Tb2(WO4)3@N-GQDs-FA as an efficient nanocatalyst for the efficient synthesis of β-aminoalcohols in aqueous solution

Article abstract of DOI:10.1016/j.molliq.2021.115555

In the current study, Tb₂(WO₄)₃@N-(GQDs) modified with folic acid (FA) was synthesized during the chemical reaction of terbium (III) tungstate nanoparticles with nitrogen doped graphene quantum dots (N-GQDs) and introduced

Full text of DOI:10.1016/j.molliq.2021.115555

Journal of Molecular Liquids 329 (2021) 115555
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Journal of Molecular Liquids
journal homepage: www.elsevier.com/locate/molliq
Tb2(WO4)3@N-GQDs-FA as an efficient nanocatalyst for the efficient
synthesis of β-aminoalcohols in aqueous solution
Sajjad Azizi a,1, Mahdieh Darroudib,1, Jafar Soleymania, Nasrin Shadjouc,
⁎
a
Pharmaceutical Analysis Research Center, Tabriz University of Medical Science, Tabriz, Iran
Department of Energy Science and Technology, Faculty of Science, Turkish- German University, 10634820 Istanbul, Turkey
b
c
Department of Nanotechnology, Faculty of Science and Chemistry, Urmia University, Urmia, Iran
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 9 January 2021
Received in revised form 28 January 2021
Accepted 30 January 2021
Available online 2 February 2021
In the current study, Tb2(WO4)3@N-(GQDs) modified with folic acid (FA) was synthesized during the chemical
reaction of terbium (III) tungstate nanoparticles with nitrogen doped graphene quantum dots (N-GQDs) and in-
troduced as a heterogeneous catalyst for the synthesis of β-aminoalcohols derivatives. The as-prepared Tb2
(WO4)3@N-GQDs-FA is stable at −4 °C for at least two month. Herein, the reaction time, solvent, and catalyst
amount were optimized. The Tb nanostructure exhibited a high efficiency, less reaction time, excellent selectivity,
and simple procedure for these transformations. The performance Tb2(WO4)3@N-GQDs-FA nanocatalyst catalyst
is thoroughly investigated which shows several advantageous including to facile preparation from readily avail-
able materials. Shorter reaction times, easy work-up, green reaction media, higher yields (near 97%), and no need
to use the chromatographic column are the advantages of the reported synthetic method. The Tb2(WO4)3@N-
GQDs-FA heterogeneous catalyst has been recovered through filtration and also reused for multiple cycles. The
recovered catalyst can be used for another nine successive reaction without noticeable loss in activity. The reac-
tion time is also reduced and products can be obtained by convenient workup, and environmental-friendly
procedure.
Keywords:
Tungstate nanoparticles, graphene quantum
dots
Heterogeneous catalysis
Folic acid
β-Aminoalcohols
© 2021 Elsevier B.V. All rights reserved.
1. Introduction
different catalytic system was reported to overwhelm these limita-
tions, such as Zn(OTf)2 [29], LiBF4, CaCl2 [30], [i-PrO]2AlOOCCF3
β-aminoalcohols are ubiquitous in pharmaceutical molecules and
natural products. The development of methods for the preparation of
aminoalcohol scaffolds as a biologically active compound is a signif-
icant endeavor in the field of organic chemistry [1–6]. However, the
reactivity of this disubstituted structure could be challenging since
this 1,2-dipolar substitution relationship between amino and hy-
droxyl groups create a dissonant pattern about C skeleton [7,8]. The
prevalence of this moiety has spurred the catalyst development for
β-aminoalcohols preparation, which nucleophilic opening of
aziridine and epoxide rings, and the aminohydroxylation of alkene
and are the most advanced procedures [9–25]. As a result, consider-
able attention to develop environmental and viable routes to
syntheisiz aziridine or epoxide rings' ring-opening have been devel-
oped [26]. The aminolysis procedure in the absence of a catalyst
could be considered as a favored method in some cases; however, it
also has some demerits as prolonged reaction time or high tempera-
ture [27,28]. Otherwise, the aminolysis reaction in the presence of
[31], CoCL2 [30], Bi(OTf)3 [32] and LiOTF [32] under microwave radi-
ation, alumina [33], silica under high pressure [34], SBA modified by
Fe(III) salen [35] have been implemented to make important ad-
vances in regioselectivity, reaction time, temperature, environmen-
tally friendly condition. Thus, developing an efficient catalytic
protocol for epoxide ring-opening under ambient temperature is
necessary.
