Applied Clay Science 168 (2019) 184–195

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Applied Clay Science

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

Research paper

A novel magnetic heterogeneous catalyst based on decoration of halloysite T

with ionic liquid-containing dendrimer
⁎ ⁎
Samahe Sadjadia, , Masoumeh Malmirb, Majid M. Heravib,
a
Gas Conversion Department, Faculty of Petrochemicals, Iran Polymer and Petrochemicals Institute, PO Box 14975-112, Tehran, Iran
b
Department of Chemistry, School of Science, Alzahra University, PO Box 1993891176, Vanak, Tehran, Iran

A R T I C LE I N FO A B S T R A C T

Keywords: A magnetic catalyst is synthesized through growth of dendrimer of generation 3 (G3) on the surface of halloysite
Halloysite (Hal) nanotubes followed by decoration of dendrimer terminal groups with ionic liquid (IL) and incorporation of
Dendrimer Fe species. The structure of the catalyst was confirmed by using several characterization techniques. Moreover,
Magnetic catalyst the catalytic activity of the catalyst for oxidation of benzaldehydes to the corresponding benzoic acids in the
Cyclodextrin
presence of hydrogen peroxide was investigated. Notably, to improve the yield of the reaction, β-cyclodextrin (β-
CD) was employed as phase transfer agent. The contribution of dendrimer and IL to the catalysis was confirmed
by comparing the catalytic activity of the catalyst with that of control the catalysts (the catalyst without IL, Fe
species and dendrimer). Furthermore, the effect of dendrimer generation was elucidated by comparing the
catalytic activities of the catalysts prepared by growth of dendrimers of G1, G2 and G3 on Hal. Studying the
recyclability of the catalyst, it was found that the catalyst could be recovered and recycled for several reaction
times with slight loss of leaching of Fe species.

1. Introduction
Recently, Hal that is a natural kaoline-like clay has received tre-
mendous attention and its use in various research fields such as cata-
lysis, polymer and material sciences, drug delivery and cleaning has
been disclosed (Cavallaro et al., 2018a; 2018b; Janacek et al., 2018;
Kumar-Krishnan et al., 2016; Kurczewska et al., 2018; Sabbagh et al.,
2017; Štubňa et al., 2018; Szczepanik et al., 2017; Szczepanik and
Słomkiewicz, 2016; Tan et al., 2014; Yuan et al., 2015; Zhai et al., 2010;
Zhang et al., 2013a). The outstanding performance of Hal can be as-
signed to its biocompatible and non-toxic nature, high thermal and
chemical stability, unique tubular morphology as well as its chemical
composition (Al2(OH)4Si2O5·2H2O) and surface property (Massaro
et al., 2017b; 2017c; 2016; Pasbakhsh and Churchman, 2015; Tully
et al., 2016; Zhang et al., 2016). The surface feature of Hal can be
modified chemically and physically by surface functionalization
(Battistoni et al., 2017; Massaro et al., 2017a; 2017c; 2016; Sadjadi
et al., 2017c; Vinokurov et al., 2017; Yang et al., 2015; Yuan et al.,
2008; 2016; Zhang et al., 2013b; 2014).
Magnetic catalysts have gained growing attention due to their facile
recovery and recycling. In this context, Hal has also been used for de-
veloping magnetic catalysts (Liz and Yang, 2012; Maleki et al., 2018;
Wei et al., 2016). One of the first examples of magnetic Hal was
reported by (Liu and Zhao, 2009), in which Hal was modified with
mercaptoacetic acid and then successfully applied for supporting Ag(0)
nanoparticle through polyol process to afford an efficient catalyst for
reduction of 4-nitrophenol in the presence of sodium borohydride. In
another study, Wang et al. reported reduction of 4-nitrophenol in the
presence of magnetic Hal-supported gold nanoparticles, Au/Hal/Fe3O4,
in which, Au nanoparticles were encapsulated within Hal lumen, while
magnetic nanoparticles were immobilized on the surface of Hal (Mu
et al., 2014b). The catalyst could be separated from the reaction mix-
ture by using external magnet and showed high recyclability. In this
line, the utility of Ag/Hal/Fe3O4 nanocomposite, in which Ag nanorods
were located within the lumen of Hal and magnetic nanoparticle were
immobilized on the external Hal surface, for reduction of 4-nitrophenol
to 4-aminophenol has been confirmed (Mu et al., 2014a). Similar to the
previous study, the catalyst exhibited high catalytic activity and re-
cyclability. Recently, sol-gel methodology has been applied for the
synthesis of La1-xAgxFeO3/Hal. The catalyst served as an efficient and
recyclable photocatalyst for degradation of methylene blue under
visible light irradiation (Li et al., 2016). As a last example of magnetic
Hal-based catalysts, synthesis of Fe3O4-Hal-SO3H can be mentioned.
The catalyst that prepared via synthesis of magnetic Hal followed by
decoration with SO3H was successfully used for catalyzing synthesis of
dihydropyrimidinone derivatives. Apart from high catalytic activity,

