Materials Science & Engineering C 103 (2019) 109814

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Materials Science & Engineering C

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

Needle ball-like nanostructured mixed Cu-Ni-Co oxides: Synthesis, T

characterization and application to the selective oxidation of sulfides to
sulfoxides
Fereshteh Hosseini-Eshbalaa,b, Alireza Sedrpoushana, , Mohammad Nabi Dehdashtia,
⁎

Bernhard Breitb, Farajollah Mohanazadeha, Hojat Veisic

a
Department of Industrial Chemistry, Iranian research Organization for Science and Technology, Tehran, Iran
b
Institute of Organic Chemistry, Albert-Ludwigs-Universität Freiburg, Freiburg i. Bg., Germany
c
Department of Chemistry, Payame Noor University, Tehran, Iran

ARTICLE INFO ABSTRACT

Keywords: A mixed nano-metal oxides of Cu-Ni-Co has been synthesized. Several characterization techniques (EDS, XRD,
Sulfide TEM, and SEM) have been used to provide insight into the nature and structure of the catalyst. The size of this
Mixed nano metal oxides mixed metal oxide is 22 nm. The SEM images indicate that the sample with spherical particles, of which spherical
Heterogeneous catalysis assembly is comprised of elongated rod/needle-like subunits pointing radially outward, creates a needle ball-like
Sulfoxide
structure. To efficiently catalyze the selective oxidation of sulfide towards sulfoxide, this heterogeneous catalyst
uses an oxidizing agent (hydrogen peroxide- H2O2) and a solvent (acetonitrile) in mild conditions. The influence
of reaction temperature and sulfide/oxidant molar ratio was evaluated with respect to sulfide conversion and
chemoselectivity towards the sulfoxide product. Under optimized conditions, product yields in the range from 70
to 97% were obtained.

1. Introduction
Because of the growing demand for environment-friendly technol-
ogies in chemical reactions in industry, catalytic processes (e.g. toxic
and expensive reagents removal, minimization of by-products, and
simplifying of workup procedures) have drawn a great deal of attention
recently [1]. Among the long-standing challenges of organic chemistry,
the selective oxidation of sulfides to sulfoxides is notable [2,3]. In this
regard, many scientists aimed to develop a new method for chemose-
lective mono-oxidation of sulfides.
Since the early reports of synthesizing sulfoxides by Maercker in
1865, notable progress has been made in this field [4], such as using
different oxidants, (e.g. concentrated nitric acid [5], high-valence metal
salts, m-chloroperoxybenzoic acid, halogens, nitrogen pentoxide, and
sodium metaperiodate [6–11]).
Disadvantages of these methods are the use of toxic and corrosive
reagents [12] or the necessity of complex reaction procedures [13]
along with overoxidation of sulfoxides to the corresponding sulfones or
similar undesired side products [14,15]. To overcome these limitations,
several studies have been carried out to develop novel and efficient
catalytic systems by using aqueous 30% H2O2 as the final green oxidant.
The advantages of the oxidant hydrogen peroxide are low cost, en-
vironment-friendly specifications, effective–oxygen content, and
yielding water as the only major byproduct [16].
Using a homogeneous catalyst leads to the problem of separation of
the expensive catalyst from the product, which makes a separation
procedure for the recovery unavoidable [17]. Therefore, it is necessary
to find catalytic systems for activation of hydrogen peroxide throughout
such transformation, it should be easy to recover and reuse after the
reaction [18]. Although significant advances have been achieved in this
field, an unsolved challenge remains the development of a hetero-
geneous catalyst that allows for a high yielding chemoselective mono-
oxidation of sulfides to sulfoxides.
One of the highly diverse classes of materials and widely used
groups of solid catalysts, featured with critical structure-related prop-
erties is metal oxides. Many of them can demonstrate super-
conductivity, magnetism, colossal magnetoresistivity, ferroelectricity,
conductivity, and/or gas-sensing capabilities. The acid-base and redox
properties make them a good choice. They are also part of a larger
group of catalysts in heterogeneous catalysis [19]. Transition and noble
group metals are typically employed as catalysts and their activity is
rooted in their outer electron configuration [20]. Some of the metal

⁎
Corresponding author.
E-mail address: Alirezasedrpoushan@gmail.com (A. Sedrpoushan).