Nanomaterials, due to their unique electrical and optical properties
and also large surface to volume ratio, have been subjects of different
field of study. To date, remarkable progress has been made in develop-
ing novel nanocatalysts [36–44]. Quantum dots (QDs) are one of the ex-
tensively researched nanoparticle systems. The synthesis of graphene
quantum dots (GQD) has become a popular topic in recent years
[45–52]. The term GQD is usually used to describe miniscule fragments,
limited in domains or size of single-layer to tens of layers of graphene.
GQD often possess unique properties like optical, stable
photoluminescence, pronounced quantum confinement effect, which
makes them attractive for energy, optoelectronic, catalytic, biological,
and environmental applications [50–53]. While graphene usually does
not have a bandgap, GQD contains a bandgap due to edge effects and
quantum confinement. The bandgaps modify graphene's carrier
⁎
Corresponding author.
E-mail address: n.shadjou@urmia.ac.ir (N. Shadjou).
Equal contribution and co-first author.
1
https://doi.org/10.1016/j.molliq.2021.115555
0167-7322/© 2021 Elsevier B.V. All rights reserved.

S. Azizi, M. Darroudi, J. Soleymani et al.
Journal of Molecular Liquids 329 (2021) 115555
behavior and may lead to different applications. GQD was also found to
have four quantum states at given energy levels, unlike semiconductor
QD, which has just two [54–61]. According to previous reports, these ad-
ditional quantum states could make GQDs beneficial for quantum com-
puting. The GQD has a large surface and mostly contains a rich surface of
functional groups on carbon [61,62]. The richest functional groups are
carboxylic groups and amine groups, which can be electron acceptor
and donor, and thus can be instantly conjugated to ions (terbium
GQD). Terbium is an essential rare earth element that has a very low
concentration in the earth's crust [45,63–65]. Its unique electronic lay-
out state determines its critical application in color television, optical ac-
tuators, catalysis, and the fluorescence lamp.
β-aminoalcohols has been used extensively in the synthesis of
therapeutic due to its structural similarity to neurotransmitters and hor-
mones [66–69]. We aimed to produce β-aminoalcohols regioselectively
through utilize unexplored opening of styrene oxide and aniline [9,18].
Herein, we have prepared Tb2(WO4)3@N-GQDs-FA nanocatalyst, and
also characterization, the ability of terbium tungstate functionalized
with a GQD matrix was investigated in the catalytic performance in
order to the synthesis of β-aminoalcohols under mild and green condi-
tions at room temperature. Tb2(WO4)3@N-GQDs-FA shows a yield of
97% for the preparation of β-aminoalcohols (with wt% catalyst loading).
The catalytic activities of nanocatalyst are further improved.
solid particles. The obtained Tb2(WO4)3@N-GQDs was dialyzed possible
unreacted materials.
2.2.3. Preparation of NHS-FA
FA-NHS was prepared according to the EDC/NHS reaction. In brief,
60 mg of FA, 12 mg of NHS, and 10 mg of EDC were dissolved in about
12 mL of DMSO-d6, and then 150 μL of TEA was added and agitated at
room temperature for about 18 h. Subsequently, TEA molecules were
evaporated using a vacuum. Finally, the produced FA-NHS was kept at
−4 °C for the next uses.
