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New Journal of Chemistry Accepted Manuscript

Facile one-pot tandem reductive amination of aldehydes from
Published on 28 September 2016. Downloaded by Heriot Watt University on 28/09/2016 05:30:38.
nitroarenes over a hierarchical ZSM-5 zeolite containing palladium

Received 00th January 20xx,
Accepted 00th January 20xx
nanoparticles
DOI: 10.1039/x0xx00000x Roozbeh J. Kalbasi a* and Omid Mazaheri b
www.rsc.org/njc In the present work, palladium nanoparticles supported on hierarchical ZSM-5 zeolite (Pd/H-hierarchical ZSM-5) was
evaluated as a novel acid-metal bi-functional heterogeneous catalyst for direct one-pot reductive amination of nitroarenes
using aldehyde in the presence of NaBH4 and water as a mild reducing agent and green solvent, respectively. The
structural and morphological properties of the prepared catalyst were investigated by XRD, BET, FT-IR, NH3-TPD, SEM,
TEM, XPS, DRS-UV and ICP-AES techniques. The reaction was carried out at room temperature, in short reaction time
without producing any by-products. The stability of the catalyst was good and it could be reused six times without much
loss of activity in reductive amination reaction.
KEYWORDS: Tandem reductive amination; Hierarchical ZSM-5 zeolite; Palladium nanoparticles; Heterogeneous catalyst;
Acid-metal bifunctional catalyst.
6
compounds. In this regards, one of the economical and clean
1. Introduction pathways is direct reductive amination of aldehydes and
Amines are basically valuable compounds, which have been ketones using nitroarenes instead of amines. In recent years,
widely used in dyes, rubber materials, agricultural chemicals, few studies have been reported on these types of three-step
herbicides, chelating agents, pharmaceuticals, surfactant reactions ,which start by using nitroarenes and usually need
7-13
1
textile auxiliaries, polymers. There are several methods for several hours to perform reaction. In this method, after
the preparation of substituted amines: (a) using alkyl halides reduction of nitroarenes to amines, the carbonyl compounds
or sulfonates as alkylating agents, alkylation of ammonia, react with amines to produce imines. Finally, the C=N bond of
primary or secondary amines; (b) reduction of nitrogen- the imine is hydrogenated with hydride compounds or
containing functional groups such as nitro, carboxamide molecular hydrogen (H2) to yield the secondary and tertiary
derivatives, cyano, and azide and (c) reaction of aldehydes or amines. (Scheme 1).10, 12,13
ketones with ammonia, primary or secondary amines in Bi-functional catalysts can be used to perform one-pot
presence of different reducing agents which for this cascade reductive amination reaction with nitroarenes in three
transformation, the two synthetic methods were commonly steps, which have to have metallic and acidic character. In this
used: direct and indirect methods.2-4 respect, recently a variety of catalytic systems have been
7,11
Direct Reductive amination represents one of the most developed which in the midst of them, heterogeneous
convenient and versatile methods of amine synthesis that catalysts have many benefits like recovery capabilities and
7,8,11,14,15
offers significant advantages over other amine syntheses, like easy separation in comparison to homogeneous ones.
facilitating the separation steps, the mild reaction conditions, Recently, various metal nanoparticles have been used as
wide commercial availability of substrates and increasing hydride transfer catalysts in the reduction systems, for
16-19
yields.5 Also, the operational simplicity and reducing the use of instance: Pt, Ni, Cu, and Pd. However, an effective control
reagents adds to the values of this method as a practical of particle size and a uniform dispersion of nanoparticles in
alternative to the reductive amination of carbonyl catalytic applications are typically anticipated. Nonetheless,
nanoparticles usually aggregate to yield bulk-like materials
that extremely reduce the activity of catalysts and selectivity.
Accordingly, they must be immobilized in the pores of
20
heterogeneous supports such as ordered mesoporous silica
or embedded in matrices such as macromolecular organic
ligands or polymers.21-23
This journal is © The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 1
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DOI: 10.1039/C6NJ02262F
ARTICLE Journal Name
NO2 NH2 O
H N HN
Pd/H-hierarchical ZSM-5 Pd/H-hierarchical ZSM-5 Pd/H-hierarchical ZSM-5
NaBH4 NaBH4 NaBH4 H