https://doi.org/10.1016/j.msec.2019.109814
Received 4 February 2019; Received in revised form 26 May 2019; Accepted 27 May 2019
Available online 30 May 2019
0928-4931/ © 2019 Elsevier B.V. All rights reserved.
F. Hosseini-Eshbala, et al.
Fig. 1. X-ray diffraction (XRD) pattern of the Cu-Ni-Co nanocatalyst.
oxide catalysts, including transition metals, are highly important given
their advantages like inexpensive production, ease of regeneration and
selective reactivity. The catalytic properties can be explained by the
availability of partially filled d-shells of the metal ion and the effect of
the oxide ligand field on the partially filled d-shell.
Mixed metal oxides have been described as efficient heterogeneous
catalysts for several oxidation processes [21]. Mixed metal oxides can
be regarded as oxygen-containing combinations with several metallic
ions or as supports in proportions that can be changed or determined
using strict stoichiometry [22]. Mixed metal oxides are usually pro-
duced as powders or single crystals. They act as a key role in different
fields of physics, materials science, chemistry, and geochemistry. In-
dustrial applications include the use are piezoelectric devices, sensors,
and catalysts [23–28]. For long, many have tried to comprehend the
way mixed-metal oxides behave at a fundamental level. Basically,
adding metals in an oxide matrix leads to compounds with new novel
structural and/or electronic properties. The metal↔metal or metal↔
oxygen↔metal interactions in mixed-metal oxides can yield electronic
properties that are not found single-metal oxides. It is noticeable that
some of the mixed metal oxides are better with respect to catalytic
activity comparing with metal oxides in different reactions. The higher
active acidic or basic sites, and higher surface areas, which increases
the reaction rate and the reaction yield that may influence chemos-
electivity explain this phenomenon.
Evidently, ternary metal oxide nanostructures have profound sci-
entific features (as optical, electronic, and catalytic properties) and
contain a wide range of technological applications (e.g. transistors and
computational devices). Hence, we speculated whether a nano-size
well-dispersed mixed metal oxide catalyst with increased surface area
and physical-chemical interactions could be an ideal solution for the
monooxidation of sulfides to sulfoxides. Inspired by previous work from
Valand on oxidation of styrene and dichlorophenol (DCP) [29] we re-
ported here a novel class of inexpensive mixed nano-metal oxides of Cu-
Ni-Co without an additional support as a highly active and selective
heterogeneous catalyst for our studies employing hydrogen peroxide as
a sustainable co-oxidant.
2
Materials Science & Engineering C 103 (2019) 109814
2. Experimental section
2.1. Catalyst preparation
Appropriate amounts of the metal precursors, Cu(NO3)2·3H2O
(1 mmol, 0.25 g), Ni(NO3)2·6H2O (1 mmol, 0.331 g), Co(NO3)2·6H2O
(1 mmol, 0.332 g) and NH4F (6 mmol, 0.253 g), urea (15 mmol) were
dissolved at room temperature in distilled water (70 mL) under con-
tinuous stirring for 30 min. Subsequently, the solution was transferred
into the autoclave and heated to 120 °C for 6 h. After cooling the au-
toclave to room temperature the resulting precipitate was washed with
water and ethanol and dried for 12 h. The resulting material was then
calcinated at 350 °C to give the ternary metallic nanocatalyst.
2.2. Instrumentals section
The composition of the catalyst was determined using energy dis-
persive spectrometer (EDS). The catalyst was examined using a Zeiss
‘Ultra plus’ SEM (scanning electron microscope). Powder XRD pattern
was carried out on an EQUINOX 3000 Advance instrument.
2.3. Catalyst testing
The oxidation of sulfide was done at 40 °C using catalyst (25 mg),
30% H2O2 (0.23 mL, 7.5 mmol) and sulfide (5 mmol) in acetonitrile
(10 mL) for 25 h in a 25 mL flask fitted with a reflux condenser in an oil
bath capable of stirring. The progress of the reaction was monitored by
thin-layer chromatography (TLC (EtOAc/n-hexane)). When the reaction
was completed, through decanting, the catalyst was separated and
cleaned using acetone before being dried in vacuum. The obtained
catalyst was utilized for several times in the same condition (like the
first run). All products of the reaction were determined and char-
acterized by a comparison of the physical data and the data collected
from authentic samples.
F. Hosseini-Eshbala, et al. Materials Science & Engineering C 103 (2019) 109814

Fig. 2. (a) Low-magnification and (b,c) high-magnification SEM images of the Cu-Ni-Co nanocatalyst.