2.2.4. Preparation of Tb2(WO4)3@N-GQDs-FA
20 mL of Tb2(WO4)3@N-GQDs solution was added to the 12 mL of
the NHS-FA solution and stirred at room temperatures for about 3 h. Fi-
nally, Tb2(WO4)3@N-GQDs-FA black-brown solution was centrifuged
and dialyzed (3000 Da) toward deionized-waste for at least 3 days.
The as-prepared Tb2(WO4)3@N-GQDs-FA is stable at −4 °C for at least
two months.
2.3. General procedure for syntheis of β-Aminoalcohols
To investigate the catalytic performance of the Tb2(WO4)3@N-
GQDs-FA catalyst toward β-aminoalcohols preparation, styrene
oxide and aniline was chosen as the test substrates. The optimization
of the reaction conditions of styrene oxide and aniline in the pres-
ence of Tb2(WO4)3@N-GQDs-FA in different conditions are summa-
rized in Table 2. The reaction mixture was monitored by TLC. After
completion of the reaction, the Tb2(WO4)3@N-GQDs-FA catalyst
was separated through centrifuging and the residue was purified
from the reaction mixture by silica plate. To clarify the scope and re-
strictions of the Tb2(WO4)3@N-GQDs-FA catalytic system in reaction
with styrene oxide, under carefully optimized reaction condition,
various aromatic and aliphatic amines were examined (Table 1).
The ring-opening reaction was found to be fast, and nearly comple-
tion of conversion was obtained within 30 min, which led to the
quantitative β-aminoalcohols yield.
2. Experimental
2.1. Methods and materials
All the commercial-grade chemicals and reagents were used without
further purifications purchasing from Merck Company. The reaction
was monitored using analytical thin-layer chromatography (TLC) with
ethyl acetate/n-hexan as eluents. Due to the need to achieve final pure
and isolated target molecules, a scaled-up TLC was used. The definite
characterization of all products was done with 1H NMR (500 MHz)
and 13C NMR (125 MHz) spectra recorded with a Bruker DRX-500
Avance spectrometer using DMSO‑d6as a solvent at ambient tempera-
ture. All yields referred to isolated products. The Infrared spectra (IR)
of the sample were recorded from KBr disc by Fourier-Transform (FT-
IR) Shimadzu FT-IR-8400S spectrometer in the range of 500 to
4000 cm−1. The transmission electron microscopy (TEM) images were
obtained by a Carl Zeiss LEO 906 electron microscope operated at
100 kV (Oberkochen, Germany). The Zeta potential of GQD GQD-Tb
was measured by ZETASZER ZS90. The UV–Vis spectrometer was per-
formed using Shimadzu UV 3600 spectrometer. Fluorescence spectra
were analyzed by a Jasco FP 750 spectrophotometer (Tokyo, Japan).
Table 1
Optimization of β-Aminoalcohol preparation.
Entry Catalyst (mg) Time (min) Solvent
Temperature (°C) Yield, %
1
2
3
4
5
6
7
8
10
10
10
10
10
10
10
0
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
0
Water
Solvent-free r.t
r.t
60
10
71
5
15
N
97
0
5
33
54
79
97
97
97
97
97
0
10
41
67
97
97
97
97
97
MeOH
Acetonitrile
Toluene
n-Hexane
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
r.t
r.t
r.t
r.t
r.t
r.t
r.t
r.t
r.t
r.t
r.t
r.t
r.t
r.t
Reflux
r.t
r.t
r.t
r.t
r.t
r.t
r.t
r.t
r.t
2.2. Synthesis of nanomaterials
2.2.1. Preparation of Tb2(WO4)3 NPs
The terbium (III) tungstate nanoparticles were synthesized accord-
ing to an optimized process which was previously reported by Rahimi
et al. [7,8]. Generally, 0.01 M terbium ion (Tb3+) was added over to
the tungsten ion solution (0.005 M) and then stirred. After that, the
white solid was filtered and washed several times with absolute ethanol
and water. Finally, as prepared participated was dried at 80 °C for at
least 4 h.