⁎
Corresponding authors.
E-mail addresses: s.sadjadi@ippi.ac.ir (S. Sadjadi), m.heravi@alzahra.ac.ir (M.M. Heravi).

https://doi.org/10.1016/j.clay.2018.11.012
Received 3 August 2018; Received in revised form 12 November 2018; Accepted 13 November 2018
0169-1317/ © 2018 Elsevier B.V. All rights reserved.
S. Sadjadi et al. Applied Clay Science 168 (2019) 184–195

Fig. 1. The route for the synthesis of the Fe-Hal-PAMAM-IL.

Fig. 2. The transmission electron microscopy (TEM) images of Fe-Hal-PAMAM-IL catalyst.

185
S. Sadjadi et al.
Fig. 3. The thermal gravimetric analysis of the pristine Hal, Hal-Si, Hal-PAMAM (G3), Fe-Hal-PAMAM-IL (G1-3) catalyst.
Fig. 4. The Fourier-transform infrared (FTIR) spectra of the (A) pristine Hal, (B) Hal-PAMAM-G1, (C) Hal-PAMAM-G2, (D) Hal-PAMAM-G3, (E) Hal-PAMAM-G3-Cl,
(F) Hal-PAMAM-G3-IMI-SO3H and (G) Fe-Hal-PAMAM-IL catalyst.
the catalyst was highly recyclable.
Dendrimers that are hyper branched 3-D macromolecules (Deraedt
et al., 2014; Grayson and Frechet, 2001; Nithya et al., 2018) can be
synthesized through various methodologies, especially divergent and
convergent methods. Dendrimers have diverse applications ranging
from drug delivery and diagnosis to the synthesis of nanomaterials and
catalysis (Bronstein and Shifrina, 2011; Gates et al., 2010). The unique
structure of dendrimers, in which a core is surrounded with repeating
branches, forms an interior microenvironment that access to it can be
controlled with the dendrimer periphery. This microenvironment can
affect the reaction in terms of selectivity, conversion and reactivity
(Vriezema et al., 2005).
CDs are one of the most popular class of phase transfer catalysts.
Application of these compounds in the catalysis is increasingly growing
due to their biocompatible nature, low cost and diversity in size of their
cavity (Jahjah et al., 2011; Manivannan and Ramaraj, 2012; Strimbu
et al., 2003). Forming inclusion complex with hydrophobic substrates,
CDs can serve as a molecular transfer shuttle and transfer the substrates
at the aqueous/organic interface (Bai et al., 2013; Gogoi and Sarma,
2017; Hapiot et al., 2014; Hapiot and Monflier, 2017; Kaboudin et al.,
2016; Menuel et al., 2016; Noël et al., 2014a; 2014b; Thanh Chau et al.,
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Applied Clay Science 168 (2019) 184–195
2013; Yi et al., 2013).
The oxidation of carbonyl compounds plays a significant role in the
organic synthesis (Trost, 1991). To date, many approaches for oxidation
of aldehydes to carboxylic acids have been developed (March, 1985).
Traditional oxidants such as chromate and permanganate are corrosive
and have harmful environmental impacts (Dalcanale and Montanari,
1986; Hurd et al., 1933). Recently, as part of the growing tendency
towards green chemistry, environmentally friendly catalytic processes
such as use of molecular oxygen or hydrogen peroxide (H2O2) as oxi-
dants have been expanded (Bordoloi et al., 2008). H2O2 is a cheap,
readily available, mild, and environmentally friendly reagent with a
high content of “active” oxygen. This oxidant has been widely used for
the oxidation of organic compounds (Cang et al., 2015; Jeong et al.,
2014; Qian et al., 2002; Yan et al., 2005).
In the following of our interest in the use of Hal for development of
heterogeneous catalysts (Bahri-Laleh et al.; Sadjadi and Atai, 2018;
Sadjadi et al., 2018a; 2018b) and considering the high efficiency and
recyclability of Hal-based magnetic catalysts, herein we wish to report a
novel magnetic Hal-based catalyst with facile recovery and high cata-
lytic activity and recyclability. The synthesis of the catalyst was
achieved through growth of dendrimer of generation three via multi-
S. Sadjadi et al. Applied Clay Science 168 (2019) 184–195

Fig. 5. X-ray diffraction (XRD) patterns of (A) pristine Hal and (B) the catalyst.

Fig. 6. Vibrating sample magnetometer (VSM) analysis of Fe-Hal-PAMAM-IL catalyst.

