DFNS/α-CD/Au as a Nanocatalyst for Interpolation of CO2 into Aryl Alkynes Followed by SN2 Coupling with Allylic Chlorides

Article abstract of DOI:10.1007/s10562-020-03451-1

Abstract: In the present study, to effectively carbonylate cinnamyl chloride and phenylacetylene with CO₂, α-cyclodextrin doping dendritic fibrous nanosilica (DFNS) supported nanoparticles of gold was used as a catalyst (DFNS/α-CD/Au NPs). In the catalyst, the nanoparticles of Au were in situ reduced on the surfaces of DFNS. Transmission electron microscopy (TEM), scanning electron microscope (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), and X-ray energy dispersive spectroscopy (EDS) were utilized for characterizing the nanostructures DFNS/α-CD/Au. It was found that the nanostructures of DFNS/α-CD/Au can be nominated due to their effective and novel catalytic behaviour during the synthesis of 3a,4-dihydronaphtho[2,3-c] furan-1(3H)-ones from cinnamyl chloride, phenylacetylene, and CO₂. Graphic Abstract: [Figure not available: see fulltext.].

Full text of DOI:10.1007/s10562-020-03451-1

Catalysis Letters
https://doi.org/10.1007/s10562-020-03451-1
DFNS/α-CD/Au as a Nanocatalyst for Interpolation of CO2 into Aryl
2
Alkynes Followed by SN Coupling with Allylic Chlorides
Zhiyong Wang1 · Xuhao Li2 · Li Feng2 · Bingzhi Liu2 · Farzaneh Shamsa3
Received: 18 August 2020 / Accepted: 1 November 2020
© Springer Science+Business Media, LLC, part of Springer Nature 2020
Abstract
In the present study, to efectively carbonylate cinnamyl chloride and phenylacetylene with CO2, α-cyclodextrin doping
dendritic fbrous nanosilica (DFNS) supported nanoparticles of gold was used as a catalyst (DFNS/α-CD/Au NPs). In the
catalyst, the nanoparticles of Au were in situ reduced on the surfaces of DFNS. Transmission electron microscopy (TEM),
scanning electron microscope (SEM), X-ray difraction (XRD), Fourier transform infrared spectroscopy (FT-IR), and X-ray
energy dispersive spectroscopy (EDS) were utilized for characterizing the nanostructures DFNS/α-CD/Au. It was found
that the nanostructures of DFNS/α-CD/Au can be nominated due to their efective and novel catalytic behaviour during the
synthesis of 3a,4-dihydronaphtho[2,3-c] furan-1(3H)-ones from cinnamyl chloride, phenylacetylene, and CO2.
Graphic Abstract
Cl
+
O
DFNS/CD/Au
CO
+
R
2
O
R
Keywords Nanocatalyst · Green chemistry · One-pot synthesis · Nanoparticle · Carbon dioxide
1 Introduction
The conservation of CO2 to benefcial organic chemicals has
been extensively researched by scientists [1–5]. In the chem-
ical industry, the transportation sector, and power plants,
CO2 is known as a greenhouse gas and a waste compound [6,
7]. In addition, it is non-toxic, non-fammable, inexpensive,
and easily available carbon feedstock [8, 9]. However, CO2
is not generally used in the industry due to its low reactivity
[10]. Optimal reaction conditions, signifcant energy input,
and highly active catalysts are key factors for the appropriate
conversion of stable thermodynamic CO2 molecules [11].
Rawat et al. reported the synthesis of MgO@Ag-7 as a new
catalyst for the placement of CO2 into aryl alkynes, followed
by SN2 binding with allylic chlorides to prepare a wide range
of ester and lactone heterocycles in excellent efciency for
* Zhiyong Wang
weeklywang@163.com
* Li Feng
f19860314@126.com
* Farzaneh Shamsa
Farzaneh.Shamsa@gmail.com
1
Department of Basic Course, Shenyang University
of Technology, Liaoyang 111003, Liaoning, China
2
School of Civil and Transportation Engineering, Guangdong
University of Technology, Guangzhou 510006, Guangdong,
China
3
Young Researchers and Elite Club, Neyshabur Branch,
Islamic Azad university, Neyshabur, Iran
Vol.:(0123456789)
1 3

