Preparation and characterization of supported bimetallic gold–iron nanoparticles, and its potential for heterogeneous catalysis

Article abstract of DOI:10.1007/s11164-019-04039-0

Bimetallic gold–iron catalysts supported on ZrO₂ and TiO₂ were prepared by under potential deposition. The characterization of the catalysts was performed using an inductively coupled plasma, energy-dispersive spectroscopy, diffuse r

Full text of DOI:10.1007/s11164-019-04039-0

Research on Chemical Intermediates
https://doi.org/10.1007/s11164-019-04039-0
Preparation and characterization of supported
bimetallic gold–iron nanoparticles, and its potential
for heterogeneous catalysis
Ghaniya Ferouani · Nawal Ameur1,2 · Redouane Bachir1
1
Received: 18 August 2019 / Accepted: 4 November 2019
©
Springer Nature B.V. 2019
Abstract
Bimetallic gold–iron catalysts supported on ZrO and TiO were prepared by under
2
2
potential deposition. The characterization of the catalysts was performed using an
inductively coupled plasma, energy-dispersive spectroscopy, diꢀuse reꢁectance
ultraviolet–visible spectroscopy (DR/UV–vis), and transmission electron micros-
copy. The catalytic properties of the prepared materials in synthesis of isoxazol-
5
-(4H)-ones in a one-pot three-component reaction of aromatic aldehydes, ethyl ace-
toacetate, and hydroxylamine hydrochloride were studied. The chemical structures
1
1
of the diꢀerent reaction products were conꢂrmed by H NMR, C NMR. The note-
worthy advantages of our simple method, which occurred in eꢃcient, simple, clean,
green, mild conditions, and easy workup, gave diꢀerent isoxazol-5-(4H)-ones with
good to high yields (66–78%). The reuse of the catalyst shows that this catalyst can
be used up to three cycles without any change in the yield of products.
Keywords Green nanocatalysis · Au–Fe/ZrO · Au–Fe/ZrO · One-pot synthesis ·
2
2
Catalyst reuse
Introduction
Heterocyclic compounds are of great importance to both gold nanoparticles having
proved an interesting activity in catalytic reactions; for this reason it has recently
become a very attractive subject for many scientists [1, 2]. The birth of the catalysis
Electronic supplementary material The online version of this article (https://doi.org/10.1007/s1116
4
-019-04039-0) contains supplementary material, which is available to authorized users.
*
Ghaniya Ferouani
g-ferouani@live.com
1
2
Laboratory of Catalysis and Synthesis in Organic Chemistry, University of Tlemcen, BP 119,
Tlemcen, Algeria
High School of Electrical and Energetic Engineering of Oran (ESGEE), Bir El Djir, Algeria
Vol.:(012
1
3456789)
3