Table 1 2. Experimental
Elemental composition (atomic %) of Halloysite (Hal) and the catalyst (Fe-Hal-
PAMAM-IL). 2.1. Preparation of catalyst: Fe-Hal-PAMAM-IL
Elements Si Al Fe S Cl
Dendrimer-conjugated Hal (Hal-PAMAM) was prepared according
Hal 51.5 45 3.5 – – to a reported method with minor modification (Gan et al., 2005; Pan
Catalyst 6.3 5.5 26.4 0.1 61.7
et al., 2005). Briefly, suspension of 2 g Hal in dry toluene (100 mL) was
subjected to ultrasonic irradiation of power 100 W for half an hour. To
steps procedure and subsequent decoration of dendrimer with IL and keep the reaction temperature constant and avoid increase of the
ion exchange with Fe species. The reason behind design of the catalyst temperature in the course of ultrasonication, the icy water bath was
is taking advantage of magnetic species for efficient and facile recovery employed. Next, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane
of the catalyst. Moreover, it is believed that multi heteroatoms in the (7 mL) was added to the homogenized Hal suspension and the resulting
backbone of IL decorated dendrimer can induce electrostatic interac- mixture was refluxed for 24 h at 110 °C. Upon completion of the reac-
tions and play an important role in immobilizing magnetic species. The tion, the reaction mixture was cooled to ambient temperature and the
catalytic activity and recyclability of the catalyst for oxidation of ben- colloid was filtered off, washed with dry toluene repeatedly and dried
zaldehydes to the corresponding benzoic acids is investigated (Scheme at 80 °C overnight.
S1). Moreover, the utility of β-CD as phase transfer agent is confirmed. To grow dendrimer on the surface of amine-modified Hal, amine-
Finally, the role of IL and dendrimer in the catalysis as well as the effect functionalized Hal (2 g), was dispersed in 50 mL methanol containing
of dendrimer generation on the catalytic activity are studied. 20 mL methacrylate. The solution was then refluxed for 24 h at 65 °C.
The resulting product was washed with methanol 3 times; then, 4 mL
ethylenediamine and 20 mL methanol were added and the mixture was
refluxed for 12 h. After washing with methanol for 3 times, the first
generation dendrimer-conjugated Hal was produced. The Hal-PAMAM