Z. Wang et al.
the frst time [12]. Many of these naturally occurring furan
and annulated furan derivatives and their unnatural analogs
have a wide range of biological activity and are important
precursors for the synthesis of natural products. [13, 14]
Especially, naphtho [2,3-b] furan-4,9-dione derivatives as
represented by avicequinones [15] and maturinones [16]
have shown a diversity of biological activities of medi-
cal importance, such as anticancer, antibacterial and anti-
infammatory activity [17].
literature to call them, including wrinkled, fbrous, dendritic,
Nanofower, lamellar, and dandelion. Recently, cyclodextrins
(CD) have been used for the preparation of supported metal
or metal oxide catalysts [54–58]. These polyhydroxylated
compounds are able to stabilize host-guest complexes and
molecule-ion adducts with inorganic metal salts [57–61]. In
this Review, to avoid confusion, an attempt has been made
to consider the same name utilized in the respective origi-
nal works. However, for ease of reading, we use dendritic
fbrous nanosilica (DFNS) for this class of materials [62].
Therefore, α-cyclodextrin (α-CD) supported on the DFNS
surface, called DFNS/α-CD, were produced and utilized
to construct DFNS supported gold NPs (DFNS/α-CD/
Au) catalysts by reducing Au on the surface of DFNS. The
α-CD compound was employed in the anatomy of a cata-
lyst to avoid nanoparticles from leaching. In the case of the
DFNS/α-CD/Au catalyst, Au NPs supported on DFNS can
used for the synthesis of 3a, 4-dihydronaphtho [2,3-c] furan-
1(3H)-ones from cinnamyl chloride, phenylacetylene, and
CO2 demonstrating the positive promoting infuence of Au
NPs (Scheme 1). This indicates the high catalytic power of
gold nanoparticles to perform this reaction.
The employment of new metal NPs in catalysis has long
attracted the attention of researchers due to their robust cata-
lytic activities [18–22]. Among the reported metal nanopar-
ticles deployed in catalysis, Au nanoparticles are the most
resistant metal nanoparticles, and have been considerably
researched due to their size-related characteristics that can
be used in diferent implementations [23–33]. This charac-
teristic can decrease the yield of the catalysts. To address
this weakness, gold nanoparticles are usually fxed on solid
supports with mesopores, including Al2O3 [34–36], SBA-
15 [37–39], SBA-16 [40], and MCM-41 [41, 42]. When
employing one of these Au-supported catalysts, small Au
NPs are mainly intersperse on internal surfaces and pores.
As a result, active sites within the pores are not easily acces-
sible, which limits their applications. Therefore, catalyst
support with good availability and high surface areas (i.e.
not inside the pores) is extremely advantageous. Access to
active gold sites in mesoporous silica was limited because of
the normal tubular anatomy and the blockage of the pores,
reducing the overall catalyst activity. Therefore, there is an
immediate need for a resistant catalyst. Considering our pre-
vious study on nanocatalysis, [43, 44] we decided to use
dendritic fbrous nanosilica (DFNS).
2 Experimental
3 Materials and Methods
Highly pure chemicals were bought from Fluka and Merck.
Melting points in open capillaries were discovered employ-
ing an Electrothermal 9100 apparatus and were not cor-
rected. FTIR spectra were identified on a VERTEX 70
spectrometer (Bruker) in the transmission mode in spec-
troscopic grade KBr pellets for powders. Particle size and
nanoparticle anatomy were perceived employing a Philips
CM10 transmission electron microscope working at 100 kV.
X-ray difraction data were acquired deploying Bruker D8
Advance model with Cu ka radiation. Thermogravimetric
Recently, dendritic fbrous nanosilica has been discovered
by Polshettiwar et al. [45–48]. It has illustrated exceptional
activities from all angles, such as gas absorption, catalysis,
energy storage, solar-energy harvesting, biomedical appli-
cations and sensors. It is called fbrous Nanosilica (KCC-
1) because of the fbrous structure of it in our main report
[49–53]. Nevertheless, the fbres were thin sheets 3.5–5.2 nm
thick and therefore, many other names are utilized in the
Cl
+
O
DFNS/CD/Au
K2CO3, 90 oC, 30 min
CO
+
R
2
O
R
Scheme 1 Synthesis of 3a,4-dihydronaphtho[2,3-c]furan-1(3H)-ones in the presence of DFNS/α-CD/Au NPs
1 3

