanol and deionized water and dried overnight in a vacuum
at room temperature.
was investigated on
a Quantum Design vibrating sample
magnetometer (VSM). XPS was tested on a PHI-5702 to study the
chemical constitution and the atomic valence states of the catalyst.
Transient photocurrent response measurements were performed
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Fe3O4@TiO2 (anatase) was obtained by calcination of amorphous
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DOI: 10.1039/C8NJ06508J
TiO2 encapsulating Fe3O4. Then, with the addition of Pd to the
support Fe3O4@TiO2(anatase), Pd ions were converted to Pd NPs by
photoreduction.
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Scanning electron microscope (SEM) and transmission electron
microscopy (TEM) was used to investigate the morphologies of
prepared materials. The SEM image of Fe3O4-Pd@TiO2(anatase)
(Figure S1) demonstrates that the overall morphology of Fe3O4-
Pd@TiO2(anatase) have a microspheres structure with an average
diameter of 130 nm. Figure 1a shows the typical TEM images of
Fe3O4-Pd, which are performed to clarify the basement structure.
The Pd NPs with an average diameter of 10 nm distributes on the
Fe3O4 basement structure with an average diameter of 100 nm.
Through the Figure 1b, Fe3O4-Pd@TiO2 shows a well-defined core-
shell structure and average diameter is about 150 nm. Pd NPs has
been encapsulated in homogeneous TiO2 shells. As is shown in
Figure 1c, High-resolution TEM (HRTEM) images manifest that the
Fe3O4-Pd@TiO2(anatase) is prepared by calcination at 500 °C with
the protection of nitrogen gas. As a result, the diameter of TiO2
layer is decreased and obtained anatase-TiO2, which obviously has a
pore structure. Meanwhile, the lattice fringe of TiO2, Pd NPs and
Fe3O4 are shown in Figure S2. It proves that Fe3O4-
Pd@TiO2(anatase) with porous structure has been successfully
prepared. On the other hand, Fe3O4@TiO2 is prepared by coating a
continuous layer of amorphous TiO2 shells on Fe3O4 microspheres
(Figure 1d). It can be observed that amorphous TiO2 is
homogeneous packaged on Fe3O4 microspheres and the thickness
of these outer amorphous TiO2 shells is about 30 nm. As shown in
Figure 1e, Fe3O4 microspheres is wrapped in anatase-TiO2 shells,
which are obtained from amorphous TiO2 by calcination at 500°C,
and Pd NPs load on the surface of the anatase-TiO2. It illustrates
that the structure of Fe3O4@TiO2(anatase)-Pd is successfully
prepared. The Pd nanoparticles is evenly distributed on the surface
of Fe3O4@TiO2(anatase), and the average size of Pd nanoparticles is
about 5-10nm. The EDX spectra and elemental mapping images in
Figure 1f, S3 indicates the existence of Fe, O, Ti, Pd in Fe3O4-
Pd@TiO2(anatase), and the uniform coverage of TiO2 shells on the
Fe3O4-Pd. It is noted that the Cu peaks are derived from Cu grid in
TEM analysis. Fabricating Fe3O4@TiO2(anatase)-Pd and Fe3O4-
Pd@TiO2(anatase) is for compare the catalytic activity of palladium
in the inner and outer of TiO2 shell for hydrogenation of aryl
cyanide reaction.
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Scheme 1. Schematic illustration for synthetic strategy of the
mesoporous microsphere.
using an electrochemical workstation (CHI 660E) in 0.1 M HCl
solution and 400w mercury high voltage lamp as the light source. A
calibrated Ag/AgCl electrode was used as the reference electrode,
and a Pt wire was used as the counter electrode.
Process for the hydrogenation of cyanobenzene
Catalyst powder (20mg) was suspended in a 0.1mol/L HCl
solution under an ultrasonic treatment for 0.5h, and then
transferred to a quartz tube containing cyanobenzene (0.05 mmol)
and oxalic acid (0.2 mmol). The quartz tube was photoirradiated by
a 400W mercury high pressure lamp under magnetic stirring at
room temperature. After the reaction, the catalyst was retrieved by
an extra magnet and the solution was neutralized with NaOH
solution. In the end, the solution was washed by saturated salt
water, extracting by ethyl acetate. After removing ethyl acetate by
reduced pressure distillation, products were determined by a GC-
MS.