9
1
2.5
5
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
7.5
20
30
40
10
10
10
10
10
10
10
10
10
10
10
2.2.2. Preparation of Tb2(WO4)3@N-GQDs nanocomposite
Tb2(WO4)3@N-GQDs was synthesized according to following
method. 1 g of citric acid and 0.4 mL of ethylenediamine was added
into 15 mL water and stirred to dissolve. Then, 50 mg of as-prepared
Tb2(WO4)3 NPs were added to the mixture. Next, the mixture was
transferred into a 50-mL Teflon-lined stainless hydrothermal synthesis
autoclave and heated to 180 °C and kept for about 8 h. Afterward, the
mixture was cooled to room temperature. Finally, as-synthesized
nanomaterials were centrifuged (10.000 rpm for 15 min) to remove
5
10
20
30
40
50
60
70
2

S. Azizi, M. Darroudi, J. Soleymani et al.
Journal of Molecular Liquids 329 (2021) 115555
Scheme 1. Preparation of Tb2(WO4)3@N-GQDs-FA
Fig. 1. TEM image of Tb2(WO4)3@N-GQDs-FA in diferent magnification.
3. Results and discussion
and amine group of Tb2(WO4)3@N-GQDs. The zeta potential analysis
of Tb2(WO4)3@N-GQDs-FA nanocomposite was determined to check
the influence of Tb ions, which doped on the surface charge and slow
the exact doping of N-GQDs-FA nanocomposite with Tb2(WO4)3 spe-
cies. Thus, the nanomaterial exhibited a negative external charge,
which confirmed the fixing FA and Tb2(WO4)3 ion groups on the super-
ficial spaces of the N-GQD composite (Fig. 3).
The scanning electron microscopy micrograph (SEM) was used to in-
dicate the morphology of Tb2(WO4)3@N-GQDs-FA, which exhibited the
fibrous-like structure of catalyst (Fig. 4). The chemical composition of
Tb2(WO4)3@N-GQDs-FA nanocomposites was also studied through EDX
analysis, which confirmed the presence of Tb and W in the catalyst
along with the other elements, indicating the formation of the desired
structure of nanocomposite. The loading Tb metal was found to be
0.018 mmol/g of the catalyst (0.02 wt%). As shown in Fig. 5, the EDX mea-
surement confirmed that the nanocatalyst contains C, N, O, Na, Tb, and W.
3.1. Material characterization
The prepared GQD was simply synthesized through refluxing in the
mixture of concentrated citric acid and EDTA at 180 °C in an oil bath. The
synthetic method of the functionalized Tb2(WO4)3@N-GQDs-FA has
been illustrated in scheme 1. The TEM image of the prepared GQD is
shown in Fig. 1. It revealed the morphology of functionalized GQD
with an average size at 2–5 nm and a narrow size range at 4 nm. Also,
the surface electron density was measured by the Zeta potential ana-
lyzer and demonstrated an average size at 0.90 nm (Fig. 2).
To determine functional groups, surface state, and composition of
the Tb2(WO4)3@N-GQDs-FA, the characterization was measured by
the FT-IR. The FT-IR spectrum exhibited a broad absorption peak at
3330 cm−1, which is attributed to the hydroxyl and N\\H on the surface
of the modified N-GQDs. In additions, two addorption peaks at 1551,
and 1643 cm−1 belong to the stretching vibrations of the C_C and
C_O bonds of N-GQDs, respectively and the peaks could be seen at
the range of 680 and 540 cm−1 relating to Tb3+ bonds. Also, the peak
around 1500 cm−1 is related to amide bonds between carboxyl of FA
3.2. Absorption properties
The optical properties of synthesized Tb2(WO4)3@N-GQDs-FA and
GQD solution using the UV–Vis absorption were studied (Fig. 6). The
3

S. Azizi, M. Darroudi, J. Soleymani et al.
Journal of Molecular Liquids 329 (2021) 115555
Fig. 2. FLS and Zeta potential analyzer Tb2(WO4)3@N-GQDs-FA.