DFNS/α-CD/Au as a Nanocatalyst for Interpolation of CO2 into Aryl Alkynes Followed by…
analysis (TGA) was performed on NETZSCH STA449F3 at
10 °C min−1 under nitrogen. The concentrations of Au ele-
ment and Ag element were measured by Varian 710 induc-
tively coupled plasma spectrometry (ICP-MS). The samples
for ICP were dissolved in aqua regia (HCl/HNO3). Product
purifcation and reaction controlling were performed by TLC
on silica gel polygram SILG/UV 254 plates.
into 150 mL of acetone. The precipitate formed in acetone
was collected using fltration.
3.4 Universal Approach to the Synthesis
of the DFNS/α‑CD/Au NPs
200 mg DFNS/α-CD and 0.027 mmol HAuCl4.3H2O
(10 mM, 2.67 mL) were released in the suspension. The
mixture was stirred continually for 1 h at 25 °C. The fresh
solution of ice-cold NaBH4 (30 mM, 2.65 mL, 0.08 mmol)
was added dropwise to the suspension. The colour of the
solution changed rapidly to red. The resulting solid was sep-
arated by centrifugation, washed by DI (deionized water) as
well as ethanol, and then dried overnight at 40 °C.
3.1 Universal Approach for the Synthesis
of the DFNS NPs
First, 3.0 g of tetraethyl orthosilicate (TEOS) was dissolved
in cyclohexane (25 mL) and 1-pentanol (1.0 mL) solutions.
Then, cetylpyridinium bromide (CPB) (1.2 g) and urea
(0.7 g) were stirred in a constant amount of water (25 mL),
and added. The blend was stirred continuously at 25 °C for
45 min. After adjusting in a Tefon-sealed autoclave, it was
heated at 110 °C for 4 h. The produced silica was seperated
and centrifuged, washed using an acetone-deionized water
mixture, and dried utilizing a drying oven. In the presence
of air, the produced material was calcined at 500 °C for 4 h.
3.5 Universal Approach to the Synthesis
of the 3a,4‑Dihydronaphtho[2,3‑c]
furan‑1(3H)‑Ones
20 mg of DFNS/α-CD/Au NPs, 1.0 mmol of cinnamyl chlo-
ride, and 1.0 mmol of phenylacetylene were poured in the
reactor vessel without the use of any co-solvent. The reac-
tor vessel was then subjected to continuous pressure with
carbon dioxide and K2CO3 (1.0 mmol), and then heated at
90 °C for 30 min. Upon completion, reaction progress was
analysed using TLC. EtOH was released in the DFNS/α-CD/
Au NPs and the reaction mixture was vacuum-fltered. The
resulting solvent was removed and the product was purifed
by recrystallization using n-hexane/ethyl acetate.
3.2 Universal Approach to the Synthesis
of the N‑Phenylaminomethyl‑Modifed NPs
24 mg aniline (0.2 mmol) was added in anhydrous N,N′-
dimethylformamide (DMF, 2.2 mL). Then, 4 mg Tetrabuty-
lammonium iodide as well as 0.3 mL anhydrous NEt3 were
released in the solution. Next, chloromethyltrimethoxysilane
(30 μL) was released. The solution was heated to 70 °C in
the presence of N2 gas for 24 h. The solvent was detached.
The resulting mixture was added to a suspension of PhMe/
EtOH (1 mL EtOH as was as 40 mL PhMe) and a constant
amount of as-synthesized DFNS (200 mg). After that, the
suspension was refuxed under the attendance of N2 gas for
12 h, centrifuged, and washed using MeOH. Finally, the
reaction mixture was refuxed for 12 h in the presence of N2
gas. The material was centrifuged, and washed by MeOH
solution.
4 Results and Discussion
In this paper, we hypothesized that gold NPs can be loaded
into DFNS fbres (Step D), and that placing gold nanopar-
ticles among DFNS fbres through DFNS blocking can pre-
vent the release of gold through the fbres. This occlusion
was performed using α-cyclodextrin (α-CD) (Step C) via an
aniline bond as an interface (Step B) (Scheme 2).
The structures and morphologies of the DFNS, DFNS/
α-CD, and DFNS/α-CD/Au NPs were characterized using
SEM and TEM. Figure 1a depicts a picture of TEM (DFNS
samples) by corrugated radial structures of uniform spheres
(350 nm in diameter) and high-quality textures. Wrinkled
fbres with a thicknesses of about 9 nm were observed.
The fbres are arranged in 3D from the centre after growth.
Moreover, the open pores were made conically using radial
structures. The SEM image demonstrates the solid fbre
nature of the whole sphere (Fig. 1d). In addition, increas-
ing access to active surfaces as well as mass transfer of the
reactants through the open channel of the mentioned hier-
archical fbre structure was facilitated. The TEM and SEM
images of DFNS/α-CD NPs proved that, after modifcation,
3.3 Universal Approach to the Synthesis
of the DFNS‑Modifed α‑Cyclodextrin
1.22 g α-cyclodextrin (1.0 mmol) as well as 0.21 g N,N′-
dicyclohexylcarbodiimide (1.0 mmol) were dissolved
in 30 mL DMF in the presence of a small amount of 4 Å
molecular sieves Ar. 0.25 g DFNS/Aniline was dissolved in
10 mL DMF, and then released dropwise in the solution. The
reaction whisked was stirred two times, each for 48 h in an
ice bath at 25 °C. Then, it set aside for 5 h until the precipi-
tate was completely settled. The precipitate was separated
using fltration. Next, the remaining sediment was poured
1 3