Results and discussion
Catalyst synthesis and characterization
The preparation process of Fe3O4-Pd@TiO2(anatase) and
Fe3O4@TiO2(anatase)-Pd are illustrated in Scheme 1 schematically.
During Fe3O4-Pd@TiO2(anatase) preparation, with the addition of
Pd2+ to the support Fe3O4, Pd ions were converted to Pd NPs by
sodium borohydride reduction firstly. Then, Fe3O4-Pd was
encapsulated in amorphous TiO2 shell and calcined at 500 °C.
Furthermore, During Fe3O4@TiO2(anatase)-Pd preparation, firstly,
The X-ray diffraction (XRD) patterns of Fe3O4, Fe3O4-Pd,
amorphous Fe3O4-Pd@TiO2 and Fe3O4-Pd@TiO2(anatase) were
recorded. Figure 2a shows the XRD pattern of Fe3O4 microspheres.
Characteristic diffraction peaks are observed at 2θ of 30.11, 35.51,
43.31, 57.11, and 62.81, which correspond to the diffraction of
(220), (311), (400), (511), and (440) planes of Fe3O4 (JCPDS no. 01-
0640). All the peaks are matched well with the cubic crystalloid of
Fe3O4, and the sharp and strong peaks confirm that the products
are well crystallized. As is shown in Figure 2b, the peaks at about
40.1, 46.6 and 68.1° are corresponds to the (111), (200), (220)
planes of the Pd NPs (JCPDS no. 46-1043), further confirming that
the reduction process resulted in the formation of Pd NPs. For
comparison, the peak around 40.1˚ in Fe3O4-Pd, Fe3O4-Pd@TiO2 and
Fe3O4-Pd@TiO2(anatase) samples (Figure 2b-d) can be attributed to
Figure 1. TEM images of (a) Fe3O4-Pd (b) Fe3O4-Pd@TiO2 (c) HRTEM
images of Fe3O4-Pd@TiO2(anatase) (d) Fe3O4@TiO2 (e)
Fe3O4@TiO2(anatase)-Pd (f) EDX spectra of Fe3O4-Pd@TiO2(anatase).
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Figure 2. XRD patterns of (a) Fe3O4 (b) Fe3O4-Pd (c) Fe3O4-Pd@TiO2 Figure 4. VSM of (a) Fe3O4 (b) Fe3O4-Pd, (c) Fe3O4-Pd@TiO2, (d)
(d) Fe3O4-Pd@TiO2(anatase).
Fe3O4-Pd@TiO2 (anatase), and (e) Fe3O4@TiO2(anatase)-Pd.
Fe3O4-Pd @TiO2(anatase) are found to be 334.8 and 340 eV,
respectively (Figure 3c). The binding energies of Pd 3d5/2 and
3d3/2 for Fe3O4@TiO2(anatase)-Pd are found to be 335 and 340
eV, respectively (Figure 3d). It demonstrates that all the loaded
Pd is in a state of zero valent.
the Pd species, indicating that the successful immobilization of
Pd nanoparticles on the surface of Fe3O4, while the reduction
of Pd peaks may be ascribed to encapsulating of TiO2 (Figure
2c, 2d). The appeared peak at 25.2, 48.0, 53.8, 62.1 and 68.7˚
are corresponds to the (101), (200), (105), (213), (116), planes
of the anatase shell (JCPDS no. 21-1272) in Figure 2d.
Noteworthy, none peaks attributed to anatase occurred in the
XRD patterns (Figure 2c), demonstrating the amorphous
nature of the Fe3O4-Pd@TiO2.
To examine the chemical constitution and the atomic
valence states of the catalyst, X-ray photoelectron
spectroscopy (XPS) measurements were performed (Figure 3).