Scheme 1. Reaction steps and intermediates proposed in the direct one-pot reductive amination of aldehydes from nitroarenes.
It has been proven that in the direct reductive amination of (TEM) observations were performed with on a Philips CM30
carbonyl compounds with nitrobenzene, the acidic properties electron microscope at an accelerating voltage of 300.00 kV.
of supports can be effective to boost the reaction.24,25 Since Scanning Electron Microscope (SEM) studies were performed
zeolites are good candidates among the variety of the supports on Hitachi S4160 FESEM. The Pd amount content of the
to be used in this reaction. Despite that, because of diffusion catalyst was appraised estimated by inductively coupled
restriction in its microporous framework, the results indicated plasma atomic emission spectrometry (ICP-AES) using perkin-
26
a clogging and poisoning. During the past decade, significant Elmer optima 4300.
13 1
efforts have been devoted to developing methods that The products were characterized by C NMR and H NMR
introduce mesoporosity in zeolite materials with shape spectra (Bruker DRX-500 Avance spectrometer at 125.47 MHz
selective properties by different methods that decreasing and 500.13, respectively). Melting points were measured with
accessibility limitations and the diffusion of larger molecules in an electro thermal 9100 apparatus. All the products were
27 1
biomass promotion. The conflation of mesopores in the known compounds and they were characterized by H NMR,
13
zeolite materials can decrease pore blockage due large C NMR and FT-IR.
molecules adsorbing to the surface and thus enhance 2.2. Catalyst Preparation
28,29
activation of the support. 2.2.1. Preparation of KIT-6. Firstly, pursuant to the reported
To address this issue, we will introduce synthesis and procedure, high quality ordered mesoporous KIT-6 was
application of dispersed palladium nanoparticles incorporated prepared to generate the hierarchical zeolite.30 The large pore
in ZSM-5 zeolite with hierarchy structure as a novel acid-metal 3D (Ia3d) cubic mesostructure, designated as KIT-6, was
bi-functional heterogeneous catalyst. Furthermore, the prepared using tetraethylorthosilicate (TEOS) and Pluronic
catalyst was used effectively for the direct one-pot reductive P123 (EO20PO70EO20) template as the silica precursor and a
amination of nitroarenes compounds using aldehyde in the structure directing agent, respectively. The detailed synthesis
presence of a small amount of NaBH4 as a reducing agent and procedures are explained as follows: 6 g of n-butanol (0.161
water as a green solvent at room temperature without any by- mol) and 6 g (1.03 mmol) of P123 were dissolved in 270 g (15
products. mol) of distilled water and 11.4 g (0.115 mol) of concentrated
hydrochloric acid (37 wt. % HCl). Then after, 12.9 g (0.061 mol)
of TEOS was added to this mixture. The mixture was stirred for
2. EXPERIMENTAL 24 h at 318 K in order to form the mesostructure product.
2.1. Catalyst Characterization Finally, the reaction mixture was heated for 24 h at 370 K for
The samples were analyzed using the X-ray powder diffraction hydrothermal treatment under static conditions. The solid
(XRD) of the catalyst was performed on a Bruker D8Advance X- product filtered, washed with deionized water and dried at
ray diffractometer using nickel-filtered Cu Kα radiation at 40 373 K. Subsequently, the samples were calcined for 6 h at 823
kV and 20 mA. FT-IR spectroscopy (using a Perkin-Elmer 65 in K to remove the organic template.
-1
KBr matrix in the range of 4000-400 cm ). The BJH pore size 2.2.2. Preparation of hierarchical ZSM-5 zeolite.
distribution, BET specific surface areas and MP-plot of the Hierarchical zeolite prepared by KIT-6 as an indirect template
31
samples were determined by adsorption-desorption of (silica source) via the method described in recent literature.
nitrogen at liquid nitrogen temperature using a Series BEL In brief, solution of sodium aluminate and
SORP 18. Temperature-programmed desorption of NH3 (NH3- tetrapropylammonium hydroxide (TPAOH, 40 wt.%) were
TPD) was recorded on FINESORB-3010 equipped with a impregnated into 1 g of KIT-6 powder. The synthesis gel
thermal conductivity detector. The DRS UV-vis (Al2O3:60SiO2:4Na2O:4800H2O:18TPAOH) was obtained as the
Spectrophotometer was recorded with JASCO spectrometer, final molar ratio. The mixture was stirred for 12 h at 293 K.
V-670 from 190 to 2700 nm. Moreover, X-ray photoelectron Then, the aged synthesis mixture was transferred into a
spectrum (XPS) was carried out recorded on ESCA SSX-100 Teflon-lined stainless steel autoclave followed by reaction for
(Shimadzu) using a non-monochromatized Mg Kα X-ray as the 48 h at 448 K. Then, the solid product was filtered, washed
excitation source. In order to get detailed information on the with deionized water and dried at room temperature at 393 K
size of Pd nanoparticles Transmission Electron Microscope overnight. In the end, the sample was calcined for 6 h at 823 K
2 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 20xx

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to remove the TPAOH template, and the hierarchical ZSM-5 by ion-exchange method. Furthermore, palladium
zeolite was obtained. nanoparticles have been reduced by hydrazine hydrate and
2.2.3. Preparation of acidic hierarchical zeolite (H- immobilized on hierarchical zeolite. Subsequently, the Pd/H-
hierarchical ZSM-5). The acid form of hierarchical zeolite was hierarchical ZSM-5 zeolite with excellent properties was
prepared by ion-exchange method. In short, 1 g of hierarchical fabricated by this simple method for the reductive amination
zeolite was mixed up with 100 mL aqueous solutions of NH4Cl of nitro aromatic compounds in water medium and in the
presence of low amount of NaBH4 as a reducing agent.