Z. Wang et al.
Scheme 2 Schematic description of the synthesis of DFNS/α-CD/Au NPs
1 3

DFNS/α-CD/Au as a Nanocatalyst for Interpolation of CO2 into Aryl Alkynes Followed by…
Fig. 1 TEM photos of DFNS NPs (a); DFNS/α-CD NPs (b); DFNS/α-CD/Au NPs (c); FESEM images of DFNS NPs (d); DFNS/α-CD NPs (e);
and DFNS/α-CD/Au NPs (f)
1 3

Z. Wang et al.
the morphology of DFNS did not difer (Fig. 1b, e). Fig-
ure 1c, f illustrate that FESEM and TEM photos of the Au
NPs. As observed, the as-prepared metal NPs were spherical
without considerable aggregation. The Au diameter NPs was
10–20 nm. Here, NPs were attached to the DFNS wall.
Figure 2 shows the XRD pattern of DFNS and DFNS/
α-CD/Au NPs. The broad peak in the range of 20–30° is
related to amorphous silica as opposed to the XRD pattern
of DFNS NPs (refer to Fig. 2a). In addition, Fig. 2b shows
the peaks of 2θ = 38.1°, 44.3°, 64.5°, and 77.7°, which
refect the presence of gold nanoparticles in the structure of
DFNS/α-CD/Au catalyst (JCPDS 04-0784). This proves the
development of gold particles on the surface of DFNS/α-CD.
The wide peak in the range of 20–30° belongs to amorphous
silica. XRD analysis may simply be indexed for the cubic
phase of gold NPs. Figure 2b demonstrates the presence of
Au nanoparticles [sharp peaks of (111), (200), (220), (311),
and (222)].
Fig. 3 TGA diagram of (a) DFNS, (b) DFNS/N-phenylaminomethyl,
and (c) DFNS/N-phenylaminomethyl/α-CD NPs
Thermogravimetric analysis of this material was done at
diferent temperatures (from room temperature to 700 °C)
to confrm the thermal stability of DFNS/α-CD/Au nano-
particles (refer to Fig. 3). Weight reduction at 180 °C was
due to the removal of both physisorbed and chemisorbed
solvents on the surface of the silica material. Organic
weight reductions (in range of 200–410 °C) of DFNS/N-
phenylaminomethyl/α-CD and DFNS/N-phenylaminomethyl
NPs are 28.3% and 9.7%, respectively. The results confrm
the organic structures supported on the DFNS surface.
The representative spectra of FT-IR of DFNS as well as
DFNS/α-CD/Au are represented in Fig. 4. The bands per-
ceived at 1628, 805, and 1106 cm−1 in the FT-IR spectrum
for DFNS and DFNS/α-CD/Au showed that is belonged to
the tensile state of the normal silanol group (Si–OH), the
water absorbed on the solid surface, and Si–O–Si vibrations,
respectively. The DFNS/α-CD/Au composite indicates bands
at about 1094, 795 and 464 cm−1. The broad and strong
absorption band (at 3000–3540 cm−1) is belonged to the
-OH tensile vibrations. In addition, the narrow peak of about
2940 cm−1 is related to -CH fragments. The characteristic
absorption bands belong to the O-C-O moiety in α-CD
(1080–1125 cm−1), which stands in the DFNS/α-CD/Au
range of material. It should be noted that, the absorption
band of about 1700–1730 cm−1 was attributed to the carba-
mate-type association between cellulose and α-CD.
The total pore volume, BJH pore diameter, and BET sur-
face area were 1.51 cm3/g, 13.64 nm, and 497 m2/g. The
factors related to DFNS/α-CD NPs reduced to 1.03 cm3/g,
10.21 nm, and 402 m2/g for DFNS. DFNS/α-CD nitrogen
uptake evaluation. Furthermore, a uniform structure with
reduced pore diameter, surface area, and pore volume factors
was recorded compared to pristine DFNS. The pore volume
Fig. 4 FTIR spectra of (a) DFNS, and (b) DFNS/α-CD/Au
Fig. 2 XRD analysis of (a) DFNS, and (b) DFNS/α-CD/Au
1 3