2.4. The NMR spectra data for some selected compounds

Entry 1 (methyl phenyl sulfoxide). 1H NMR (CDCl3): 2.7 (s, 3H,

–CH3), 7.5 (m, 3H, aromatic), 7.6 (m, 2H, aromatic).
Entry 4 (diphenyl sulfoxide). 1H NMR (CDCl3): 7.53 (m, 10H).
Entry 5 (1-(propylsulfinyl)propane). 1H NMR (CDCl3): 1.09 (t,
6H), 1.88 (m, 4H), 2.9 (m, 4H).
Entry 7 (2-(phenylsulfinyl)ethanol). 1H NMR (CDCl3):, 2.62 (s,
1H), 2.99 (t, 2H), 3.63 (t, 2H), 7.2 (m, 5H).
Entry 9 ((propylsulfinyl)benzene). 1H NMR (CDCl3): 0.94 (t, 3H);
1.59 (m, 2H); 2.81 (dd, 2H); 7.22 (m, 5H).
Entry 10 (methyl 2-(phenylsulfinyl)acetate). 1H NMR (CDCl3):
4.1 (s, 3H, CH methyl); 4.2 (s, 2H); 7.9 (m, 5H).
Entry 11 (allyl phenyl sulfoxide). 1H NMR (CDCl3): 5.25 (m, 2H),
6.45 (dd, 1H), 7.25 (m, 5H).
Entry 12 (2-(phenylsulfinyl)acetonitrile). 1H NMR (CDCl3): 3.45
(s, 2H), 7.35 (m, 5H).
Fig. 3. EDS of Cu-Ni-Co nanocatalyst.

3
F. Hosseini-Eshbala, et al. Materials Science & Engineering C 103 (2019) 109814

Table 1
EDS quantitative results.
Elt Line Int K Kr W% A% ZAF Formula Ox% Pk/Bg

O Ka 286.5 0.2089 0.1756 28.92 60.64 0.6072 0.00 79.95

Co Ka 151.5 0.2372 0.1994 20.16 11.47 0.9893 0.00 17.70
Ni Ka 132.2 0.2615 0.2198 23.11 13.20 0.9513 0.00 17.42
Cu Ka 113.8 0.2924 0.2458 27.81 14.68 0.8839 0.00 16.95
1.0000 0.8407 100.00 100.00 0.00

Fig. 4. TEM images of the Cu-Ni-Co nanocatalyst.

Table 3
O Effect of reaction temperature during the oxidation of sulfide over the CuNiCo
S o catalyst.
R1 R2 1.5 eq. H2O2 (30%aq.)/ 40 C R1
S
R2 Entry Temperature (°C) Yield (%)
Cu-Ni-Co
1 r.t 34
Scheme 1. Catalytic oxidation of sulfides to sulfoxides 2 40 97
3 55 97

Reaction conditions: Methyl phenyl sulfide = 1 mmol, H2O2 = 1.5 mmol, cat-
Table 2 alyst = 5 mg, solvent = CH3CN (2 mL), time = 25 h.
Solvent optimization on the oxidation of methyl phenyl sulfide.
3. Results and discussion

Based on further exploration of catalytic methodologies for a few

critical transformations in organic synthesis [30,16b], the application
of Cu-Ni-Co oxide catalyst as a heterogeneous catalyst in sulfides oxi-
dation are discussed in the following section.

3.1. Characterization

The mineralogical classification based on the crystal symmetry gives

Yields indicates the isolated yield of the sulfoxide.
Reaction conditions: 5 mg Cat., 1 mmol methyl phenyl sulfide, 1.5 mmol 30%
H2O2, 2 mL solvent at 40 °C.
us the bases for determining the structures of these compounds by XRD
analysis. The powder X-ray diffraction of the prepared ternary oxide
displayed overlapping of diffraction peaks (Fig. 1). The powder XRD
patterns (Fig. 1) of the prepared ternary Cu-Ni-Co oxides show the
different metal oxides phases of CuO (JCPDS card no. 5-066), NiO
(JCPDS 4-00835), and Co3O4 (JCPDS 42-1467) [29].
The morphology and size of the ternary Cu-Ni-Co oxide catalyst
were investigated by SEM images with higher magnification (Fig. 2)
and the dispersion in the image was also supported by EDS mapping
(Fig. 3 and Table 1). EDS microanalysis results were obtained in the
expected range (Fig. 3). The size of this mixed metal oxide is 22 nm.

4
F. Hosseini-Eshbala, et al. Materials Science & Engineering C 103 (2019) 109814

Table 4
Oxidation of different sulfides to sulfoxides using Cu-Ni-Co.