(1 M) in the reflux condition for 48 h, then the mixture was
washed with deionized water, dried for 12 h at 383 K and 3.1. Catalyst characterization
finally was calcined for 6 h at 823 K to prepare H-hierarchical The expected crystalline structure of H-hierarchical ZSM-5 and
ZSM-5. Pd/H-hierarchical ZSM-5 were confirmed by powder XRD

2.2.4. Preparation of palladium nanoparticles supported measurements in Fig. 1S (ESI†) and Fig. 1, respectively. The
on hierarchical zeolites (Pd/H-hierarchical ZSM-5). Pd/H- major phases of H-hierarchical ZSM-5 show reflections at 2θ
hierarchical ZSM-5 was prepared through in situ reduction of values of 7-9˚ and 23-25˚, which completely agree with the
Pd ions inside the channels of H-mZSM-5, according to our
32
previous report. The preparation of Pd/H-hierarchical ZSM-5
was carried out as follows:
H-hierarchical ZSM-5 (0.1 g) and 10 mL of an aqueous acidic
solution (CHCl = 0.09 M) of Pd(OAc)2 (0.0088 g, 0.0392 mmol)
were placed in a round bottom flask. The mixture was heated
to for 5 h at 353 K while being stirred. Next, 0.6 mL (2.47
mmol) aqueous solution of N2H4•H2O (80 vol.%) was added to
the mixture drop by drop in 20–25 min. Afterward, the
solution was stirred for 1 h at 333 K. After that, it was filtered
and washed sequentially with methanol and chloroform to
remove excess N2H4•H2O and was dried at room temperature
to yield Pd/H-hierarchical ZSM-5 zeolite. The Pd content of the
catalyst was estimated by decomposing the accurate amount
of the catalyst by hydrochloric acid, nitric acid, fluoric acid and Figure 1. XRD pattern of Pd/H-hierarchical ZSM-5 (2θ = 5-90).
-1
perchloric acid. ICP-AES estimated 0.332 mmolg Pd content
of Pd/H-hierarchical ZSM-5. characteristic peaks of MFI structure.33 In addition, the wide-
2.3. General procedure for direct reductive amination of angle XRD pattern of the Pd/H-hierarchical ZSM-5 (2θ = 5-90◦)
aldehydes from nitroarenes. A mixture of nitrobenzene (2 (Fig. 1) show peaks of 2θ values 39.92◦, 46.54◦, 67.90◦ and
mmol) and benzaldehyde (2 mmol) in water (3 mL) was placed 82.0◦, which are assigned to the corresponding (111), (200) and
in a round bottom flask and stirred for 1 min at room (220) and (311) indices of the face-centered cubic (fcc) lattice
temperature. Afterward, to the resulting mixture, Pd/H- of metallic Pd.34,35 The XRD results imply that after the
immobilized of palladium nanoparticles on hierarchical
hierarchical ZSM-5 (0.04 g) and NaBH4 (6 mmol) were added
zeolites, zeolite structure has not changed, indicating a
and the mixture was stirred at room temperature until TLC
successful synthesis of the Pd/H-hierarchical ZSM-5 (Fig. 1).
showed the complete disappearance of the benzaldehyde.
The FT-IR spectra were carried out to identify of pure H-
Then, the reaction mixture was quenched with water (10 mL)
hierarchical ZSM-5 and Pd/H-hierarchical ZSM-5, which are
and the product was extracted with diethylether (2 × 10 mL). shown in Fig. 2S (ESI†) and Fig. 2. A broad band at around 3440
After they finished, the organic phase was dried over cm-1 is observed in both samples which represent the O-H
anhydrous Na2SO4, filtered and concentrated. In the end, the stretching vibration of the adsorbed water molecules and
products were obtained very pure just by extract with hydroxyl groups of zeolite surface. Additionally, the band
diethylether in the majority of the reactions. In a few cases, around ~3650 cm-1 is generally attributed to the bending
column chromatography was used to obtain the pure product. vibration of Si-OH-Al groups that shown to be acidic (more
The product was identified with a melting point, FT-IR specifically Bronsted acid sites) and in agreement with prior
1 13 36,37 -1
spectroscopy techniques, HNMR and CNMR. reports. The band at about 1630 cm can be attributed to
adsorbed water, which is principally close to related
38,39 -1
3. RESULTS AND DISCUSSION reports. The peaks around 1220 cm (external asymmetric
-1
stretch), 1150-1050 cm (internal asymmetric stretch), ~800
As a first step towards the accomplishment of the synthesis of -1
cm-1 (symmetric stretch) and 450 cm (T–O bend) are
the hierarchical zeolite, high quality ordered mesoporous KIT-6
characteristic of highly siliceous materials. In the FT-IR spectra
silica was prepared by sol-gel technique. After that, KIT-6 was
of H-hierarchical ZSM-5 and Pd/H-hierarchical ZSM-5, the new
used as an indirect template for the synthesis of zeolite. -1
band at around 550 cm corresponds to the double five rings
Moreover, the acid form of hierarchical zeolite was prepared