DFNS/α-CD/Au as a Nanocatalyst for Interpolation of CO2 into Aryl Alkynes Followed by…
100
Table 1 Structural parameters of DFNS, DFNS/α-CD, and DFNS/
96
96
93
93
α-CD/Au materials determined from nitrogen uptake experiments
90
90
80
Catalysts
SBET (m2 g−1
)
Vt (cm3 g−1
)
DBJH (nm)
70
60
50
40
30
20
10
0
DFNS
DFNS/α-CD
DFNS/α-CD/Au
497
402
296
1.51
1.03
0.68
13.64
10.21
5.13
58
17
100
90
80
70
60
50
40
30
20
96
96
0
1
2
3
4
CO2 Pressure (MPa)
82
Fig. 6 The infuence of CO2 pressure
64
43
100
90
80
70
60
39
96
96 96
89
27
14
68
10
0
50
30
40
50
60
70
80
90
100
47
Temperature (oC)
40
30
27
20
Fig. 5 Infuence of reaction temperature
10
9
0
0
5
10
15
20
25
30
35
40
decreased signifcantly with increasing N-phenylaminome-
thyl as well as α-CD into the catalyst structure. It can be
attributed to the high load of sensing probe that occupies
a large volume in the silicate walls. The formation of Au
NPs further reduced the porosity properties. It is interest-
ing to note that a decrease in pore volume was observed at
the time of gold nanoparticles formation (from 1.03 cm3g−1
of DFNS/α-CD to 0.68 cm3g−1 of DFNS/α-CD/Au). This
reduction proved the placement of gold nanoparticles among
DFNS fbres (refer to Table 1).
Time (min)
Fig. 7 The infuence of reaction time
100
90
96
96
96
96
80
70
69
60
50
40
30
20
10
0
Temperature has been shown to dramatically accelerate
the reaction. Through the lens of practical utilization, heat
elimination is crucial to conserve energy since the reaction
of CO2 insertion in alkynes is signifcantly exothermic.
Reaction yields increased from 14% to 96% in at 30–90 °C
during 0.5 h. When the temperature was raised to 90–100 °C,
no signifcant increase in the reaction of cinnamyl chloride,
and phenylacetylene with CO2 yield was observed. Through
the lens of energy saving, 90 °C was identifed as the best
temperature for reaction (Fig. 5).
42
17
0
5
10
15
20
25
30
35
Catalyst (mg)
Fig. 8 The infuence of catalyst amount
Figure 6 shows the infuence of CO2 pressure. Increasing
the concentration of CO2 in the reaction phase increased
the yield of 3a,4-dihydronaphtho[2,3-c]furan-1(3H)-ones.
Therefore, by increasing the CO2 pressure from 0.5 MPa
to 1.5 MPa, the yield of product gradually increased. The
3a,4-dihydronaphtho[2,3-c]furan-1(3H)-one concentra-
tion was decreased and reduced the reaction activity by
further enhancing the CO2 pressure to 2.5 MPa. In Fig. 7
shows the yield dependency of 3a,4-dihydronaphtho[2,3-c]
furan-1(3H)-one on the reaction time. The yield of 3a,4-
dihydronaphtho[2,3-c]furan-1(3H)-ones was considerably
enhanced in 5–30 min, and there was no considerable altera-
tion with prolongation of the of reaction time. The reaction
was completed in approximately 30 min. As shown in Fig. 8,
the yield of 3a,4-dihydronaphtho[2,3-c]furan-1(3H)-ones
1 3