Figure 3a, b presents XPS all elemental analysis of the Fe3O4-
Pd@TiO2(anatase) and Fe3O4@TiO2(anatase)-Pd. The peaks
corresponding to oxygen, titanium, palladium, and iron
elements are clearly observed within the sample. The high-
resolution spectrum of Pd 3d is analyzed in detail in Figure 3c,
d. The binding energies of Pd 3d5/2 and Pd 3d3/2 for
The magnetic properties of Fe3O4, Fe3O4-Pd, Fe3O4-Pd@TiO2,
Fe3O4-Pd@TiO2 (anatase), and Fe3O4@TiO2(anatase)-Pd were
studied by VSM at room temperature. Figure 4 shows that
magnetization curves reveal the superparamagnetic behavior
for these magnetic microspheres and their saturation
magnetization values are determined to be 82.0, 61.5, 34.8,
30.2, and 27.7emu/g, respectively. The saturation
magnetization decreases significantly because the surface of
Fe3O4 is loaded with Pd NPs and coated with TiO2 shell.
Although the saturation magnetization values of these
composite materials are lower than that of Fe3O4, an external
magnet can still quickly separate the catalyst from the reaction
system (shown in the inset of Figure 4).
The photocurrent densities of catalyst exhibit an obvious
increase in light-on cycles and decrease in light-off cycles. As shown
in Figure 5, photocurrent densities of all three materials exhibit
observably strong responses to light. The photocurrent densities of
Fe3O4@TiO2(anatase) increases sharply from 0 μA/cm2 to 0.35
μA/cm2, and Fe3O4@TiO2(anatase)-Pd increases greatly from 0
μA/cm2 to 1.45 μA/cm2. As is expected, the photocurrent intensity
of Fe3O4-Pd@TiO2(anatase) increases from 0μA/cm2 to 1.58μA/cm2,
which is significantly greater than the Fe3O4@TiO2(anatase) and
Fe3O4@TiO2(anatase)-Pd. This suggests that more effective
separation of electrons and holes and fewer recombination of
electrons and holes occur in Fe3O4-Pd@TiO2(anatase) in this case. In
the process, we choose HCl solution as electrolyte, cyanobenzene
and oxalic acid as reactant. The photocurrent intensity test keeps
on consuming oxalic acid and HCl solution from the electrolyte, thus
forming an activatory hydrogen species (Pd-H) which can react with
cyano easily. Since the reduction (H+/H2) in the reaction system will
constantly consume electrons, the separation of electrons and
holes are accelerated, which make the photocurrent density of
increases. In addition, due to the higher charge density in the
material after
Figure 3. XPS spectra for (a) Fe3O4-Pd@TiO2(anatase), (b)
Fe3O4@TiO2(anatase)-Pd, and (c, d) show Pd 3d5/2, Pd 3d3/2
binding
energies
of
Fe3O4-Pd@TiO2(anatase)
and
Fe3O4@TiO2(anatase)-Pd, respectively.
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Catalyst testing for the hydrogenation reduction of cyano
aromatic compounds
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Catalytic reduction of cyanobenzene is evaluate on the
catalytic activity of the Fe3O4-Pd@TiO2(anatase). The reaction
between cyanobenzene and oxalic acid is carried out as a
model reaction for optimizing the solvent and time for the
hydrogenation of aromatic nitrile. The reaction is
implemented at room temperature and HCl solution is used as
solvent to research the effect of different reaction time on the
yield. The results are summarized in Table 1. Notably, when
the reaction time is 1 hour, the yield reaches the highest
(yielding products of 90.7%), and after 1 hour, the yield holds
steady. Therefore, the effect of different solvents for the
photocatalytic reduction of PhCN to BnNH2 is studied with 1
hour as the optimal reaction time.
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Figure 5. Transient photocurrent response curves of
Fe3O4@TiO2(anatase), Fe3O4@TiO2(anatase)-Pd and Fe3O4-
Pd@TiO2(anatase). All tests were carried out with an applied
voltage (0.5 V).
Table 1. The effect of different solvents on the photocatalytic
reduction of PhCN to BnNH2.a
the reactant is involved, the diffusion time is longer, therefore, it
takes a long time for all curves to attain the steady state in light-on
and light-off stages. Furthermore, the above results have good
reproducibility. The Fe3O4-Pd@TiO2(anatase) exhibits the most
effective separation of electrons-holes pairs and the largest
photocurrent density, which is due to form a more stable
schottky junction by Pd in TiO2 and will offer the benefits for
photocatalysis.