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2 -1
(Si–O–Si or Al–O–Si groups) of the typical structure of MFI-type with a high BET surface area (223 m g ), pore size (4.6 nm)
31 3 -1
zeolites. Both the FT-IR spectra and the XRD can represent and pore volume (0.26 cm g ) (Table 1). In addition, the co-
that MFI-type zeolite (H-hierarchical ZSM-5) has been presence of micropores is suggested by t-Plot and MP-Plot
successfully synthesized. methods (Table 1). Apparently these results demonstrate the
-
Furthermore, the ratio of the intensities of 550 and 450 cm formation of a new hierarchical zeolitic structure with an
1
bands was used to figure out the (IR) crystallinity of the acceptable porosity and surface area. Based on the results, H-
prepared samples. The results roll up in Table 1. hierarchical ZSM-5 illustrates both mesoporous and

microporous structures.
All three cases of the specific surface area, pore diameter
(calculated by BJH) and pore volume of Pd/H-hierarchical ZSM-

5 are lower than those of H-hierarchical ZSM-5 (Table 1),
according to this results, palladium nanoparticles distributed
on the outer surface and their incorporation inside the (micro
and meso) pores of the hierarchical zeolites. Nonetheless, this
isotherm is still similar to type IV that is the characteristic of a
mesoporous material.
Fig 4S (ESI†) and Fig. 4 shows the pore size distribution
curves (using BJH method) of the synthesized zeolite. As can
be seen, the samples of H-hierarchical ZSM-5 and Pd/H-
Figure 2. FT-IR spectrum of Pd/H-hierarchical ZSM-5. (× Impurity: carbonyl hierarchical ZSM-5 have a narrow range pore size distribution
bond of acetone, which was used for rinse off the silicon wafer while with a pore diameter of about ~4 nm displaying the existence
preparation of KBr pellet). of a mesoporous structure in these zeolites. After the
incorporation of palladium nanoparticles, the pore size
High IR crystallinity matters to a high degree of ordering of distribution has slightly changed that indicates the distribution
the aluminosilicate (Al–O–Si) phase in a manner similar to that of palladium nanoparticles on the surface of zeolites.
40
in ZSM-5 zeolite. MP-Plot methods and t-Plot corroborate the presence of
The BET specific surface areas, the pore sizes and the pore microporosity of H-hierarchical ZSM-5 zeolite structures as
volumes of both samples were computed by BET, BJH, MP-Plot well (Table 1, Fig. 5S(ESI†)). These microporous structures are
and t-Plot methods (Table 1). The N2 adsorption–desorption still visible after the incorporation of palladium nanoparticles
isotherms for these samples are shown in Fig. 3S (ESI†) and Fig. (Fig. 5).42-44
3. Moreover, the corresponding pore size distribution curves The aforementioned results indicate that H-hierarchical
(micro and meso pores) are drawn in Fig. 4-5S (ESI†) and Figs. ZSM-5 and Pd/H-hierarchical ZSM-5 still show a hierarchical
4-5 for H-hierarchical ZSM-5 and Pd/H-hierarchical ZSM-5, structure with a suitable surface area, pore diameter and pore
respectively. As shown, according to the IUPAC nomenclature, volume, which make it reasonable to act as a catalyst.
two samples demonstrate isotherms of type IV, which are the According to the TPD results, the numbers of acid sites
typical characteristics of mesostructure materials (Fig. 3 and 3S were 0.96 mmol g-1 and 0.90 mmol g-1 for H-hierarchical ZSM-5
41
(ESI†)). and Pd/H-hierarchical ZSM-5, respectively (Table 1), which
indicates that despite of distribution palladium nanoparticles
on H-hierarchical ZSM-5, the acidic properties of Pd/H-
hierarchical ZSM-5 are still maintained.
Figure 3. N2 adsorption/desorption isotherm of Pd/H-hierarchical ZSM-5.
Figure 4. Pore size distribution of Pd/H-hierarchical ZSM-5 obtained by BJH

As shown, the H-hierarchical ZSM-5 can be applicable as a
method.
suitable supply for the deposition of palladium nanoparticles

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Table 1. Physicochemical properties of H-hierarchical ZSM-5 and Pd/H-hierarchical ZSM-5 samples obtained from N2 adsorption.
NH3
SBET Vmesopore Dmesopore Dmesopore Smicropore Smicropore Vmicropore Dmicropore IR crystallinity
Sample chemisorbed
(m2g-1)a (cm3g-1)a (nm)a (nm)b (m2g-1)c (m2g-1)d (cm3g-1)c (nm)c (%)e
(mmol/g)f
H-hierarchical

223 0.26 4.60 4.80 269 293 0.10 0.7 99 0.96
ZSM-5
Pd/H-hierarchical
154 0.23 4.1 4.20 236 234 0.07 0.7 94 0.90
ZSM-5
a
Calculated by BET method. b Mean pore diameter determined by using BJH method from the adsorption branch of the isotherm curves. c Calculated by MP-
Plot method. d The micropore surface area was estimated by the t-plot analysis using the adsorption branch of the isotherm curves. e IR crystallinity defined
as (I550/I450)/0.72×100% 40 with I550 and I450 the intensities of the bands at 550 and 450 cm-1, respectively. f NH3 TPD.
According to the literature results, the UV-vis spectrum of