Z. Wang et al.
was enhanced with increasing DFNS/α-CD/Au NPs cata-
lyst value. No product was obtained in the absence of the
catalyst. The result of adding 10–15 mg of catalyst to the
sample reaction was the average yield of product. The best
result was achieved in the presence of 20 mg of catalyst.
The catalytic activities were studied under optimal reac-
tion conditions to investigate the amplitude and limitations
of the DFNS/α-CD/Au NPs (refer to Table 2). Alkynes bear-
ing an electron-donating substituent (Table 2, entries 2 and
3) were changed to 3a,4-dihydronaphtho[2,3-c]furan-1(3H)-
ones in high efciencies. In order to obtain the product in
a good yield that is likely because of the reduced electron
density of the alkynes nitrogen atom, an electron-withdraw-
ing group considered for alkynes (Table 2, entries 4 and 5).
To further examine the performance of the catalyst, vari-
ous control tests were done and the related information is
illustrated in Table 3. First, a standard reaction was per-
formed utilizing DFNS. Results showed that no value of
the favorable product was produced after 30 min of reaction
time (Table 3, entry 1). In addition, when DFNS/α-CD was
deployed as a catalyst, a no reaction was observed (Table 3,
entry 2). The DFNS or α-CD could not provide sufcient
catalytic activity under mild reactions. Concerning these
unsatisfactory results, we continued research to enhance the
efciency by adding Au NPs (Table 3, entry 3). Our results
show that the reaction cycle was primarily catalysed deploy-
ing the types of Au NPs supported in the DFNS nanostruc-
ture. Nano-sized particles enhance the amount of catalyst
activity due to the increase in surface area to volume, so they
signifcantly increase the sensitivity between the reactants
and the catalyst and act like a homogeneous catalysts.
In green chemistry, for reaction of allylic chlorides and
alkynes by CO2, the reusability of a catalyst is introduced as
an important feature. Hence, reusability of the DFNS/α-CD/
Au NPs was investigated considering optimized mode. The
DFNS/α-CD/Au NPs were directly separated from the liq-
uid reaction after a completed run of reaction. After clean-
ing the catalysts, the compound can be reused immediately.
Figure 9 shows that the catalyst was reused for ten continu-
ous runs. We have obtained 91% of product at the 10th run,
which shows only a 5% drop in performance compared to
96% of fresh catalyst. Besides, for the production of 3a,4-
dihydronaphtho[2,3-c]furan-1(3H)-one the value of Au
leached in the solution was evaluated using ICP after each
run. Figure 10 shows that reuse of the catalyst in ten con-
secutive runs did not reduce catalytic activity, considering
minimal (<0.05 ppm) leaching of Au (as investigated by
ICP-OES).
after utilizing the heterogeneous catalyst, the amount of
gold nanoparticles leaching from the surface of the DFNS
and remaining in the reaction mixture was very low. After
30 min, the product was acquired with 49% efciency. In
the process of reaction, it was proved that the catalyst acts
heterogeneously and only a slight leaching was observed in
the reaction. Second, to prove the heterogeneous pattern of
the catalyst, we carried out the mercury poisoning investi-
gation. Mercury (0) is dramatically deactivated the metal
catalyst (active surface) and blunted the catalyst activity.
The experimental set in this research proved the catalyst
heterogeneous behavior. After 15 min of the reaction, about
300 M mercury was released to the reaction compound. For
more than 30 min, the reaction area was stirred. After 30 min
of catalyst poisoning, no more conversion was perceived.
Figure 11 indicates the kinetics form of the reaction in the
presence of Hg (0). Negative results of heterogeneity tests
(Hg (0) poisoning as well as hot fltration), illustrated that
the solid catalyst is completely heterogeneous and no acquir-
able gold leaching happened upon the synthesis of 3a,4-
dihydronaphtho[2,3-c]furan-1(3H)-one.
The Au NPs load in the DFNS/α-CD/Au and DFNS/Au
NPs was determined by ICP-MS as 1.9 and 2.0%, respec-
tively. Almost equal load values were obtained in both
nanocomposites. In addition, leaching of gold NPs was
investigated by the ICP-MS analysis of the catalyst after
ten reaction cycles. The amount of Au NPs in the DFNS/
α-CD/Au NPs after ten reuse was 1.7%, which showed a
negligible Au NPs leaching. The amount of Au NPs in the
DFNS/Au NPs was 0.8%, indicating leaching of Au NPs.
This remarkable ability of the DFNS/α-CD/Au structure can
be attributed to the α-CDs, which were able to efectively
reacted by preventing the accumulation of Au NPs and the
releasing and retrieval of Au NPs during the reaction pro-
cess (Table 4). Comparison of TEM images of the utilized
catalyst (Fig. 12a) with the fresh catalyst (Fig. 1f) shows
a decrease in the number of gold nanoparticles among the
fbers of DFNS/Au NPs after ten times recycling. However,
application of DFNS/α-CD/Au NPs did not change the num-
ber of gold nanoparticles (Fig. 12b). The structural stability
of DFNS/α-CD/Au NPs was due to the presence of α-CD in
the catalyst anatomy.
5 Conclusions
In this paper, a series of DFNS/α-CD/Au NPs catalysts
were provided using in situ gold NPs on the DFNS sur-
face. DFNS/α-CD/Au catalysts with proper mesoporous
structure along with the α-CD species were properly
incorporated into the DFNS framework. To form smaller
Au particles and enhance the surface area of the cata-
lysts, increasing the amount of α-CD doping rate was
Furthermore, a comprehensive study was conducted to
demonstrate the catalyst heterogeneous nature. First, the hot
fltration test for the synthesis of 3a,4-dihydronaphtho[2,3-c]
furan-1(3H)-one demonstrated that the catalyst is removed
after 15 min at a yield of 47%. The outcomes proved that,
1 3