Yield Time Mp/Bp (oC)

Entry Sulfide Product
(%) (h) Found LitRef

1 97 25 34-36 33-3430a

2 97 25 188-190 18930a

3 96 27 123-124 122–
12430a

4 90 25 70-71 70.530a

5 95 25 74-75 7530a

6 93 25 34-36 34-3630a

7 89 25 40-43 42-4330l

8 75 27 111-114 112-11430a

9 91 27 97-99 102-10330a

10 95 25 46-47 47-4930a

11 80 28 100-102 107-1103

12 90 27 64-66 64-6630m

13 83 27 101-103 102-10330a

14 84 25 120-121 119-1204b

15 80 27 110-112 109-1114b

1
16 70 29 201-204 202–2044b

17 85 27 133-134 132–1344b

18 88 28 34-37 34–354b

19 80 27 41-42 39-414b

Reaction conditions: sulfide (1 mmol), 1.5 mmol 30% H2O2, 2 mL acetonitrile, Cu-Ni-Co (5 mg).

Based on the FESEM1 image (Fig. 2) it is clear that the sample contains
spherical particles with a diameter in the μm range. The single particle
pictured in Fig. 1 is indicative of the fact that this spherical assembly is
formed of elongated rod/needle-like subunits pointing radially out-
ward, forming a needle ball-like structure. The elongated rod/needle-
like subunits were also confirmed with the transmission electron mi-
croscopy (TEM) images presented in Fig. 4. Based on TEM images, a
1
Low-magnification field-emission scanning electron microscopy.
bundle of the subunits is the elements of a larger spherical assembly.
3.2. Catalyst evaluation
3.2.1. Optimization
After the initial characterization of the prepared catalyst, to mea-
sure the catalytic activity, oxidation of sulfides to the corresponding
sulfoxides or sulfones with aqueous 30% H2O2 as terminal green and
effective oxidant was employed (Scheme 1). The effects of solvent, the
volume of catalyst, reaction temperature, reaction time, and the