Pd(OAc)2 revealing a peak at 400 nm refer to the existence of
Pd2+.45 As mentioned in Section 2, we used hydrazine hydrate
as a reduction agent to prepare Pd nanoparticle supported on
hierarchical zeolite from Pd2+/H-hierarchical ZSM-5. In spite of
a fact that we just mentioned, there were not any peaks at 400
nm in the UV-vis spectrum of Pd/H-hierarchical ZSM-5, which
illustrated a complete reduction of Pd2+ to Pd nanoparticles.
The chemical composition of Pd/H-hierarchical ZSM-5 was
also analysed by XPS (Fig. 7). The XPS results of Pd
nanoparticles dispersed in H-hierarchical ZSM-5 zeolite for Pd
3d spectrum with the binding energies of Pd 3d5/2 and Pd 3d3/2
lying at about 335.3 and 340.7 eV, respectively (Fig. 7). Which
indicate Pd nanoparticles are stable as a metallic state in H-
hierarchical ZSM-5 zeolite (the XPS spectrum of Pd2+ ions
appears two peaks at about 337 and 342 eV refer to Pd 3d5/2
Figure 5. Pore size distribution of Pd/H-hierarchical ZSM-5 obtained by MP- and 3d3/246) in comparison to the standard binding energy (Pd0
Plot method. with Pd 3d5/2 of about 335 eV and Pd3/2 of about 340 eV47). In
this context, it could be concluded that the Pd peaks in H-
0
Fig. 6 presents the result of the UV-vis spectrum of Pd/H- hierarchical ZSM-5 shifted to higher binding energy toward Pd
2+
hierarchical ZSM-5. After reduction of Pd /H-hierarchical ZSM- standard binding energy. As we know, the situation of Pd 3d
0
5 by hydrazine hydrate the UV-vis spectrum of Pd /H- peak is generally influenced by the local chemical/physical
hierarchical ZSM-5 was studied. environment around Pd species besides the formal oxidation
state, and shifts to higher binding energy when the charge
21,47
density around it decreases.
Figure 6. UV-vis spectrum of Pd/H-hierarchical ZSM-5.

Figure 7. XPS spectrum of Pd3d of Pd/H-hierarchical ZSM-5.

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In other words, the existence of the acidic sites of the Also, the TEM images of Pd/H-hierarchical ZSM-5 (Fig. 9b-c)
0
zeolite (with the electron withdrawing nature) around the Pd indicative of the places with darker contrast. Apparently, it
species conduct toward a decrease in the charge density could be related to the presence of palladium nanoparticles.
0 37
around Pd and the slight increase in binding energy. Also, the small dark dots in the images with an average
The full XPS spectrum of Pd/H-hierarchical ZSM-5 showed diameter of ~3-6 nm can be related to palladium nanoparticles
peaks of silicon, aluminum, carbon, oxygen and palladium. The and are located into the mesopores (Fig. 9d). As shown, the
presence of Al, Si and O confirm that ZSM-5 was obtained. mesopore structure still remains after the incorporation of Pd

Carbon has also been detected after the template removal nanoparticles in H-hierarchical ZSM-5 (Fig. 9b-c).
corresponds to remaining organic template of TPAOH inside The SEM was conducted to identify the morphologies of H-
the zeolite pores (Fig. 8). Recent studies have surely shown hierarchical ZSM-5 and Pd/H-hierarchical ZSM-5 that are
that even after template removal, a small amount of template shown in Fig. 10. In this regard, H-hierarchical ZSM-5 has a
48-50
stays inside the small cages in the MFI type zeolite. crystalline structure with small cubic regular particles and a
Moreover, calibration of XPS instrument is done by using the size about 3 μm (Fig. 10a). As shown, it can be concluded that
binding energy of the reference substance which always there is no difference in particle surface morphology between
causes present carbon pollution with a C1s binding energy of the H-hierarchical ZSM-5 and Pd/H-hierarchical ZSM-5 (Fig.
284 eV.51,52 10b), indicating that the supporting of Pd nanoparticles takes
place inside the channels of H-hierarchical ZSM-5 which is not
detectable in the SEM images (these particles shown in the
TEM section). This observation is also supported by the
decrease in pore volume and in surface area as shown in Table
1. It’s also noteworthy to mention that, the crystalline
structure of the zeolite is not destroyed during the loading of
Pd nanoparticles on the H-hierarchical ZSM-5.
Figure 8. Full XPS spectrum of Pd/H-hierarchical ZSM-5.
In order to gain insights into the morphology of the catalyst,

TEM analyses were carried out on H-hierarchical ZSM-5 (a) and Figure 10. Scanning electron microscopy (SEM) photographs of (a) H-
Pd/H-hierarchical ZSM-5 (b-d), which depicted in Fig. 9. This hierarchical ZSM-5 and (b) Pd/H-hierarchical ZSM-5.
images are demonstrated the formation of the ordered
mesostructure in H-hierarchical ZSM-5 with pore diameter 3.2. Catalytic activity
about 6-7 nm and the distribution of the palladium Synthesized Hierarchical zeolite was characterized by
nanoparticles in the H-hierarchical ZSM-5 (Fig. 9 (a-c)). several methods in the previous section. Here we introduce
the application of this catalyst to the reductive amination
reaction because it has many specific characteristics contrast
to traditional zeolite. Over the past two decades, many studies
devoted to industrial and academic research groups to the
development of environmentally friendly synthesis.
Accordingly, using water as a reaction medium in transition
metal-catalyzed processes has merited increasing attention
and nowadays it is one of the most essential targets of
53,54
sustainable chemistry. Water is an inexpensive, nontoxic
solvent, readily available, non-inflammable that provides
significant advantages over common organic solvents both
11,55
from an environmental and an economic standpoint. Thus,
the effect of different parameters on the one-pot tandem
reductive amination of aldehydes with nitroarenes over Pd/H-
hierarchical ZSM-5 as acid-metal bifunctional catalyst was
Figure 9. Transmission electron microscopy (TEM) of (a) H-hierarchical ZSM-
surveyed at room temperature in water and the results are as
5 and (b-d) Pd/H-hierarchical ZSM-5.
follows:

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Table 2. Effect of Pd(OAc)2 molar ratio on the catalytic activity.a

Pd content of catalyst Reaction time Conversion of benzaldehyde Yield (%)c
Entry Pd(OAc)2 (wt%)
(mmol/g catalyst)b (min) (%)c amine imine
20 65 55 45
1 4.2 0.167
45 100 98d 2

2 8.1 0.332 20 100 98d 2
3 11.6 0.464 18 100 98d 2
4 15 0.598 15 100 98d 2
a
Reaction conditions: benzaldehyde (2 mmol), nitrobenzene (2 mmol), Pd/H-hierarchical ZSM-5 (0.10 g), H2O (3 mL) and NaBH4 (6 mmol) at room
temperature. b Estimated by ICP-AES. c Conversion of benzaldehyde and yield were analyzed by GC, and n-dodecane was used as the internal standard. d
Isolated yield after work-up.
At the first screening of experiments, different amounts of Table 3. Effect of NaBH4 on the direct one-pot reductive amination.a
Pd(OAc)2 were examined to recognize the effect of palladium Amount
nanoparticles concentration on the reaction. So, while the Reaction Conversion of Yield (%)b
Entry of NaBH4
other parameters were constant, the amount of Pd(OAc)2 to time (min) benzaldehyde (%)b
(mmol) amine imine
prepare Pd/H-hierarchical ZSM-5 was changed from 4.2 wt% to
20 36 21 15
15 wt% and then measured by the ICP-AES technique which
1 2
showed in Table 2. As can be seen in Table 2, the activity of 60 77 66 11
catalytic increased steadily between 4.2 and 8.1 wt%. By
increasing the amount of Pd(OAc)2. As the catalytic reaction 20 62 53 9
2 4
mechanism involves Pd nanoparticle mediated electron
-
transfer from BH4 ion to the nitro compounds (in the first 35 95 90 5
step) and to the imine intermediates (in the third step), the
-
amount of H sites on the catalyst surface are increased by 3 6 20 100 98c 2
increasing palladium nanoparticles, and a larger amount of
hydrides can be transferred to the nitro compounds and then
56 4 8 20 100 98c 2
imine groups through the catalyst. The excess amount of
Pd(OAc)2 cause the reaction time decrease with mild slope and a
Reaction conditions: benzaldehyde (2 mmol), nitrobenzene (2 mmol),
because of the expensive price of palladium acetate, we chose Pd/H-hierarchical ZSM-5 (0.10 g) and H2O (3 mL) at room temperature. b
8.1wt% of Pd(OAc)2 as an optimum amount. Conversion of benzaldehyde and yield were analyzed by GC, and n-
The effect of NaBH4 amount (as a hydride donor) on the dodecane was used as the internal standard. c Isolated yield after work-up
reductive amination was investigated in the presence of Pd/H-
hierarchical ZSM-5. The results revealed that there is a direct Table 4. Effect of catalyst amount on the direct one-pot reductive amination
relationship between yield and the amount of NaBH4 up to 6 reaction.a
mmol (Table 3). With further increase in the NaBH4 amount, Amount of Reaction time Yield of amine
Entry
the yield of the reaction leveled off at 98% between 6 and 8 catalyst (g) (min) (%)b
mmol NaBH4. Fewer values were not enough for the reduction 20 74c
of the amount of nitro and imine compounds and the excess 1 0.03
38 98
amount didn't have any effect on the reaction as well.
Therefore, the best value of NaBH4 was 6 mmol. 2 0.04 20 98
The effect of amount of Pd/H-hierarchical ZSM-5 was
3 0.05 20 98
determined for the reductive amination reaction. It can be
seen that with an increase in the amount of the catalyst from 5 0.10 20 98
0.03 g to 0.04 g, a considerable decrease in the reaction time a
Reaction conditions: benzaldehyde (2 mmol), nitrobenzene (2 mmol), H2O
was observed from 38 to 20 minutes (Table 4) which are due
(3 mL) and NaBH4 (6 mmol) at room temperature. b Isolated yield after work-
to the availability of more acidic and metallic sites.
up. c Yield was analyzed by GC, and n-dodecane was used as the internal
standard.