N2 adsorption-desorption isotherms and the corresponding
pore size distribution curve for the precursor Fe3O4-
Pd@TiO2(anatase) samples are showed in Figure 6. A slight
hysteresis loop is observed in the high-pressure region (P/P0 =
0.7-1.0), indicating the existence of porous structure in Fe3O4-
Pd@TiO2(anatase). It is shown in the inset of Figure 6, the pore
size is calculated by the BJH method is to be 13 nm, and the
most of pores are located in the area of mesoporous, which is
correspond with the TEM result. Specific surface area of Fe3O4-
Pd@TiO2(anatase) microspheres is calculated by the BET
method is to be 128.9 m2·g-1. The mesoporous structure is
benefited for increasing specific surface area and improving
catalytic performance.
Entry
Solvent
Temperatur Time(h)
Yield(%)b
e (℃)
1
2
3
4
5
6
7
8
9
HCl solution
HCl solution
HCl solution
HCl solution
water
25
25
25
25
25
25
25
25
25
25
0.5
1
63.5
90.7
90.4
90.3
40.1
5.3
-
1.5
2
1
NaOH
1
acetone
1
acetonitrile
methanol
ethanol
1
-
1
-
10
1
-
a
Reaction conditions: catalyst amount containing Pd (0.014
mmol), PhCN (0.49 mmol), oxalic acids (1.96 mmol), solvent
(5.0 mL), reaction time 60 min.
b Determined by GC or GC-MS.
As a result ， as shown in Table 1, four protons are
integrated into BnNH2 and the highest BnNH2 yield is in the HCl
solution group, whereas the water group result in a low yield
of BnNH2. So it is demonstrable that these protons are
provided by oxalic acid and can be facilitated form under acidic
conditions. The yield drastically decreases in a sodium
hydroxide solution. Under the condition of alkaline, protons
combine with hydroxide roots, resulting in a low yield of
BnNH2. In acetone and acetonitrile systems, these solvents are
Figure 6. Nitrogen adsorption-desorption isotherms and pore size
distribution (inset) of Fe3O4-Pd@TiO2(anatase).
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aprotic, no reduction of PhCN occurred. When methanol and Schottky junction can capture electrons rapidly aVniedwbAerticcolemOnelinae
ethanol are used as solvents, no BnNH2 is produced, a small highly active reaction site, which proviDdOesI: 1e0l.e10c3tr9o/Cn8sNfJo06r5t0h8eJ
amount of toluene is generated. The results indicate that the reduction reaction at the interface, thus contributing to the
alcohol solvent can induce strong hydrogenation of PhCN, remarkable enhancement of photocatalytic activity and
which can lead to the elimination of nitrogen atoms. These selectivity.53, 54 Therefore, the higher photocatalytic efficiency
results clearly indicate that the presence and concentration of is due to the higher charge separation efficiency and charge
protons have an important influence on the yield of BnNH2 of transfer rate on anatase surface, which are caused by Schottky
the resulting catalysts.
junction interface and large interface area. Furthermore,
amorphous catalysts have no catalytic activity due to the lack
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Table 2. The effects of different kinds of TiO2 on the of optical activity of amorphous TiO2. (entry4, 5)
photocatalytic hydrogenation of cyanobenzene in acidic
aqueous suspensions of Fe3O4-Pd@TiO2.a
The as-obtained Fe3O4-Pd@TiO2(anatase) displays excellent
catalytic performance when it is compared to Fe3O4-
Pd@TiO2(rutile), amorphous Fe3O4-Pd@TiO2 and amorphous
Fe3O4@TiO2-Pd, meanwhile, we also compared the catalytic
activity of Fe3O4-Pd@TiO2(anatase) with Fe3O4@TiO2(anatase)-
Pd (entry1, 3). The results demonstrate that the Fe3O4-
Pd@TiO2(anatase) still have a higher conversion of PhCN and
selectivity of BnNH2 than Fe3O4@TiO2(anatase)-Pd for the
reaction of reduction of PhCN to BnNH2. When Pd is
embedded in porous TiO2, the formed Schottky junction is
more stable and the separation efficiency of photo-generated
electrons and holes is higher than Pd on the surface of TiO2,
which is proved by transient photocurrent response curves
(Figure 5). Simultaneously, the unique architecture not only
can efficiently suppress the aggregation of Pd NPs, but also can
protect Pd NPs from falling off during reactions.