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S. Sadjadi et al.
Fig. 7. The N2 adsorption-desorption and Barrett-Joyner-Halenda Method
(BJH- plot) of the Fe-Hal-PAMAM-IL catalyst. Va: volume of gas adsorbed, Vp:
pore volume, rp: average pore radius, P: partial vapor pressure of adsorbate gas
in equilibrium with the surface at 77.4 K (b.p. of liquid nitrogen), in Pascal, P0:
saturated pressure of adsorbate gas, in Pascal, dVp/drp: pore size distribution is
classically represented by the derivatives of pore volume and pore radius.
Table 2
Textural properties of the Fe-Hal-PAMAM-IL and Hal.
Catalyst SBETc (m2 g−1) Vtd (m3/g) dBJH–KJS ads/des
e
(nm)
a
Fe-Hal-PAMAM-IL 5.38 0.06 44.9
Hal b 51 0.2 5.42
a with that of Hal-Si, an additional weight loss (~2.5 wt%) at ~250 °C
Halloysite decorated with ionic liquid terminated dendrimer ion exchanged
with iron species.
b
Pristine halloysite.
c
SBET (Brunauer, Emmett and Teller surface areas).
d
Vt (total pore volume was estimated at a relative pressure of P/P0 = 0.990).
e
dBJH–KJS adsorption/des (pore diameters derived from the adsorption/deso-
rption branch by the Barrett-Joyner-Halenda Kruk-Jaroniec-Sayari method).
with dendrimers of G2 and G3 were achieved by repeating the proce-
dure of adding methacrylate and ethylenediamine.
To decorate the dendrimer terminal groups with ionic liquid, a
mixture of Hal-PAMAM (2 g) and 1,4-dichlorobutane (5 mL) in 50 mL
dry acetonitrile were refluxed for 24 h. Upon completion of the reac-
tion, solvent was removed, and the residue (Hal-PAMAM-Cl) was wa-
shed with dichloromethane and dried at 80 °C in oven for 6 h.
Next, to a suspension of Hal-PAMAM-Cl (2 g) in dry toluene
(50 mL), a solution of imidazole (1.7 g) in dry toluene (50 mL) was
added and the mixture was refluxed overnight under nitrogen atmo-
sphere. Upon completion of the reaction, the solvent was removed and
the product was obtained after washing with toluene and drying
overnight at 80 °C. Then, Hal-PAMAM-IMI (2 g) was dispersed in dry
toluene (50 mL) and 1, 4-butane sultone (1.85 g) was added in a
dropwise manner into the suspension over 30 min. The mixture was
stirred for 8 h and then the solvent was evaporated. Subsequently,
Conc. HCl (2 mL) was added dropwise into the mixture of the above-
mentioned residue in ethanol (30 mL). Subsequently, the mixture was
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Applied Clay Science 168 (2019) 184–195
heated at 50 °C for 8 h and the solvent was evaporated under reduced
pressure to furnish ionic liquid product.
Finally, Fe-Hal-PAMAM-IL was prepared by mixing powder of Hal-
PAMAM-IL (2 g) with anhydrous FeCl3 (0.5 g) in dry toluene at room
temperature for 3 h. The obtained dark brown Fe-Hal-PAMAM-IL was
washed with small amount of dry toluene. Then, the solvent was eva-
porated and the resulting clear brown powder was dried in oven at
60 °C for 6 h (see Fig. 1).
2.2. General procedure for oxidation of benzaldehyde to benzoic acid
Hydrogen peroxide 30% (5.0 mmol), aldehyde (1.0 mmol), Fe-Hal-
PAMAM-IL (0.05 mol%) and β-CD (1 wt%) were mixed under solvent
free (S.F.) condition. The reaction mixture was then heated for 2.5 h at
90 °C. After complete conversion (monitored by TLC), 10 ml of hot
EtOH was added into the reaction mixture to dissolve the resulting
products. Then, the catalyst was filtered off, washed with EtOH and
dried at 60 °C for 6 h. The filtrate on the other hand, was cooled to room
temperature to let the dissolved products crystalize. Then, the pure
product was achieved by recrystallization from hot EtOH.
3. Result and discussion
3.1. Catalyst characterization
The transmission electron microscopy (TEM) images of Fe-Hal-
PAMAM-IL are illustrated in Fig. 2. Comparing the tubular morphology
of pristine Hal (Fig. S1) and that of the catalyst, it can be seen that upon
growth of dendrimer and incorporation of IL and Fe species, morpho-
logical change is induced to some extent. Notably, the Fe species are
also detectable as small black spots.
In the following, thermal gravimetric analysis, TGA, was performed
to study the thermal stability of Fe-Hal-PAMAM-IL, Fig. 3. Apart from
recording the thermogram of the catalyst, the thermogram of pristine
Hal and those of the intermediate compounds, synthesized in the course
of preparation of the catalyst, Hal-Si and Hal-PAMAM, were also ob-
tained. According to the previous reports, thermogram of Hal exhibits
two main weight losses due to loss of water and dehydroxylation
(Sadjadi et al., 2018a; 2018b). Comparing the isotherm of pristine Hal
can be detected that can be attributed to the decomposition of N-(2-
aminoethyl)-3-aminopropyltrimethoxysilane. The thermograms of Hal-
PAMAM and of Fe-Hal-PAMAM-IL show additional weight losses that
can be attributed to the loss of dendrimer and Fe species.
The Fourier-transform infrared (FTIR) spectra of pristine Hal, Hal-
PAMAM (G1), Hal-PAMAM (G2), Hal-PAMAM (G3), Hal-PAMAM (G3)-
Cl, Hal-PAMAM (G3)-IMI-IL and Fe-Hal-PAMAM (G3)-IL are shown in
Fig. 4. As depicted in Fig. 4, the FTIR spectrum of Hal showed bands at
1035 cm−1 (SieO stretching), 3695 cm−1 and 3622 cm−1 (inner sur-
face eOH and inner eOH groups), 540 cm−1 (Al-O-Si vibration), 2922
and 1631 cm−1 (Sadjadi et al., 2017c). As depicted, the FTIR spectra of
Hal-PAMAM (G1), Hal-PAMAM (G2), Hal-PAMAM (G3), Hal-PAMAM
(G3)-Cl showed the characteristic bands of dendrimer, i.e. the band at
1735 cm−1, which is the characteristic band of (-C=O) group. The
quantitative study of Hal-PAMAM (G1), Hal-PAMAM (G2), Hal-PAMAM
(G3) spectra indicated that Hal-PAMAM (G3) possessed the highest
number of (eC]O) functionalities followed by Hal-PAMAM (G2) and
Hal-PAMAM (G1). The FTIR spectrum of Hal-PAMAM (G3)-Cl is almost
similar to that of Hal-PAMAM (G3). This is not beyond expectation as
the characteristic bands of 1,4-dichlorobutane overlapped with that of
Hal. The FT-IR spectra of Hal-PAMAM (G3)-IMI-IL and Fe-Hal-PAMAM-
IL are also similar to that of Hal-PAMAM (G3) and contain the char-
acteristic bands of Hal and dendrimer. Notably, the characteristic bands
of IL, i.e. the band at 1085 cm−1 and at 891 cm−1 (SO3H functionality)
overlapped with that of Hal.
To shed light to the structural properties of Fe-Hal-PAMAM-IL, it
S. Sadjadi et al. Applied Clay Science 168 (2019) 184–195

Fig. 8. (A) Energy-dispersive X-ray spectroscopy (EDX) analysis of the catalyst and (B) Elemental analysis of the catalyst.