G. Ferouani et al.
by gold began with a prediction of Geoꢀrey Bond and Graham Hutching [3] who
during the 1970s anticipated that if gold was subdivided into very small particles,
it would have very diꢀerent properties from those in its massive state. At the end of
the 1980s, Haruta and al. [4] discovered that gold catalysis is very active in the oxi-
dation reaction of carbon monoxide at low temperature (25–70 °C), a reaction which
no other metal was capable to have in such temperature. This marked the birth of the
catalysis by gold, which aroused an increasing interest of the scientiꢂc and industrial
community.
Nano-bimetallic catalysts, which are widely used in many important industrial
processes, are often better than their monometallic counterparts in terms of catalytic
activity and/or selectivity [5–7]. Bimetallic catalysts supported on metal oxides are
of great interest [8, 9] and especially those containing gold proved to be useful in
various catalytic applications, i.e., carbon monoxide oxidation [2, 10, 11], hydrogen
production [12], and biomass processes [13].
These last two decades have witnessed a great interest in green organic synthe-
sis methods for their ease of use and their respect for the environment and eco-
nomical manipulations [14–17]. Among these methods, one-pot multi-component
reactions (MCRs) with more than two reactants combined in a single-step process
have been extensively coveted [11, 12, 18–20]. They are simple workup procedures
which allow the synthesis of complex molecules without intermediates isolation.
Moreover, the use of heterogeneous catalysts in one-pot multi-component reaction
is becoming more and more interesting. Indeed, this has several advantages such
as catalyst separation, reusability, long catalytic life, and atom economy and eco-
friendly protocols [16, 21–27]. Recently, diꢀerent pertinent works using heterogene-
ous catalysts in organic synthesis are realized such as Cu/Al O , Ag/Bentonite, and
2
3
CuO/eggshell catalysts used in the reduction in nitro-compounds and organic dyes
[
28–30], Ag nanoparticles implicated as catalyst for the cyanation of aryl and heter-
oaryl aldehydes [31], Pd/coral reef in the synthesis of nitriles [32], Pd/MnO used in
2
the one-pot synthesis of tetrazole derivatives [33], and Cu/ZrO for the extraction of
2
7
-hydroxy-4-methoxy-isoꢁavon from Commelina [34] and others.
In this work and for the ꢂrst time, we report the synthesis of a novel heterogene-
ous bimetallic gold Au–Fe/ZrO and Au–Fe/TiO catalysts made by under poten-
2
2
tial deposition (UPD). Their potential suitability as catalysts for “green reactions”
is proved for the ꢂrst time, according to our belief, using bimetallic catalysts, cata-
lyzed one-pot multi-component reaction of isoxazol-5-(4H)-ones derivatives under a
solvent-free condition at room temperature.
The products we want to synthesize are important ꢂve-membered heterocycles char-
acterized by a nitrogen–oxygen bond, useful in various syntheses of other heterocycles
such as 1,3-oxazin-6-ones, pyrroles, imidazoles, tetrahydropyridines, pyridopyrimi-
dines, and 2H-azirines [35–38]. The isoxazol-5(4H)-ones derivatives exhibited a grow-
ing interest due to their attractive pharmacological properties [39]. They have been
broadly used as antibacterial [40], anticonvulsant, antifungal, antidiabetic, anticancer,
and hypoglycemic [38, 41–43] and are described as GABA-A receptors and potent
inhibitors of PTP1B [44]. The 3,4-disubstituted isoxazole-5(4H)-ones backbone is also
a structural component of a variety of natural products and drugs such as ibotenic acid
and isoxazole-4 carboxylic acid, [45] which are active agrochemical compounds used
1
3

Preparation and characterization of supported bimetallic…
Fig. 1 Interesting isoxazol-5-(4H)-one containing compounds
O
O
catalyst
N
O
ArCHO
Ar
NH OH.HCl
+
2
+
O
solvent free, RT,3h
O
Scheme 1 Synthesis of isoxazol-5(4H)-ones derivatives
as fungicides and insecticides [46], with a wide variety of applications in light-conver-
sion molecular devices, [47] nonlinear optical research, and optical storage and ꢂlter
dyes in photographic ꢂlms [48, 49] (see Fig. 1).
There are various methods for the synthesis of substituted isoxazole-5 (4H)-ones
[
40, 50–52]. For instance, a number of catalysts were used in a three-component con-
densation of β-oxoesters, hydroxylamine hydrochloride, and aromatic aldehydes,
including sodium acetate in aqueous ethanol under visible light [53], pyridine in H O
2
under ultrasonic irradiation [54], potassium hydrogen phthalate (KHP) in H O at 50 °C
2
[
55], and sodium sulꢂde in ethanol at room temperature [56]. Other methods also used
include DABCO in ethanol [57], 2-HSBA [58], boric acid [59], NBS [60], LiBr [40],
and sulfated polyborate under a solvent-free condition at 80 °C [46] and which were
also reported for the preparation of isoxazole-5(4H)-ones.
We have developed a new rapid and eꢃcient protocol with good and inexpensive
green gold nanocatalysis under mild reaction conditions (solvent-free condition at room
temperature) (Scheme 1).
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3