At the same time, we have also investigated the influence of
the electric effect and steric hindrance effect of the
substituents to the yields. Under the optimized conditions and
the presence of a certain amount of Fe3O4-Pd@TiO2(anatase),
various aromatic cyanides are allowed to react with oxalic acid
for a certain period of time. The results are summarized in
Table 3, it can be observed that the reactions of various
aromatic cyanides with oxalic acid proceeded efficiently (Table
3, entries 1-15). The yield of corresponding aromatic amine is
60-93%. The results show that the aromatic cyanides with
electron-withdrawing group can be hydrogenated much easier
than the aromatic cyanides with electron-donating group.
Furthermore, if there is a substituent in ortho position of
cyano, either the electron-withdrawing group or the electron-
donating group, the yield will decrease, which may be caused
by the high steric hindrance of the ortho-group.
Entry Photocatalytic
TiO2 Crystal
phase
PhCN
BnNH2
conv.(%)b sel.(%)c
1
2
3
4
5
Fe3O4-Pd@TiO2
Fe3O4-Pd@TiO2
Fe3O4@TiO2-Pd
Fe3O4-Pd@TiO2
Fe3O4@TiO2-Pd
Anatase
Rutile
99%
65%
96%
-
80%
45%
76%
-
Anatase
Amorphism
Amorphism
-
-
a Reaction conditions: catalyst amount containing Pd (0.014
mmol), PhCN (0.49 mmol), oxalic acids (1.96 mmol), HCl
solution (5.0 mL), reaction temperature r.t., reaction time
60 min.
b, c Determined by GC or GC-MS.
The effect of different catalyst structures and TiO2 of
different crystal type on the photocatalytic reduction of PhCN
to BnNH2 is shown in Table 2. In all the contrast reactions, HCl
solution is chosen as the solvent for 1 hour reaction. The
photocatalytic activities of Fe3O4-Pd@TiO2(anatase) are
compared with Fe3O4-Pd@TiO2(rutile) (entry1, 2). The results
show that Fe3O4-Pd@TiO2(anatase) exhibits the higher
conversion of PhCN and selectivity of BnNH2 than Fe3O4-
Pd@TiO2(rutile) for catalyzing the reaction. The high
conversion and selectivity also benefits from the large surface
area and optical activity of anatase phase. Although both rutile
and anatase belong to orthogonal crystal systems, the degree
of distortion of their TiO6 octahedral is different. The almost
perfect orthogonal crystal system of rutile has little lattice
distortion ， but the crystal lattice of anatase is severely
distorted.48-51 There are more defects and dislocations in the
crystal lattice, and more oxygen vacancy can be generated to
capture electrons, making it easy to separate photo-generated
electrons and holes.52 Pd NPs and anatase can be used for
forming a metal-semiconductor schottky junction. It can
promote transfer of photo-generated electrons from the
conduction band (CB) of TiO2 to surface of Pd, making
electrons and holes located on different area and effectively
inhibiting the recombination of electrons and holes, thus
improving the optical activity of Pd-TiO2. Furthermore,
Table 3. Fe3O4-Pd@TiO2(anatase) catalyzed reduction of
various aromatic cyanide.a
Entry
R
Time(h)
Yield(%)b
TOF(h-1)
12.3
1
2
3
2-CH3
4-CH3
2-OCH3
4
1
5
69
82
60
58.6
8.6
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On the basis of experimental results and some previously
View Article Online
we surmised a poDssOibI:l1e0.1m03e9c/hCa8nNiJs0m650fo8Jr
4
5
4-OCH3
3,5-(OCH3)2
2-OH
1
1.5
1.5
1.5
0.75
2
87
85
78
90
93
72
70
75
71
87
86
92
62.1
40.5
37.1
42.9
88.6
25.7
25.0
35.7
25.4
41.4
61.4
65.7
57
reported work,30,
Fe3O4-Pd@TiO2(anatase)
catalyzing
hydrogenation
of
benzonitrile (scheme 2). Initially, under ultraviolet
photoirradation, electrons and holes of TiO2 are separated and
photo-generated electrons migrate from the conduction band
(CB) of TiO2 to surface of Pd. Oxalic acid provides four
hydrogen atoms (protons) to combine with electrons on the
surface of Pd to form an activated hydrogen species (Pd-4H),
which is promoted by acidic conditions. Oxalic ion as a hole
scavenger is oxidized to CO2 by holes. Later, two H atoms of
Pd-4H is transferred to a carbon atom and nitrogen-atom of
cyanobenzene, forming an intermediate Ph-CH=NH, and then
two H atoms of Pd-2H is transferred to Ph-CH=NH, forming Ph-
CH2-NH2 and Pd(0) after dissociation. Meanwhile, Pd(0) enters
the next catalytic cycle.