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Table 3 and HNO3. ICP analysis of the filtrate showed that the loading of Fe was
Comparison of the catalytic activity of the present catalyst with the other 6.5 wt%.
prepared catalysts in the oxidation of benzaldehydesa. The study of surface property of Fe-Hal-PAMAM-IL was achieved by
Entry Catalyst Yield l (%) Time (h.min) recording nitrogen adsorption–desorption isotherm of the catalyst,
Fig. 7. The shape of the obtained isotherm is in good agreement with
1 Fe-Hal-PAMAM-IL (G3)b 95 2.30 type II isotherms with H3 hysteresis loops (Yuan et al., 2008). The
2 Hal-PAMAM-IL (G3)c 85 2.30
Brunauer–Emmett–Teller (BET) analysis also showed that the specific
3 Fe-Hal-PAMAM (G3)d 70 2.30
4 Fe-Hal-PAMAM-IL (G2)e 55 2.30 surface area of Fe-Hal-PAMAM-IL (5.38 m2 g−1) was significantly lower
5 Hal-PAMAM-IL (G2)f 50 2.30 than that of the pristine Hal (51 m2 g−1, obtained from BET). This ob-
6 Fe-Hal-PAMAM (G2)g 50 2.30 servation can confirm that the growth of the dendrimer was accom-
7 Hal-PAMAM-IL (G1)h 75 2.30
plished on the surface of Hal. As confirmed in TEM images, the den-
8 Fe-Hal-PAMAM (G1)i 55 2.30
9 Fe-Hal-PAMAM-IL (G1)j 80 2.30
drimer of generation 3 is almost huge and can cover the surface of Hal
10 Fe-Hal-N-SO3Hk Trace 4 significantly.
The comparison of total pore volume of the catalyst (Fe-Hal-
l
Isolated yield. PAMAM-IL) with that of the pristine Hal (Hal) confirmed that this
a
Reaction condition: benzaldehyde (1.0 mmol), H2O2 (5.0 mmol), catalyst parameter decreased upon incorporation of IL-decorated dendrimer and
(0.05 mol%), β-cyclodextrin (1 wt%) at 90 °C under solvent free condition. Fe species, Table 2. Moreover, the value of pore diameter of the catalyst
b
Fe-Hal-PAMAM-IL (G3): Halloysite decorated with ionic liquid terminated
significantly increased compared to the pristine Hal. This observation
dendrimer of generation three, ion exchanged with iron species.
c can be attributed to the pores of the dendrimer structure.
Hal-PAMAM-IL (G3): Halloysite decorated with ionic liquid terminated
dendrimer of generation three. In Fig. 8 the Energy-dispersive X-ray spectroscopy (EDX) and ele-
d
Fe-Hal-PAMAM (G3): Halloysite decorated with dendrimer of generation mental mapping analyses of the catalyst are depicted. As illustrated, the
three ion exchanged with iron species. EDX analysis of the catalyst showed Si, Al and O atoms that can be
e attributed to the Hal structure. The presence of C, N and S atoms can
Fe-Hal-PAMAM-IL (G2): Halloysite decorated with ionic liquid terminated
dendrimer of generation two, ion exchanged with iron species. confirm the conjugation of IL. Moreover, C, O and N atoms can be as-
f
Hal-PAMAM-IL (G2): Halloysite decorated with ionic liquid terminated signed to the dendrimer functionality. The observation of Fe atoms can
dendrimer of generation two. confirm the immobilization of Fe species. Using this analysis, the con-
g
Fe-Hal-PAMAM (G2): Halloysite decorated with dendrimer of generation tent of IL was estimated to be 6.6 wt% and the content of dendrimer
two ion exchanged with iron species.
h
was calculated to be ~ 10 wt%.
Hal-PAMAM-IL (G1): Halloysite decorated with ionic liquid terminated
The elemental mapping analysis of the catalyst showed that Fe
dendrimer of generation one.
i species are dispersed almost uniformly. Regarding S atom, it is found
Fe-Hal-PAMAM (G1): Halloysite decorated with dendrimer of generation
one, ion exchanged with iron species. that the dispersion is not uniform. This is expectable, as the IL is located
j
Fe-Hal-PAMAM-IL (G1): Halloysite decorated with ionic liquid terminated on the periphery of dendrimer.
dendrimer of generation one, ion exchanged with iron species.
k
Fe-Hal-N-SO3H: amine- functionalized halloysite decorated with sulfonic 3.2. Catalytic activity
acid-[FeCl4]−.
To study the catalytic activity of the catalyst and elucidate whether