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As shown from this table, a higher amount of catalyst (0.05

g) had no any appreciable effect on the yield. It might be
mentioned that using low amounts of NaBH4 and catalysts in
this reaction shows the extraordinary catalytic activity of this
catalyst.
The reusability of the catalyst was tested by using Pd/H-
hierarchical ZSM-5 in recycling experiments (Chart 1). After

each cycle, the catalyst was filtered off, washed with water (10
mL) and ethanol (3 mL × 5 mL). Thereafter, it was dried in an
oven at 60 ˚C and reused in the reaction with a fresh reaction

mixture. It should be noted that after each run, some of the
catalysts were lost in the filtration process.
Herein, to solve this problem, after each run the amount of
remaining catalyst was determined and the molar ratio of the
reactants was changed according to the remaining amount of
the catalyst. Nonetheless, it’s noteworthy that there was a
very low amount of lost catalyst after each cycle.
The catalyst was reused up to 6 times without any Figure 11. XRD patterns of the used Pd/H-hierarchical ZSM-5 after the
modification and 17% loss of activity was observed. It’s fifth run of the recycle reaction.
noticeable that there was very low Pd leaching (2.7 %
measured by ICP-AES) during the reaction and the catalyst It should be mentioned that in the presence of palladium
exhibited high stability even after six runs (Chart 1). hydride, the efficiency of the catalyst doesn't detract since
palladium hydride is reversible in metallic form by slightly
heating. In addition, the existence of palladium hydride crystal
in reused catalyst indicates that this catalyst is very suitable for
hydride transfer.
SEM images of the catalyst recovered from the fifth run of
the recycle reaction are presented in Fig. 12, too. In contrast,
between these images and SEM images of the fresh catalysts
(Fig. 10), it’s indicated that the structure of the ZSM-5 zeolite is
well retained even after the fifth runs of the recycle reaction.
Since, the catalysts exhibit high stability over 6 runs which is
essential for the applications of catalyst.
Chart 1. The catalysts reusability and leaching of palladium for direct

one-pot reductive amination reaction.
Moreover, the XRD pattern of the used catalyst after five

Figure 12. Scanning electron microscopy (SEM) photographs of the
cycles showed that the structure of the catalyst is well retained
◦ used Pd//H-hierarchical ZSM-5 catalyst after the fifth run of the
(Fig. 11). Also, the XRD pattern in 2θ = 45-75 shows the
◦ ◦ recycle reaction.
reflections at 45 and 53 suggesting that during the reaction,
the palladium nanoparticles remain in the form of a crystal. On
The catalytic activity of the Pd/H-hierarchical ZSM-5 in the
the other hand, XRD analysis of reused Pd/H-hierarchical ZSM-
reductive amination was compared with H-hierarchical ZSM-5,
5 indicates the presence of palladium crystals to form both,
Pd2+/H-hierarchical ZSM-5, Pd/H-ZSM-5 (prepared based on
metallic and hydride. At room temperature, palladium
traditional ZSM-5) and without a catalyst. The results are
hydrides may contain two crystalline α and β, phases. The
presented in Table 5. The result emphasizes the important role
existence of Palladium metal hydrides is the result of the very
of the acid-metal catalyst in this reaction. As shown, the
high tendency of palladium nanoparticles to accept the
reaction efficiency without catalyst will be only 5% as long as
hydride ions and then conversion to palladium hydride. This
57 100 minutes (entry 1).
process is faster in the presence of NaBH4.

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Table 5. Effect of catalyst for the direct one-pot reductive amination.a

Yield of
Entry catalyst Reaction time (min)
amine (%)b
100 5
1 Without catalyst
20 5

55 20
2 H-hierarchical ZSM-5
20 15
Pd2+/H-hierarchical 55 45
3
ZSM-5
20 25
55 75
4 Pd/H-ZSM-5
Figure 13. Heterogeneity test for direct one-pot reductive amination.
20 55
Pd/H-hierarchical Under the optimized reaction conditions, the scope of the