G. Ferouani et al.
Experimental
Catalyst preparation
Catalyst preparation was realized in two steps. The ꢂrst one concerns the mon-
ometallic 1%Au/ZrO and 1%Au/TiO catalysts prepared by deposition precipi-
2
2
tation by urea (DPU) [8]. Brieꢁy, a suspension of support (ZrO or TiO ) was
2
2
introduced into a three-necked ꢁask and heated to 80 °C. Then, a solution of gold
−
1
salt, HAuCl ·3H O (10 g L ), was mixed with urea (0.9 g). All were closed and
4
2
stirred for 16 h at the same temperature in the dark. At the end, the solid was sep-
arated by centrifugation and washed with distilled water many times. The result-
ing solids were dried at 80 °C overnight (dried catalyst). Finally, the as-prepared
−
1
catalysts were annealed under H gas at 300 °C during 4 h (2 °C min ).
2
The second step concerns the iron deposition on the monometallic catalyst by
under potential deposition (UPD) [9]. The parent Au/TiO or Au/ZrO catalysts
2
2
(
0.25 g) was introduced into a glass reactor where it is activated under hydrogen
ꢁ
ow at 150 °C (see Fig. 2). Then, a solution (50 mL) of formic acid (pH = 3.7,
3
+
−4
[
Fe ]=10 M), previously outgassed under nitrogen ꢁow in the degassing
bulb, was introduced onto the catalyst at room temperature under hydrogen ꢁow
−
1
(
200 mL min ). Finally, the solution of Fe(NO ) ·9H O dissolved in formic acid
3 3 2
and outgassed under nitrogen, was introduced onto the catalyst. After 15 min, the
solution was eliminated by ꢂltration and the catalyst was dried under nitrogen
ꢁ
ow at 120 °C and then reduced under hydrogen at 150 °C for 2 h 10.
Fig. 2 Montage using for
the preparation of bimetallic
catalysts
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3

Preparation and characterization of supported bimetallic…
Characterization techniques
The Au eꢀective contents, Fe and Cl in the catalysts, were determined by ICP
chemical analysis. TEM micrographs and EDS spectra were obtained from a
JOEL JEM-100CXII instrument operating at 120 kV with a resolution of 0.35 nm.
DR/UV–vis spectroscopy measurements were taken at room temperature with a
Lambda 800 UV–vis spectrometer in the range of 200–800 nm. This setup was
equipped with a diꢀuse reꢁectance accessory set to collect diꢀuse reꢁected light
only.
Test catalytic
A mixture of ethyl acetoacetate (10 mmol, 1.30 g), hydroxylamine hydrochloride
(
10 mmol, 0.69 g), aromatic aldehyde (10 mmol), and (0.04 g 4%) of catalyst was
stirred at room temperature. After the completion of the reaction as monitored by
TLC, the obtained solid was ꢂltered oꢀ and washed with diethyl ether.
Yield and turnover frequency (TOF) were calculated using the following
equations:
n
− nfinal
initial
Yield = 100 ×
n
initial
n
− nfinal
initial
TOF =
Time(h) × Weight of catalyst (g)
Results and discussion
Catalyst characterizations
Figure 3 shows the corresponding spectra of TiO , Au/TiO , and Au–Fe/TiO cata-
2
2
2
lysts. Titania shows the presence of the anatase phase (JCPDS Files No.: 21-1272).
The metallization of this support does not show any changes in the resulting spectra.
This may be related to the low amount of metals in these materials.
Zirconia-based catalysts show the same results; no peaks related to the metallic
species are present (see Fig. 4).
The ICP analysis results of mono- and bimetallic catalysts are shown in Table 1.
It is clear that 80–90% of gold in solution were deposited in the supports by deposi-
tion precipitation with urea (DPU). However, more than 50% of Fe were deposited
on monometallic catalysts using UPD method. Finally, a very low content in Cl in
all catalysts was observed. This may be related to the washing of the catalysts and
the UPD process.
DR/UV–vis spectrum of ZrO one (see Fig. 5) shows two maxima centered at 224
2
4
+
and 267 nm related to the electronic transition between Zr and oxygenated ligand
like O or H O [8, 61, 62] _ENREF_3. The metalized catalysts show an important
2
2
band around 540 nm, which is a characteristic resonance plasmon band (SPR) of
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3

G. Ferouani et al.
Fig. 3 XRD spectra of doped-TiO catalysts
2
Fig. 4 XRD spectra of doped-ZrO catalysts
2
reduced and spherical gold nanoparticles [8, 63–65]. We may attribute the band in
the region 379–392 nm to the gold cluster nanoparticles [66].
The TiO deconvolution shows the presence of three bands localized at 207, 269,
2
and 332 nm. The ꢂrst one might be associated with the ligand–metal charge transfer
4
+
between tetrahedrical Ti and oxygenated ligand such as O–H, O–Ti, or H O [67],
2
1
3