1.1
1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
1072
1416
2068
503
679
1551
1643
3331
3900
3400
2900
2400
1900
1400
900
400
Wavelenght/ nm
Fig. 3. The FT-IR spectum of Tb2(WO4)3@N-GQDs-FA.
Fig. 4. SEM images of Tb2(WO4)3@N-GQDs-FA nanocomposite in dfferent magnification.
4

S. Azizi, M. Darroudi, J. Soleymani et al.
Journal of Molecular Liquids 329 (2021) 115555
Fig. 5. EDX SEM images of Tb2(WO4)3@N-GQDs-FA nanocomposite.
blue line represented the UV–Vis of Tb2(WO4)3, the orange line pre-
sented UV–Vis absorption of Tb2(WO4)3@N-GQDs, and the gray line,
showed Tb2(WO4)3@N-GQDs-FA. As shown in Fig. 5, the addition of
Tb2(WO4)3 in GQD altered the optical properties of the synthesized
GQD. The UV–Vis spectra of Tb2(WO4)3 demonstrated two characteris-
tic peaks at 240 and 345 nm are attributing to π-π* and n-π* transition,
which in addition to GQD, the absorbance intensity altered. As for the
Tb2(WO4)3@N-GQDs solution, both of the absorption peaks at 240 and
345 nm was found to decrease, which implied interaction between
metal ions and GQD in the solution, likely the apparent affinity of
metal ion to O atom of the donor group [35]. Furthermore, the absorp-
tion peak of Tb2(WO4)3@N-GQDs-FA demonstrated absorption peaks
at 258 and 286, and 372 nm, which have a clear blue shift by 25 nm,
and the new absorption peak can be attributed to the C_O bonded
Tb2(WO4)3 complex [36].
3.3. Fluorescence spectra
The fluorescence spectra of the Tb2(WO4)3@N-GQDs-FA, Tb2(WO4)3,
N-GQDs, FA, and N-GQDs-FA are shown in Fig. 7. All the photo-
luminescence studies were performed in an aqueous medium. Upon ex-
citation at 220 nm, the strong emission peaks are observed at 260, 330,
410, and 620 nm, which are ascribed to the intra configurational
5D4
→ → →
7F6, 5D4 → 7F5, 5D4 7F4 and 5D4 7F3 electron transmission
for Tb2(WO4)3, sequential [70,71]. Moreover, fluorescent spectra of
the N-GQDs nanocomposite upon excitation 300 nm, exhibited a strong
2.5
2
Tb2(WO4)3 NPs
Tb2(WO4)3@N-GQDs
Tb2(WO4)3@N-GQDs-FA
1.5
240 nm
1
344 nm
241 nm
258 nm
286 nm
346 nm
0.5
0
372 nm
200
250
300
350
400
450
500
550
Wavelength/ nm
Fig. 6. The UV–Vis absorptions of Tb2(WO4)3, Tb2(WO4)3@N-GQDs, Tb2(WO4)3@N-GQDs-FA.
5

S. Azizi, M. Darroudi, J. Soleymani et al.
Journal of Molecular Liquids 329 (2021) 115555
Fig. 7. Fluorescence spectra of Tb2(WO4)3@N-GQDs-FA, Tb2(WO4)3, N-GQDs, FA, and N-GQDs-FA.
peak at 435 nm and the N-GQDs-FA nanocomposite displayed a
quenching peak at 435 nm efficacious preparation of nanocomposite.
According to Fig. 7, Tb2(WO4)3@N-GQDs-FA has some distinct emission
peak, which is in agreement with the functionalized Tb2(WO4)3@N-
GQDs structure. Sp2 hybridation and existence of oxygen-rich functional
groups such as C\\O, C_O and –COOH on the surface of N-GQDs are
caused to the decline on the fluorescence emission.