The recyclability of Fe3O4-Pd@TiO2(anatase) is further
investigated because the recyclability of the catalyst is one of
the most important issues for practical applications. After the
reaction of benzonitrile to benzylamine under the optimized
reaction conditions, the catalyst is retrieved by an external
magnetic and washed with ethanol and deionized water,
vacuum-drying and recycling for the next time. As shown in
Figure 7, although conversion of PhCN decline slightly,
selectivity of BnNH2 still remain highly after performing at least
5 cycles. ICP analysis shows that the weight of Pd NPs
decreased by 0.3% after 5 continuous use of the catalyst. A
slight decline in the conversion may be attributed to the slight
loss of Pd nanoparticles in the recycling process. Therefore,
the results indicate that the special structure can protect Pd
NPs from leaching during reactions further confirm the high
stability and recyclability of Fe3O4-Pd@TiO2(anatase).
6
7
4-OH
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8
4-HS
9
4-CF3
10
11
12
13
14
15
3,5-(CF3)2
4-COCH3
3-COOH
4-N(CH3)2
2-NH2
2
1.5
2
1.5
1
4-NH2
1
a
Reaction conditions: catalyst amount containing Pd
(0.014 mmol), aromatic cyanides (0.49 mmol), oxalic acids
(1.96 mmol), HCl solution (5.0 mL), reaction temperature
r.t.
b Determined by GC or GC-MS.
c
The turnover frequency (TOF) was calculated by the
following formula: TOF=nyield· t-1 · nPd-1, nyield is yield of
product, t is time of reaction, npd is the molar amount of
Pd catalyst.55, 56
Mechanism
hydrogenation of benzonitrile reaction
for
Fe3O4-Pd@TiO2(anatase)
catalyzed
Figure 7. Recyclability of Fe3O4-Pd@TiO2(anatase) for the
selective reduction of aromatic cyanide to aromatic primary
amines.
Conclusions
Scheme 2. Mechanism for Fe3O4-Pd@TiO2(anatase) catalyzed
hydrogenation of benzonitrile reaction.
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In summary, a multicomponent and high-performance
Fe3O4-Pd@TiO2(anatase) with well-defined core-shell
nanostructures was successful fabricated. The as-prepared
Fe3O4-Pd@TiO2(anatase) exhibits a remarkable photocatalytic
activity, robust stability and recyclability for hydrogenation of
aromatic cyanide. The main reason is that Pd NPs and TiO2
form
a stable schottky junction resulting in effective
separation of electrons and holes. An activatory hydrogen
species (Pd-H) are formed on the surface of Pd. Furthermore,
magnetic core-shell structure not only can efficiently suppress
the aggregation of Pd NPs and protect Pd NPs from falling off
during reactions, but also allows the photocatalyst to be
facilely reused. This work provides a promising strategy for
design metal-semiconductor schottky junction by coating
active noble metal sites with mesoporous semiconductor,
which could be applied in various photocatalytic organic
synthesis reactions.
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Conflicts of interest
There are no conflicts to declare.
Acknowledgements
This research was supported by the National Natural Science
Foundation of China (21872066 and 21802058), and
Fundamental Research Funds for the Central Universities
(lzujbky-2017-kb11 and lzujbky-2017-107).
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The Fe3O4-Pd@TiO2 exhibited an extremely superior photocatalytic
activity for the selective reduction of aromatic cyanide to aromatic
primary amines.