was subjected to X-ray diffraction (XRD) analysis. Moreover, to eluci- incorporation of IL and dendrimer could enhance the catalytic activity,
date whether the structure of Hal was preserved in the course of dec- the oxidation of benzaldehyde to benzoic acid in the presence of hy-
oration of its surface with IL-containing dendrimer and incorporation of drogen peroxide was selected as a model reaction. First, it was at-
Fe species, the XRD pattern of Fe-Hal-PAMAM-IL (Fig. 5) was compared tempted to find the optimum reaction condition. In this line, the model
with that of pristine Hal. According to the literature, the characteristic reaction (oxidation of benzaldehyde) was performed in various solvents
bands of Hal are appeared at 2θ = 14.3°, 22.0°, 26.6°, 28.6°, 37.1°, and under solvent free condition. The results, Table S1 showed that the
40.4°, 57.5° and 64.7° (JCPDS No. 29–1487) (Yuan et al., 2008; Zhu reaction in the absence of the solvent resulted in the best yield of the
et al., 2012). The XRD pattern of Fe-Hal-PAMAM-IL also showed the desired product. Moreover, it was found that the yield of the desired
characteristic bands of pristine Hal. However, their intensities were product could be improved by using catalytic amount of β-CD as phase
lower than that of pristine Hal. Moreover, some new bands that can be transfer agent. The capability of CD to form inclusion complex with
assigned to the Fe species were appeared. According to the XRD results, substrates and encapsulating them within its hydrophobic cavity can
Fe species on the catalyst was determined as FeCl2.2H2O. It is worth account for this increase in the catalytic activity (Menuel et al., 2016;
noting that the intensities of Hal characteristic bands in the catalyst Nowicki et al., 2006). Then, the effect of nature of oxidant on the yield
were decreased compared to those of Hal. According to the literature of the reaction was examined. To this purpose, various oxidants such as
(Mu et al., 2014a), this observation can be due to the high content of KMnO4 and K2Cr2O7 were tested. It was found that hydrogen peroxide
magnetic species that decorated the Hal surface. was the most effective oxidant. Optimization of reaction temperature
The magnetic property of the catalyst was studied by room tem- (90 °C) was also accomplished by performing the model reaction at
perature vibrating sample magnetometer (VSM), Fig. 6. As depicted, the different temperature, Table S1. Finally, the catalyst amount was op-
maximum saturation magnetization (Ms) value of Fe-Hal-PAMAM-IL is timized to be 0.05 mol%.
22.3 emu g−1. Armed with the optimum reaction condition, the role of each
XRF analysis was also performed to determine the elemental com- component on the structure of the catalyst was studied.
position of the catalyst. As depicted in Table 1, in pristine Hal the ratio Although the incorporation of Fe species on the structure of the
of Si:Al is about 1.15. Upon introduction of magnetic species, the catalyst could improve and facilitate catalyst separation, it was a
content of Si and Al dramatically reduced, while Si:Al ratio remained question whether it could enhance the catalytic activity. To answer this
constant. The reduction of Si and Al content can be attributed to the question, a control catalyst, Hal-PAMAM-IL (the catalyst without Fe
high content of Fe (Mu et al., 2014a). species) was synthesized and its catalytic activity was compared with
Next, loading of Fe species in Fe-Hal-PAMAM-IL was estimated by that of Fe-Hal-PAMAM-IL (G3), Table 3. As tabulated, the Fe could
using coupled plasma atomic emission spectroscopy (ICP) analysis. To contribute to the catalysis and the catalytic activity of Fe-Hal-PAMAM-
this purpose, the sample for ICP analysis was prepared by digesting a IL (G3) was superior that that of Hal-PAMAM-IL. Next, it was in-
known amount of Fe-Hal-PAMAM-IL in concentrated mixture of HCl vestigated whether IL could play the role in catalysis. In this line,