60, and 70 min, resulting in the isolation of the product in a yield of
10, 41, 67, and for all others 97%, respectively (Table 1, Entry 18–26).
It is clear that the yield of reaction enhances till the time of reaction in-
creased to 30 min, and the reaction was completed after 30 min at room
temperature. Considering these results, the optimal conditions for the
optimization of model reaction were appointed 10 mg of the Tb2
(WO4)3@N-GQDs-FA nanocatalyst at room temperature and in EtOH
as a green solvent in 30 min.
Then, the optimized conditions were used for the synthesis of
β-Aminoalcohol scaffolds (Scheme 2) using a series of amine
(1 mmol) and different substituted of epoxide (1 mmol) in ethanol
(3 mL) and in the presence of 10 mg Tb2(WO4)3@N-GQDs-FA
nanocatalyst. To investigate the substrate scope, generality, and utility
of this catalytic system, the epoxide ring-opening reaction was exam-
ined under optimal reaction conditions. It can be seen that all products
were obtained in high yields (Table 2). Various amines were examined
as substrates in the optimized reaction condition. The observed catalytic
changes have been related to electronic and steric effects. The with-
drawing substituted of amines, besides steric hindrance, had less reac-
tivity, whereas the electron donor substituted of amine promoted a
high yield in the transformation (Table 2). Both aromatic and aliphatic
epoxide, including those bearing functional groups as oxabicyclic hep-
tane, ethyl oxirane, styrene oxide, and phenoxy methyl-oxirane, were
able to undergo the corresponding β-aminoalcohols preparation. Also,
the aliphatic and aromatic amines were used in the model reaction to
study the effect of substrate on the reactivity of reaction, resulting in
β-aminoalcohol products in good yields (Table 2, Entries 1–12). Under
the optimized conditions, aromatic amines such as aniline all give
both higher conversion and greater yields at room temperature within
the reaction time. However, the aliphatic amines with electron-
withdrawing groups reacted more smoothly (Table 2, Entry 5). Electron
donating groups exhibits significant reactivity, and also reactions were
completed even at a lower temperature and higher conversion. More-
over, the aromatic epoxide, which has electron-rich groups, increased
the reactivity of the transformation, whereas the aliphatic groups led
to much lower yields (Table 2, Entries 1,9,10).
3.4. Application of Tb2(WO4)3@N-GQDs-FA for β-aminoalcohols
preparation
Once the catalytic activity of Tb2(WO4)3@N-GQDs-FA nanocatalyst
had been evaluated as a catalyst for the β-aminoalcohols preparation.
Initial experiments using styrene oxide and aniline were performed as
a model reaction to optimize various parameters comprising solvent,
temperature, time, and catalyst. The results are listed in Table 1.
In order to optimize the reaction condition, the effect of solvent was
surveyed in Table 1, which exhibited among the different solvents, such
as solvent-free, H2O, EtOH, MeOH, CH3CN, Toluene, and Hexane
(Table 1, Entry 1–7) depicted that the green solvent EtOH had the
highest yield in the shortest reaction time, while other solvents and
mixed solvents yielded a lower amount of product even in longer reac-
tion time. Therefore, at the outset, EtOH was chosen as a reaction me-
dium, and the model reaction was explored in various amounts of
catalyst. When the reaction was repeated in the presence of catalyst in-
cluding 1, 2.5, 5, 7.5, 10, 20, 30, and 40 mg of Tb2(WO4)3@N-GQDs-FA
nanocatalyst, resulted in the isolation of the product in a yield of 5, 33,
54, 79 and for more amount of catalysts were 97%, respectively
(Table 1, Entry 9–15). In the absence of a catalyst at room temperature,
after 30 min, no product was obtained (Table 1, Entry 8). It is noticanle
that, catalyst-free reaction condition led to decreasing the rate of reac-
tion and a considerable amount of starting materials remain intact
even after prolonged reaction time. Also, the optimal value of tempera-
ture was interpreted, which demonstrated that raising the temperature
of reaction does not affect the yield of reactions. Notably, the yield of re-
action was independent toward temperature as in reactions with vari-
able temperature from room temperature to about 78 °C, in EtOH and
when the time is raised (Table 1, Entry 0.16 and 17). The reaction
proceeded rapidly, as exhibited, in different times 5, 10, 20, 30, 40, 50,
The proposed mechanism for the synthesis of β-aminoalcohols in
the presence of Tb2(WO4)3@N-GQDs-FA nanocatalyst is shown in
Scheme 3. This catalyst with having many polar functional groups can
OH R1
O
Tb2(WO4)3@N-GQDs-FA
EtOH, rt.