Preparation and characterization of supported bimetallic…
Table 1 ICP analyses
Catalysts
Au (wt%)
Fe (wt%)
Cl (%)
d (nm)
Au/ZrO2
Au–Fe/ZrO2
Au/TiO2
0.8
0.75
0.9
0.8
–
0.52
–
<0.02
<0.0002
<0.02
6
5.8
3.4
4.3
Au–Fe/TiO2
0.92
<0.002
Fig. 5 RD/UV–vis spectra of doped-ZrO catalysts
2
the second was related to the Ti4+ cations in octahedral environment [60, 61], and
the last one may be attributed to the anatase phase [8, 67–69]. The resonance plas-
mon band (SPR) of reduced and spherical gold nanoparticles appears at 549 nm for
mono- and bimetallic catalysts. This means that the iron deposition does not aꢀect
the gold nanoparticles (see Fig. 6).
Finally, we noticed that the iron species did not show any absorption band which
is related to the low amount of this metal (see Table 1).
TEM images of doped-TiO catalysts show that gold particles are well distrib-
2
uted on the titania surface (Fig. 7). The deposition of iron does not have important
changes in the distribution or the size of the nanoparticles (increase about 1 nm).
The analysis of one particle on the surface by EDS shows the presence of peaks
related to Au and Fe at the same time conꢂrming the bimetallic character of this
catalyst.
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G. Ferouani et al.
Fig. 6 RD/UV–vis spectra of doped-TiO catalysts
2
Figure 8 shows TEM characterization of Au–Fe/ZrO . It reveals nano-sized
2
bimetallic Au–Fe particles whose sizes range from 1 to 17 nm with a mean size
of 5.7 nm. Moreover, EDS analyses (see Fig. 8) conꢂrm the ICP results and prove
the bimetallic character of Au–Fe nanoparticles. In this case, it is clear that Fe
deposition (or the acid treatment during Fe deposition) does not aꢀect the size of
the metallic species but leads to homogenize the size distribution in comparison
with the monometallic catalyst.
By way of conclusion, the preparation of bimetallic catalysts by UPD leads
to have a good size distribution of the metallic particles with a bimetallic char-
acter. Hence, it is important to evoke the signiꢂcant role of the support nature.
In our previous work, we used the same method to prepare Au–Fe/Al O catalyst
2
3
[
9]. We observed an important agglomeration of the particles with an average
size around 37 nm in comparison with the monometallic one with a size around
nm. We related this phenomenon to the nature of the support. Alumina is a
6
non-reducible support where the interactions metal-support are weak and the acid
treatment induces the facile agglomeration of the particles [9]. In contrast, titania
and zirconia are reducible support where the interaction metal-support are strong
and the particles show an agglomeration resistance after acid treatment. Finally,
the RD/UV–vis results show that the deposition of iron particles does not change
the oxidation state of the gold nanoparticles.
1
3