5
F. Hosseini-Eshbala, et al.
Fig. 5. The recycling of the heterogeneous catalyst (Cu-Ni-Co) for selective
oxidation of methyl phenyl sulfide to methyl phenyl sulfoxide with 30% H2O2.
sulfide/oxidant molar ratio on oxidation of sulfide were optimized
using Cu-Ni-Co as the catalyst. We have investigated the role of the
catalyst volume in the oxidation reaction by using 5, 10, 15 mg of Cu-
Ni-Co while the rest of the parameters remained unchanged. The yield
and selectivity were not influenced by the volume increase of catalyst.
Therefore, all further studies were conducted with 5 mg of catalyst. The
reaction was performed by dichloromethane, acetonitrile-H2O, and
acetonitrile, which are used commonly in these type of reactions. Em-
ploying mixtures of dichloromethane-CH3OH and EtOH-H2O as solvent
led to outcomes (60–70%) (Table 2, entries 9 and 12). Afterwards, the
reaction was examined in the absence of solvent, which resulted in a
yield of 50% (entry 1). The highest performance of the catalyst was
achieved in acetonitrile as a solvent, as it completely dissolved the
sulfide substrate and therefore, facilitated the oxidation providing the
desired sulfoxide with 97% yield (Table 2, entry 5).
Furthermore, the role of sulfide/oxidant molar ratio was studied for
the oxidation of sulfide to achieve maximum conversion and selectivity
towards sulfoxide. After 25 h at 40 °C, the 1.0:0.5, 1.0:1.0, and
1.0:1.5 M ratios gave 46%, 60%, and 97% sulfide conversion, respec-
tively; however, there was no effect on the chemoselectivity towards
the desired sulfoxide. A molar ratio of 1.0:1.5 sulfide/H2O2 was thus
selected for deeper examinations.
Next, the effect of the reaction temperature was investigated. Thus
performing the reaction at either 25, 40 and 55 °C for 25 h, the yields
obtained were 34%, 97%, and 97%, respectively. As a result, the tem-
perature of the reaction was set at 40 °C for the general protocol.
With optimized reaction conditions (Table 3), the scope and gen-
erality of the developed protocol was examined.
3.2.2. The effect of ternary catalyst for sulfide oxidation
The utility of the new category of ternary metal oxide catalysts for
sulfide oxidation was studied by preparing the optimized conditions for
the reaction. The conversion in the presence of the catalysts was clearly
a function of the nature of the mixed-metal oxide.
Along with smaller particle sizes, high metal dispersion can result in
the better activity of the catalysts.
Generally, oxides of nickel (Ni) and Cu demonstrate higher Brønsted
acidity comparing with Co oxide [31]. Because of the high Lewis basic
Table 5
Comparison of the present methodology with literature for the synthesis of methyl phenyl sulfoxide.
Entry Reaction conditions
1 Molybdatophosphoric acid, CH3OH, rt
2 MCM-41@serine@Cu, solvent free, rt
3 VO(CS)@Fe3O4, solvent-free, r.t
4 Fe3O4@SiO2-FeQ3, H2O, 25 °C
5 Silica bromide, CH3CN, rt
6 VO(PDA)@Fe3O4, solvent-free, rt
7 VO-2A3HP-MCM-41, solvent free, rt
8 Cu-Ni-Co, CH3CN, rt
6
Materials Science & Engineering C 103 (2019) 109814
nature of cobalt, the ternary catalyst consists of equal allocation of
Lewis basic and Brønsted acidic sites. The oxidant, H2O2, is adsorbed on
the surface of the catalyst, because of its Brønsted acidic nature.
Under this catalysis condition, the main oxidation product yielded
was sulfoxide. With the optimized conditions, different types of sulfides
were oxidized with good yields, to sulfoxides (Table 4). It is important
to understand that the chemoselectively oxidation of the sulfides oc-
curred in the presence of functional groups resistant to oxidation, in-
cluding OH, CN, C]C, and COOMe (Table 4, entries 7, 10–13). Even
with more challenging sulfides that comprised sensitive functional
group (e.g. olefin and hydroxyl functionalities which can be oxidized
too), the corresponding sulfoxides were achieved with outstanding
yields and selectivities. With regard to allylic sulfide, no epoxidation of
the double bond or over-oxidation of sulfoxide to sulfone were wit-
nessed (see Table 4, entries 15 and 19). It is notable that with ne-
cessarily similar reaction conditions, highly selective sulfoxidation of
sulfides bearing an oxidizable primary alcohol unit is achievable while
no measurable volume of the respective carbonyl compound is observed
(see Table 4, entries 7 and 13). For substrates with lower reactivity (e.g.
diaryl sulfides), the yield of corresponding sulfoxides was notable (see
Table 4, entry 16). Moreover, aliphatic sulfides can be transformed into
the corresponding sulfoxides with outstanding yield.
A key expectation for the heterogeneous catalyst is that it is re-
cyclable and stable after the reaction so that it is possible to be sepa-
rated from the reaction medium through easy filtration and separation
for repeated uses. Accordingly, the reusability of Cu-Ni-Co catalyst in
this sulfide to sulfoxide oxidation reaction was examined. The catalyst
Cu-Ni-Co nano-metal oxide was reused four times for the oxidation of
methyl phenyl sulfide without a significant loss of activity (Fig. 5).
Following each reaction, the catalyst was isolated by decanting, cleaned
with fresh ethanol and acetone and then dried at 120 °C for 3 h before
reusing for the next reaction. We have also performed a hot filtration
test to check the leaching of the catalyst. To carry out a hot filtration
test, the reaction for the synthesis of methyl phenyl sulfoxide was ex-
amined using the optimized reaction conditions. The reaction media
was decanted after 10 h and subsequently, no further reaction progress
was observed. The ICP analysis revealed that the catalyst's Cu-Ni-Co
content after catalysis has not significant changed, showing that during
the catalytic processions, no considerable metal leaching to the solution
happens.
Furthermore, the catalytic performance of the present protocol was
compared with some recent literature-reported procedures. For this
purpose, selective oxidation of methyl phenyl sulfide to the related
sulfoxide in the presence of 30% H2O2 was selected (Table 5).
4. Conclusion
A new heterogeneous mixed Cu-Ni-Co nano-metal oxide catalyst
was synthesized from commercially available raw materials, char-
acterized by various techniques and proven highly successful for the
selective mono-oxidation of sulfides to the corresponding sulfoxides
employing H2O2 as an environment-friendly oxidant under mild reac-
tion conditions. The ternary catalyst has interesting catalytic properties
Time (min) Yield (%) Refs.
13 100 [32]
35 96 [33]
5 90 [34]
60 92 [35]
7 94 [3]
70 96 [36]
120 96 [37]
25 h 97 This work
F. Hosseini-Eshbala, et al.
in the oxidation even at low temperature. The major product of the
sulfide oxidation reaction was the corresponding sulfoxide. The con-
version and chemoselectivity towards the sulfoxide were high. Our
studies showed that different aliphatic or aromatic sulfides that form
readily oxidizable groups (e.g. hydroxyl and allylic functional groups)
are selectively converted into the corresponding sulfoxide with out-
standing yields. The superiority of this inexpensive catalyst is likely
because of a synergistic interaction between the metals with high dis-
persion.
Acknowledgements
This project was supported by the Iranian Research Organization for
Science and Technology (IROST).
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