H
N
N
R2
R1
R2
Scheme 2. Synthesis of β-aminoalcohols by Tb2(WO4)3@N-GQDs-FA nanocatalyst
6

S. Azizi, M. Darroudi, J. Soleymani et al.
Journal of Molecular Liquids 329 (2021) 115555
Table 2
Application of Tb2(WO4)3@N-GQDs-FA nanocatalyst for synthesis of β-aminoalcohols under optimized reaction.
Entry
1
Amine
Oxirane
Yield
97
90
95
70
2
3
4
71
73
5
6
78
72
80
7
8
9
76
82
71
10
11
12
7

S. Azizi, M. Darroudi, J. Soleymani et al.
Journal of Molecular Liquids 329 (2021) 115555
O
N
N
N
N
N
O
N
N
H
O
N
N
N
H
H2N
N
COOH
O
NH
N
HN
H2N
N
COOH
O
O
NH
N
HN
O
O
N
N
N
H
NH
Tb2(WO4)3@N-GQDs-FA
R2
HN
R1
N
N
N
N
O
N
H
R2
HN
H2N
N
COOH
O
R1
O
OH R1
NH
N
N
O
N
R2
N
N
H
Scheme 3. Proposed mechanism for the synthesis of β-aminoalcohols in the presence of Tb2(WO4)3@N-GQDs-FA nanocatalyst
easily activate a there membered epoxid ring through the hydrogen
demonstrated in Table 3. Encouraged by this result, we subsequently
examined various catalysts. Among different catalysts, Tb2(WO4)3@N-
GQDs-FA seemed to be the most active catalyst for the β-aminoalcohol
preparation (Table 3, Entry 1–9). The use of other catalysts for this
ring-opening reaction, such as nano Fe(OH)3, Fe3O4@SiO2-SO3H, Al2O3,
Β-CD, LiBr, Bi(OTf)3, Polymer/CuSO4, Tb-MOF led to a lower yield of
the reaction. Consequently, the proposed Tb2(WO4)3@N-GQDs-FA
nanocatalyst had some promising features, including stability, cost-
effective method, less reaction time, and commercially available
materials.
bonds interations. Then, by nucleophilic attacking of nitrogen atom in
substituted amines to the activated epoxid ring, the high yield of prod-
ucts are obtained.
3.5. Recycling of the catalyst
One of the most crucial aspect of profitable heterogeneous catalysts is
recyclability which make them attractive from economic point of view.
In order to recover the Tb2(WO4)3@N-GQDs-FA at reaction completion
point, after the accomplishment of each cycle, according to aforemen-
tioned optimized reaction condition, the solid catalyst was separated
simply by centrifugation followed by rinsing with ethanol (5 ml) for
few times and at 50 °C. After drying through vacuum overnight and
use again in a sequential run, the results exhibits that catalyst is substan-
tially recyclable under the optimized reaction condition and even after
nine times use, supported by analysis result provide in Fig. 8. Next, hot
filtration test was applied to determine the stability characteristic of
the Tb2(WO4)3@N-GQDs-FA nanocatalyst. After 2 h, the reaction mix-
tures were centrifuged followed by filtration of catalyst. Then the super-
natant was stirred at ambient temperature. Intriguingly, even after
additional 4 h, there were not any considerable changes in the transfor-
mation reaction. Compared to previously recognized catalyst for
aminolysis of epoxides, Tb2(WO4)3@N-GQDs-FA is showing decent cata-
lytic performance regarding to activity and recyclability (Table 3).