5 20 98c
ZSM-5 reaction was explored with structurally and electronically
a
diverse aldehydes with a wide range of nitroarenes. Reactions
Reaction conditions: benzaldehyde (2 mmol), nitrobenzene (2 mmol), were investigated at room temperature in water at different
catalyst (0.04 g), NaBH 4 (6 mmol) and H2O (3 mL) at room
times, which mentioned in Table 6. The results show that all
temperature. b Yield was analyzed by GC, and n-dodecane was used as
reactions are almost completed within 17 to 45 min at room
the internal standard. c Isolated yield after work-up.
temperature (Table 6). The reaction rate goes up by the
There is the important point that NaBH4 act as a mild decrease electron density at the nitro group with locating
hydride donor agent, which is poor reagent for reducing nitro electron-withdrawing group on the nitro aromatic ring (entry
groups. By using the H-hierarchical ZSM-5 catalyst (entry 2), 2). On the other hand, electron-donating groups show the
with increase acid sites of the zeolite the nitro group activated reverse effect and cause the reaction rate decreased (entries 3
and so the yield slightly increased. (20% yield in 55 minutes). and 4). Actually, by decreasing the electron density of the nitro
Using Pd2+/H-hierarchical ZSM-5 (entry 3), the yield of nitro groups, the tendency of nitro groups to accept the hydride
benzene reduction was increased to 45% due to the role of Pd ions is increased. In contrast, the existence of electron-
ions as species to transfer hydride ions from NaBH4 to nitro donating groups on the benzaldehyde ring cause increases in
groups. Also, using Pd/H-ZSM-5 (traditional ZSM-5) (entry 4), the reaction rate (entries 5 and 8). Actually, the electron-
the reaction performance was increased to 75% because of the donating groups stabilize the protonated carbonyl bond
role of palladium nanoparticles as species to transfer hydride intermediate and cause an increase in the reaction rate.
ions from NaBH4 to nitro groups. In order to prove the Additionally, the direct reductive amination from
efficiency of the hierarchical structure of Pd/H-hierarchical nitroarene was performed on a 20-time scale-up (Table 6,
ZSM-5 than traditional Pd/H-ZSM-5 zeolite, they compare with entry 9), which the results represent the high activity of the
each other that Pd/H-hierarchical ZSM-5 showed the higher catalyst.
performance (entries 3 and 4). In fact the hierarchical As shown in Scheme 2, this process is highly selective for
structure containing micro/mesoporous buildings cause easier the preparation of amines from aldehydes in the presence of
access of reactants to the active sites of the catalyst. ketones and only secondary amines of the aldehydes is
In catalyst study, one interesting point is heterogeneous produced.
nature. In this context, heterogeneity test was performed. In
this regard, the catalyst was separated from the reaction O O NO2
HN HN
mixture at approximately 50% conversion of the starting CH 3 H Pd/H-hierarchical ZSM-5 CH 3 H
material through centrifugation. 5 ml H2 O at r.t.
NaBH 4
The reaction progress in the filtrate was monitored (Fig.13). 0% 98%
No further reductive amination reaction occurred even at Scheme 2. Selective reductive amination of aldehyde from nitroarenes.
addition times, representing that the nature of reaction
process is heterogeneous and there is not any progress for the According to the results, it can be found that the catalyst
reaction in homogeneous phase. afforded an average to excellent yields of the amine products.
Compared with the other studies on the tandem reductive
amination of aldehydes the significant advantages of our
method are:7-9,11-15,58-60

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Table 6. Direct one-pot reductive amination of aldehydes with nitroarenes over Pd/H-hierarchical ZSM-5.a
O NO 2
R1
6 mmol NaBH4
H 3 ml H2O at r.t.
R1 + R2 H
N
0.04g of Pd/H-hierarchical ZSM-5

1 2
R2
Time
Entry 1 2 Product Yield (%)b TON/TOF (h-1)c
(min)
HN
1 98 20 148/443
2 98 17 148/521
3 92 30 138/277
4 96 35 144/248
5 96 10 144/867
6 97 27 146/325
7 96 35 144/248
8 95 15 143/572
9 90d 45 135/181
a
Reaction conditions: aldehyde (2 mmol), nitro aromatic compound (2 mmol), NaBH4 (6 mmol), Pd/H-hierarchical ZSM-5 (0.04 g) and H2O (3 mL) at room
temperature. b Isolated yield after work-up. c Turn-over number (mol product/mol Pd) and turn-over frequency (mol product/(mol Pd.h)). d Scale-up
condition: benzaldehyde (40 mmol) , nitrobenzene (40 mmol) , catalyst (0.80 g), NaBH4 (120 mmol) and H2O (150 mL) at room temperature.

of Chemistry
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DOI: 10.1039/C6NJ02262F
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Table of Contents
Palladium nanoparticles embedded hierarchical zeolite acts as acid-metal bi-functional catalyst for efficient reductive
amination of aldehyde from nitroarenes.
graphical abstract


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nitroarenes over a hierarchical ZSM-5 zeolite containing palladium

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ZSM-5. Pd/H-hierarchical ZSM-5 were confirmed by powder XRD

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(calculated by BJH) and pore volume of Pd/H-hierarchical ZSM-

Figure 3. N2 adsorption/desorption isotherm of Pd/H-hierarchical ZSM-5.

Figure 4. Pore size distribution of Pd/H-hierarchical ZSM-5 obtained by BJH

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According to the literature results, the UV-vis spectrum of

Figure 6. UV-vis spectrum of Pd/H-hierarchical ZSM-5.

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Figure 8. Full XPS spectrum of Pd/H-hierarchical ZSM-5.

In order to gain insights into the morphology of the catalyst,

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Table 2. Effect of Pd(OAc)2 molar ratio on the catalytic activity.a

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3 11.6 0.464 18 100 98d 2

4 15 0.598 15 100 98d 2

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As shown from this table, a higher amount of catalyst (0.05

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oven at 60 ˚C and reused in the reaction with a fresh reaction

Chart 1. The catalysts reusability and leaching of palladium for direct

Moreover, the XRD pattern of the used catalyst after five

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Table 5. Effect of catalyst for the direct one-pot reductive amination.a

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Pd/H-hierarchical Under the optimized reaction conditions, the scope of the

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New Journal of Chemistry Accepted Manuscript

reagents; Green Chem. 2016, 18, 2507-2513

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40 A. J. J. Koekkoek, H. Xin, Q. Yang, C. Li, E. J. M. Hensen,

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46 A. Gniewek, A. M. Trzeciak, J. J. Ziolkowski, L. Kepinski, J.

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