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Table 4
Fe-Hal-PAMAM-IL catalyzed oxidation reaction of various benzaldehydea.
Entry Aldehyde Benzoic acid With β-Cyclodextrin Without β-Cyclodextrin

b
Time (h.min) Yield (%) Time (h) Yieldb (%)

1 2.30 95 2.30 60

2 4 88 4 55

3 3.15 90 3.15 70

4 3 90 3 75

5 3.30 85 3.30 65

6 3.45 80 3.45 60

7 2.30 92 2.30 60

8 4 90 4 40

a
Reaction condition: benzaldehydes (1.0 mmol), H2O2 (5.0 mmol), Fe-Hal-PAMAM (0.05 mol%), β-cyclodextrin (1 wt%) at 90 °C under solvent free condition.
b
Isolated yield.

Table 5
Comparison of the efficiencies of various protocols for the synthesis of benzoic acida.
Entry Catalyst (amount) Reaction condition Time (h:min) Yielde (%) Ref

1 b
PTSA (1 mmol) H2O2 (5 mmol), 50 °C, β-cyclodextrin, S.F. 15:0 98 (Jeong et al., 2014)
2 [bmim]PF6c (3 mol%) O2, 60 °C, S.F. 12:0 66 (Howarth, 2000)
3 (PhSe)2d (2%) H2O2 (10%), r.t., H2O 6:0 99 (Sancineto et al., 2015)
4 Na2WO4·2H2O (0.5 mmol) H2O2 (5 mmol), Reflux, H2O 5:0 74 (Yan et al., 2005)
5 Fe-Hal-PAMAM-IL (0.05 mol%) H2O2 (5 mmol), 90 °C, β-cyclodextrin, S.F. 2:30 95 This work

a
Reaction condition: Benzaldehyde (1 mmol) was reacted under different reaction conditions.
b
p-toluenesulfonic acid.
c
1-ethyl-3-methylimidazolium cation ionic liquid.
d
Diphenyldiselenide.
e
Isolated yield.

another control catalyst, Fe-Hal-PAMAM (a catalyst without IL) was
prepared and its catalytic activity was compared with that of the cat-
alyst. The results, Table 2, confirmed the contribution of IL to the
catalysis. This result can be justified by considering the fact that IL itself
can act as a catalyst (Sadjadi et al., 2017a; 2018b). Notably, the catalyst
without dendrimer and IL, Fe-Hal, exhibited insignificant catalytic ac-
tivity, confirming the role of IL decorated dendrimer in the catalysis.
As in the dendrimer-based catalysts the dendrimer generation can
affect the catalytic performance, the effect of dendrimer generation on
the catalytic activity was also investigated by synthesis of the control

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Fig. 9. Recyclability of the Fe-Hal-PAMAM-IL catalyst in the oxidation reaction of benzaldehyde.

Fig. 10. The Fourier-transform infrared (FTIR) spectra of the Fresh and re-cycled Fe-Hal-PAMAM-IL catalyst after ten runs.

Fig. 11. X-ray diffraction patterns of fresh and re-cycled catalyst.