Preparation and characterization of supported bimetallic…
800
Au/TiO
2
600
d=3.4 nm
4
00
00
0
2
1
3
5
7
9
11 13 15 17 19 21
di (nm)
600
400
200
0
Au-Fe/TiO
2
d=4.3 nm
1
2 3 4 5 6 7 8 9 101112131415161718192021
di (nm)
Au-Fe/TiO
2
Fig. 7 TEM images, size distributions, and EDS analysis of doped-TiO catalysts
2
Catalytic experiments
The prepared materials were tested for their catalytic activity performance in the
synthesis of isoxazol-5-(4H)-ones via a three-component coupling reaction of aro-
matic aldehydes, ethyl acetoacetate, and hydroxylamine hydrochloride at room tem-
perature. We found that the use of Au–Fe/TiO and Au–Fe/ZrO as catalysts leads to
2
2
a yield of 70 and 78% (see Scheme 2), respectively. So, we selected Au–Fe/ZrO as
2
the best catalyst to complete the coupling study.
Table 2 shows that the results obtained, the reaction time, and the yield are
parameters which strongly depend on the nature of the substituted group on the aro-
matic aldehyde, and all products were prepared under mild conditions for a rela-
tively short reaction time with high yields. However, we noted that we did not only
obtain the products by simple ꢂltration without any puriꢂcation with a good yield,
but we also developed a simpler process, considered as the best for cost and environ-
mental acceptability.
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G. Ferouani et al.
300
200
100
0
Au/TiO
2
d=6 nm
1
2 3 4 5 6 7 8 9 101112131415161718192021
di(nm)
8
6
4
2
00
00
00
Au-Fe/ZrO
Au-Fe/ZrO
2
d= 5.7 nm
00
0
1
3
5
7
9
11 13 15 17 19 21
di (nm)
2
Fig. 8 TEM images, size distribution, and EDS analysis of doped-ZrO catalysts
2
Scheme 2 Inꢁuence of the catalyst in the synthesis of Isoxazol-5(4H)-ones derivatives
Mechanism
A tentative mechanism of this reaction is represented in Scheme 3. Oxime inter-
mediate C was formed by a 1,2-addition of ethyl acetoacetate and hydroxyl amine
in aqueous medium at room temperature, catalyzed by Au–Fe/ZrO . This catalyst
2
increases the carbonyl electrophilicity. During the subsequent Knoevenagel conden-
sation, the catalyst promotes the reaction between the activated methylene and the
1
3

Preparation and characterization of supported bimetallic…
Table 2 Synthesis of isoxazol-5(4H)-one derivatives 4a–e uses various aldehydes
Entry
Aldehyde
Product
Yield
TOF
(mol.h .g )
a
-1 -1
(
%)
CHO
N
O
O
1
2
78%
66%
0.0936
4
a
N
CHO
O
0.0792
O
NC
CN
4
b
OH
CHO
N
3
4
O
76%
75%
0.0912
0.0900
O
OH
4
c
F
F
N
O
CHO
O
4
d
N
O
O
5
69%
0.0828
O
4
e
aIsolated yields
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3

G. Ferouani et al.
Scheme 3 Suggested mechanism for synthesis of isoxazol-5-(4H)-one derivative
aldehyde. As a result, the alkene intermediate D may form. The ꢂnal step, an intra-
molecular O-attack followed by cyclization of the Knoevenagel adduct gives the title
compound.
Catalyst stability
The reusability of the catalyst is important for large-scale operations and industrial
point of view. Thus, the Au–Fe/ZrO recovery and reusability were examined. The
2
catalyst was recovered by a simple ꢂltration, washed with acetone several times, and
then dried before use for the next cycle. The reusability of the catalyst was investi-
gated in one-pot reaction of 4-methylbenzaldhyde, ethyl acetoacetate, and hydrox-
ylamine hydrochloride under a solvent-free condition at room temperature. The
results reported in Table 3 show that the catalyst can be recovered and reused several
times without loss of activity.
Spectroscopic data of some synthesized
(Z)-4-(4-methylbenzylidene)-3-methylisoxazol-5(4H)-one (4a), yield: 78%, mp
132–133 °C; 1H NMR (400 MHz, CDCl3): δppm 8.21–8.19 (2H, d, J=8.00 Hz,
Table 3 Results of the reaction
run in the presence of recycled
catalyst
Fields (%)a
TOF (mol h−1 g−1
Run
)
1
2
3
78
77
77
0.0936
0.00924
0.00924
aIsolated yields
1
3