100
95
97
96
96
95
95
93
92
92
90
85
80
75
70
91
1
2
3
4
5
6
7
8
3.6. Performance of the catalyst
9
REUSE
The performance of the prepared Tb2(WO4)3@N-GQDs-FA nanopar-
ticle, in comparison with the previously reported catalyst, is
Fig. 8. Recyclability of the Tb2(WO4)3@N-GQDs-FA nanoparticle in the aminolysis reaction
of the epoxide.
8

S. Azizi, M. Darroudi, J. Soleymani et al.
Journal of Molecular Liquids 329 (2021) 115555
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Entry Catalyst
Amount Temp
(mg)
Solvent
Time Yield
(min) (%)
1
2
3
4
5
6
Nano Fe(OH)3
Fe3O4@SiO2-SO3H
Al2O3
Β-CD
LiBr
20
RT
–
45
92
82
69
88
98
96
10
RT
EtOH
THF
Water
–
180
360
480
300
33
6000
–
Reflux
60
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5 mol%
RT
Bi(OTf)3
0.05 mol Microwave CH3CN
%
7
8
9
Polymer/CuSO4
Tb-MOF
Tb2(WO4)
–
20
10
RT
RT
RT
Cyclohexane 180
EtOH
EtOH
88
95
97
30
30
3@N-GQDs-FA
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4. Conclusion
In summary, GQDs can act as a heterogeneous catalyst for a variety
of organic reactions. We prepared a new Tb2(WO4)3@N-GQDs-FA
nanocatalyst and characterized by TEM, Zeta-DLS, SEM-EDX, IR, UV–
Vis, and fluorescence. The efficiency of Tb2(WO4)3@N-GQDs-FA
nanocatalyst was examined in the synthesis of β-aminoalcohol analogs
that have been successfully carried out through aminolysis of epoxides.
This nanocatalyst was applied to prepare β-aminoalcohols under green
and mild conditions at room temperature. In these reactions, a catalytic
amount of heterogeneous catalyst is required which can be recovered to
reuse after completion of reaction, simply by applying centrifugation.
Shorter reaction times, easy work-up, green reaction media, higher
yields (near 97%), and no need to use the chromatographic column
are the advantages of the reported synthetic method. The recovered cat-
alyst can be used for another nine successive reaction without notice-
able loss in activity. The performance Tb2(WO4)3@N-GQDs-FA
nanocatalyst catalyst is thoroughly investigated which shows several
advantageous including to facile and low cost preparation from readily
available materials. The reaction time is also reduced and products can
be obtained by convenient workup, and environmental-friendly
procedure.
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Sajjad Azizi: Methodology, Analysis data, Investigation, Writing-
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Mahdieh Darroudi: Analysis data, Writing Original draft and review
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Jafar Soleymani: Investigation.
Nasrin Shadjou: Project administration, Investigation, Funding ac-
quisition, Methodology, Supervision, Resources, Writing-review and
editing.
Data Availability Statement
The data that support the findings of this study are available from
the corresponding author upon reasonable request.
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Declaration of Competing Interest
The authors declare no conflict of interest.
Acknowledgment
[52] Z. Ma, Y. Sun, J. Xie, P. Li, Q. Lu, M. Liu, P. Yin, H. Li, Zhang, S, Yao. ACS Appl Mater In-
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We gratefully acknowledge the financial support from Urmia Uni-
versity and Tabriz University of Medical Science.
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