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catalysts with dendrimers of generation 1 and 2. Interestingly, it was
found that the catalytic activity increased in the order of Fe-Hal-
PAMAM-IL (G3) > Fe-Hal-PAMAM-IL (G1) > Fe-Hal-PAMAM-IL
(G2). Considering our previous study (Bahri-Laleh et al., 2018b), in
which the catalytic activity of two catalysts, Pd-Hal-PAMAM (G1) and
Pd-Hal-PAMAM (G2) were studied for coupling reaction both experi-
mentally and theoretically, it was found that in Pd-Hal-PAMAM (G1)
the Pd binding energy and free volume around the catalytic active site
was higher and consequently, the accessibility of the reagents to the
catalytic active site increase the catalytic activity compared to Pd-Hal-
PAMAM (G2). Considering those results, higher catalytic activity of Fe-
Hal-PAMAM-IL (G1) compared to Fe-Hal-PAMAM-IL (G2) can be at-
tributed to the higher accessibility of the reagents to the catalytic active
sites. In the case of Fe-Hal-PAMAM-IL (G3), in which sterically de-
manding dendrimer of G3 could limit the substrate accessibility, how-
ever, the highest catalytic activity was observed. To justify this ob-
servation, it was assumed that steric hindrance is not the only
determining parameter. Considering the fact that both IL and Fe species
could participate in the catalysis, high catalytic activity of Fe-Hal-
PAMAM-IL (G3) was attributed to the higher amount of IL in the
structure of the catalyst. Moreover, as IL could anchor Fe species
through electrostatic interactions, it was assumed that the higher con-
tent of IL could result in higher Fe loading and consequently, superior
catalytic activity. To verify this assumption, all the control catalysts
were subjected to TG and ICP analyses. The ICP results demonstrated
that the content of Fe species in the catalysts follow the order of Fe-Hal-
PAMAM-IL (G3) > Fe-Hal-PAMAM-IL (G2) ≈ Fe-Hal-PAMAM-IL (G1).
The TG analyses proved that the content of IL decreased in the fol-
lowing order: Fe-Hal-PAMAM-IL (G3) > Fe-Hal-PAMAM-IL (G2) ≈ Fe-
Hal-PAMAM-IL (G1). These results indicated that the content of both IL
and Fe in Fe-Hal-PAMAM-IL (G3) is higher than two other catalysts.
These factors can compensate the steric hindrance of Fe-Hal-PAMAM-IL
(G3). In the case of Fe-Hal-PAMAM-IL (G2), although the content of Fe
and IL is higher than that of Fe-Hal-PAMAM-IL (G1), this difference is
not too distinguished. Hence, the accessibility is a dominant factor.
Notably, Hal-PAMAM (G1) and Hal-PAMAM (G2) (the catalysts
without Fe and IL) were also synthesized and their catalytic activities
were compared with that of the Fe-Hal-PAMAM-IL (G1) and Fe-Hal-
PAMAM-IL (G2). Similar to the results observed for Fe-Hal-PAMAM-IL
(G3), the catalyst containing both Fe and IL led to the highest catalytic
activity, confirming the role of Fe and IL in the catalysis.
In the next step, the generality of the developed protocol was ex-
amined. To this purpose, oxidation of various benzaldehyde derivatives
with electron donating and electron withdrawing functional groups was
performed under the optimum reaction condition. To further confirm
the role of CD in the catalysis, the yields of all benzoic acid derivatives
in the presence and absence of CD was estimated, Table 4. As shown, in
all cases, the catalyst could promote the oxidation reaction efficiently to
furnish the desired products in high yields. Moreover, in all cases,
especially, in the case of sterically demanding and hydrophobic sub-
strate, Table 4 entry 8, the presence of CD could enhance the yield of
the product.
In order to demonstrate the efficiency of the developed protocol, the
yield of the model product under Fe-Hal-PAMAM-IL catalysis was
compared with some of the previously reported procedures and cata-
lysts, Table 5. As shown in this table, the efficiency of Fe-Hal-PAMAM-
IL is superior or comparative to other catalysts. Moreover, Fe-Hal-
PAMAM-IL could furnish the desired product in a shorter reaction time
and more ecofriendly procedure. Additionally, the heterogeneous
nature of Fe-Hal-PAMAM-IL not only rendered the catalyst recyclable,
but also made the work-up more facile and fast.
3.3. Catalyst recyclability
In the final step of this study, the recyclability of the catalyst was
investigated. In this line, after completing of oxidation of benzaldehyde,
193
Applied Clay Science 168 (2019) 184–195
the catalyst was separated by using an external magnet, washed, dried
(see the experimental section for more detail) and subjected to the next
run of the same reaction under similar reaction condition. This cycle
was repeated up to ten consecutive reaction runs and yield of the
product after each cycle was estimated and compared with that of fresh
catalyst, Fig. 9. As depicted in Fig. 9, recycling of the catalyst up to fifth
reaction runs showed only 7% loss of the yield of the desired product.
More precisely, after each reaction run only 1–3% loss of the yield was
observed. However, further recycling led to more loss of the catalytic
activity and the yield of the product decreased to 52% after tenth re-
action runs.
To further study the reason of decrease of the catalytic activity, the
FTIR spectrum of the recycled catalyst after ten reaction runs was re-
corded and compared with that of fresh Fe-Hal-PAMAM-IL, Fig. 10.
Notably, it can be seen that in the FTIR spectrum of the recycled cat-
alyst the characteristic bands of the catalyst are present, indicating the
stability of the catalyst in the course of recycling. However, broadening
of the bands can be observed. To further study the recycled catalyst and
elucidate whether the structure of the catalyst could change upon re-
cycling, the XRD pattern of the recycled catalyst was recorded and
compared with that of fresh catalyst, Fig. 11. As illustrated, both fresh
and recycled catalysts exhibited the characteristic peaks of Hal and
[FeCl4]−, implying that recycling of the catalyst did not diminish the
structure of the catalyst. Notably, precise comparison of two XRD pat-
terns showed that some peaks shifted slightly. According to the litera-
ture, this shift can be due to the distortion of crystalline structure of Hal
that caused by surface hydroxyl groups alteration in the course of
consecutive washing of the catalysts upon several recycling (Bahri-
Laleh et al., 2018b; Zargarian et al., 2015).
4. Conclusion
A novel heterogeneous magnetic catalyst, Fe-Hal-PAMAM-IL, was
developed by growing dendrimer of generation of 3 on the surface of
amine-functionalized Hal followed by modification of dendrimer
terminal groups with IL and incorporation of Fe species. Fe-Hal-
PAMAM-IL proved to be an efficient catalyst for the oxidation of ben-
zaldehydes to the corresponding benzoinc acids in the presence of hy-
drogen peroxide as oxidant and CD as phase transfer agent. The com-
parison of the catalytic activity of Fe-Hal-PAMAM-IL with that of
control catalysts with no IL and dendrimer confirmed the role of both
components in the catalysis. Scrutinizing the effect of dendrimer gen-
eration on the catalytic activity, it was found that the catalyst with
dendrimer of generation 3 exhibited the highest catalytic activity. This
was attributed to the higher content of catalytically active species (IL
and Fe) that compensate the lower accessibility. Finally, the recycling
experiments revealed that the catalyst could be recovered magnetically
and recycled for several reaction runs with slight loss of the catalytic
activity and Fe leaching.
Acknowledgements
The authors appreciate partial financial supports from Iran Polymer
and Petrochemical Institute and Alzahra University. S. Sadjadi and M.
M. Heravi are thankful to Iran National Science Foundation (INSF) for
supporting this research under contract No. 97009384.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.clay.2018.11.012.
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