Preparation and characterization of supported bimetallic…
H
); 7.3245 (1H, s, CH); 7.25–7.23(2H, d, J=8.00 Hz, H
); 2.37 (3H, s,
aromatic
aromatic
3
1
3
CH ); 2.21 (3H, s, CH ) ppm. C NMR (400 MHz, CDCl ): δ
168.22; 161.23;
3
3
ppm
−
1
1
49.98; 145.73; 134.15; 129.95; 129.89; 118.41; 22.06; 11.63 ppm. IR (neat/cm ):
1
730.40; 1698.34; 1169.28.
(
Z)-4-((3-methyl-5-oxoisoxazol-4(5H)-ylidene) methyl) benzonitrile (4b), Yield:
1
6
6%; mp193–194 °C, H NMR (400 MHz, DMSO-d ):): δ
8.46–8.44 (2H, d,
ppm
6
J=8.00 Hz, H
); 8.06–8.04 (3H, t, CH+H
); 2.31 (3H, s, CH ) ppm,
aromatic
aromatic 3
1
3
C NMR (400 MHz, DMSO-d ):): δ
167.73; 162.53; 149.29; 136.56; 133.68;
ppm
6
−
1
1
32.92, 130.34, 122.35, 118.74, 115.09, 11.74 ppm. IR (neat/cm ): 1720.70;
1
675.30; 1055.50; 2265.25.
(
Z)-4-(2-hydroxybenzylidene)-3-methylisoxazol-5(4H)-one (4c), yield: 76%,
1
mp 203–204 °C; H NMR (400 MHz, DMSO-d ): δ
11.00 (1H, s, OH);
6
ppm
8
.75–8.73(1H, d, J=8.00 Hz, H
); 8.09 (1H, s, CH), 7.47–7.51 (1H, t,
aromatic
H
), 7.03–7.00 (1H, d, J=12 Hz, H
), 6.95–6.91 (1H, t, H
), 2.26
aromatic
aromatic
aromatic
1
3
(
3H, s, CH ) ppm, C NMR (400 MHz, DMSO-d ): δ
168.73, 162.59, 160.11,
3
6
ppm
−
1
1
45.45, 137.19, 132.78, 119.95, 119.56, 116.90, 116.60, 11.65 ppm. IR (neat/cm ):
1
770.02; 1670.25; 1080.25.
(
Z)-4-(2-fuorobenzylidene)-3-methylisoxazol-5(4H)-one (4d), Yield: 75%; mp
1
1
59–160 °C; H NMR (400 MHz, CDCl ): δ
8.22–8.19 (1H, d, J=8.00 Hz,
ppm
3
H
); 7.92–7.90 (1H, d, J=12 Hz, H
); 7.45–7.39 (1H, m, H
);
aromatic
aromatic
aromatic
1
3
7
.32 (1H, s, CH); 7.24–7.19 (1H, m, H
); 2.24 (3H, s, CH ) ppm. C NMR
aromatic 3
(
400 MHz, CDCl ): δ
167.50; 163.76; 161.30; 160.91; 148.11 (d, J=12 Hz);
3
ppm
1
34.00 (d, J=32 Hz); 130.54 (d, J=32); 129.87 (d, J=12 Hz); 121.02 (d,
−
1
J=84 Hz); 119.72 (d, J=92 Hz); 11.59 ppm. IR (neat/cm ): 1731.15; 1640.98.
(
Z)-3-methyl-4-((E)-3-phenylallylidene)isoxazol-5(4H)-one (4e), Yield: 69%;
1
mp 172–173 °C; H NMR (400 MHz, CDCl ): δ
8.35–8.28 (dd, J=12 Hz, 1H,
3
ppm
CH), 7.66–7.64 (2H, m, CH=CH), 7.44–7.43 (3H, m, H
),; 7.32–8.26 (2H, m,
aromatic
1
3
H
); 2.25 (s, 3H, CH )ppm C NMR (400 MHz, CDCl ): δ 168.94; 159.78;
aromatic
3 3 ppm
1
51.31; 147.45; 135.00; 131.53; 129.18; 128.93; 122.47; 117.99; 11.15 ppm. IR
−1
(
neat/cm ): 1735.00; 1670.21.
Conclusion
We described the synthesis of a bimetallic gold Au–Fe/TiO and Au–Fe/ZrO cata-
2
2
lysts produced by under potential deposition, which has been used as an eꢃcient
catalyst for the preparation of heterocyclic compounds (3-methyl-4-arylmethylene-
isoxazol-5(4H)-ones) in high yields involving one-pot operations and short reaction
times. The new heterogeneous catalyst is simple, highly eꢃcient, and recyclable in
this protocol. This environmentally friendly process has many advantages, namely
solvent-free condition, small quantities of waste, ease of product isolation, eꢃ-
ciency, low cost, and mild and green conditions.
Acknowledgements The authors would like to thank the Algerian DGRST-MESRS, and the University
of Tlemcen for funding this work.
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G. Ferouani et al.
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