DFNS/α-CD/Au as a Nanocatalyst for Interpolation of CO2 into Aryl Alkynes Followed by…
Table 2 Synthesis of 3a,4-dihydronaphtho[2,3-c]furan-1(3H)-one derivatives in the presence of DFNS/α-CD/Au NPsa
Entry
1
Alkynes
Products
Yield (%)b
96
O
O
2
3
4
97
Me
MeO
F
O
O
Me
OMe
F
98
O
O
92
O
O
5
91
NC
O
O
CN
aReaction states: The blend of allylic chlorides (1.0 mmol), alkynes (1.0 mmol), and DFNS/α-CD/Au NPs (20 mg), K2CO3 (1.0 mmol), CO2
(1.5 MPa) for 30 min at 90 °C
bIsolated yields
1 3

Z. Wang et al.
Table 3 Infuence of diferent catalysts for synthesis of 3a,4-
dihydronaphtho[2,3-c]furan-1(3H)-one
Entry
Catalyst
Yield (%)a
1
2
3
DFNS
DFNS/α-CD
DFNS/α-CD/Au
–
–
96
aIsolated yield
100
90
80
70
60
50
40
30
20
10
0
Fig. 11 Reaction kinetics, Hg (0) poisoning, and hot fltration studies
for synthesis of 3a,4-dihydronaphtho[2,3-c]furan-1(3H)-one
Table 4 The loading amount of Au NPs
Entry
Catalyst
wt%
1
2
3
4
DFNS/α-CD/Au
DFNS/Au
DFNS/α-CD/Au after ten reuses
DFNS/Au after ten reuses
1.9
2.0
1.7
0.8
1
2
3
4
5
6
7
8
9
10
Reuse
Fig. 9 Reusability of catalysts for the synthesis of 3a,4-
dihydronaphtho[2,3-c]furan-1(3H)-one. The DFNS/α-CD/Au NPs
were separated after a completed run of reaction, then cleaned and
used for recyclability tests
appropriate. The gold NPs acted as the active sites. Fur-
thermore, the synthesized DFNS/α-CD/Au NPs were
found to have excellent catalytic properties in the reduc-
tion synthesis of 3a,4-dihydronaphtho[2,3-c]furan-1(3H)-
one. Therefore, any other promising NPs with proper
properties, such as reusability and high efciency, can be
expanded in the future by pursuing the method proposed
in this study.
0.2
0.16
0.12
0.08
0.04
0
0
2
4
6
8
10
Run
Fig. 10 Recyclability of the catalyst for synthesis of 3a,4-
dihydronaphtho[2,3-c]furan-1(3H)-one
1 3

DFNS/α-CD/Au as a Nanocatalyst for Interpolation of CO2 into Aryl Alkynes Followed by…
Fig. 12 TEM images of the
recovered DFNS/α-CD/Au NPs
(a), and DFNS/Au (b) after the
10th run for oxidation of phenol
22. Yang X, Huang C, Fu ZY, Song HY, Liao SJ, Su YL, Du L, Li
Acknowledgements The authors are grateful for the fnancial support
provided by the National Natural Science Foundation of China (No.
51908211).
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