Co/Cu bimetallic ZIF as New heterogeneous catalyst for reduction of nitroarenes and dyes

Article abstract of DOI:10.1002/aoc.5522

Nowadays one of the great challenges is to design new bimetallic catalysts with enhanced catalytic activity, selectivity and recycling properties. In this work, the preparation of new Co/Cu bimetallic Zeolitic Imidazolate Framework (Co-Cu/ZIF) as an efficient catalyst for the reduction of nitro compounds and organic dyes is described. Co-Cu/ZIF was characterized with different techniques such as SEM, TEM, XRD, XPS, TGA, FT-IR and UV–vis absorption indicating formation of entirely uniform cubic particles. Using this catalyst, structurally different aromatic nitro compounds were reduced efficiently to corresponding amines in excellent yields. Kinetic studies revealed that the reduction rates of nitrophenol isomers follow 3-NP > 4-NP > 2-NP order. The catalytic activity of Co-Cu/ZIF was further investigated in the reduction of organic dyes such as methyl orange (MO) and rhodamine B (RhB). This catalyst was recycled for at least ten runs in the reduction of 4-nitrophenol without a noticeable decrease in activity and reused catalyst was characterized.

Full text of DOI:10.1002/aoc.5522

Received: 2 September 2019
DOI: 10.1002/aoc.5522
Revised: 30 November 2019
Accepted: 4 December 2019
F U L L P A P E R
Co/Cu bimetallic ZIF as New heterogeneous catalyst for
reduction of nitroarenes and dyes
1,2
1
3
Mohammad Gholinejad
| Zhwan Naghshbandi | José M. Sansano
1
Department of Chemistry, Institute for
Advanced Studies in Basic Sciences
Nowadays one of the great challenges is to design new bimetallic catalysts with
enhanced catalytic activity, selectivity and recycling properties. In this work,
the preparation of new Co/Cu bimetallic Zeolitic Imidazolate Framework (Co-
Cu/ZIF) as an efficient catalyst for the reduction of nitro compounds and
organic dyes is described. Co-Cu/ZIF was characterized with different tech-
niques such as SEM, TEM, XRD, XPS, TGA, FT-IR and UV–vis absorption
indicating formation of entirely uniform cubic particles. Using this catalyst,
structurally different aromatic nitro compounds were reduced efficiently to
corresponding amines in excellent yields. Kinetic studies revealed that the
reduction rates of nitrophenol isomers follow 3-NP > 4-NP > 2-NP order. The
catalytic activity of Co-Cu/ZIF was further investigated in the reduction of
organic dyes such as methyl orange (MO) and rhodamine B (RhB). This cata-
lyst was recycled for at least ten runs in the reduction of 4-nitrophenol without
a noticeable decrease in activity and reused catalyst was characterized.
(
IASBS), P. O. Box 45195-1159, Gavazang,
Zanjan, 45137-66731, Iran
2
Research Center for Basic Sciences &
Modern Technologies (RBST), Institute
for Advanced Studies in Basic Sciences
(
IASBS), Zanjan, 45137-66731, Iran
3
Departamento de Química Orgánica and
Centro de Innovación en Química
Avanzada (ORFEO-CINQA), Universidad
de Alicante, Apdo. 99, E-03080-, Alicante,
Spain
Correspondence
Mohammad Gholinejad, Department of
Chemistry, Institute for Advanced Studies
in Basic Sciences (IASBS), P. O. Box
4
4
5195-1159, Gavazang, Zanjan
5137-66731, Iran.
Email: gholinejad@iasbs.ac.ir
K E Y W O R D S
catalyst, nitro compounds, organic dyes, zeolite imidazolate framework (ZIF)
Funding information
University of Alicante; Generalitat
Valenciana; Fondo Europeo de Desarrollo
Regional (FEDER, EU); Agencia Estatal
de Investigación (AEI); Spanish Ministerio
de Economía, Industria y Competitividad;
Spanish Ministerio de Economía y
Competitividad (MINECO); Iran National
Science Foundation, Grant/Award
Number: 97021804; Institute for Advanced
Studies in Basic Sciences (IASBS)
Research Council
[
6,7]
1
| INTRODUCTION
thermal and chemical stability.
However, despite vari-
ous applications of ZIFs in gas adsorption/storage, sepa-
ration, and chemical sensors less attention has been paid
Metal–organic frameworks (MOFs) have recently
received great attention in different industries such as gas
storage, fuel cells, supercapacitors and electrode mate-
[8–10]
for using them in design of heterogeneous catalysts.
Recently, few attempts have been made to use ZIFs as
catalyst or catalyst support in organic
transformations. For instance, ZIF-8, ZIF-9 and ZIF
[1–5]
rials for batteries.
Among them, zeolitic imidazolate
[
11–13]
frameworks (ZIFs) which are comprised of metal nodes
2+
2+
such as Co , Zn and imidazole bridging in a 3D tetra-
hedral framework have demonstrated high surface area,
nanosphere were applied as catalyst in the Knoevenagel
and phospha-Michael addition cycloaddition reactions,
Appl Organometal Chem. 2020;e5522.
wileyonlinelibrary.com/journal/aoc
© 2020 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.5522

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GHOLINEJAD ET AL.
[
14–16]
respectively.
Also, AgPd and AgAu nanoparticles
60F254 glass plate with 0.25 mm thickness and Varian
CP-3800 gas chromatograph. UV–Vis spectra were inves-
tigated on a UV–Vis spectrophotometer (JASCO, UV-
550). The morphology and microstructure of the samples
were measured by a field emission scanning electron
microscope (FE-SEM) JEOL JSM 840 and transmission
electron microscope (TEM) EOL JEM-2010. The SEM
mapping was monitored by Hitachi S3000 N. The crystal-
lographic structures of the products were characterized
by X-ray diffractometer (XRD) with Cu Kα radiation.
Thermogravimetric (TG) analysis was performed on a
thermogravimetric analyzer NETZSCH STA 409 PC/PG
supported on ZIF employed as catalysts in formic acid
dehydrogenation and oxidation of benzyl alcohol,
[17,18]
respectively.
Nowadays environmental problems as well as green
chemistry objectives encourage chemists to design new
pathways to eliminate or reduce pollutants or use wastes
as staring materials for preparation of useful chemicals.
Nitro compounds derived from industrial and agricul-
tural wastewater are classified as toxic and environmen-
[19,20]
tal pollutants.
Among them, nitrophenols have high
solubility and stability in water, which lead to health haz-
ards in human and animals.
[21–23]
ꢀ
One way to solve this
with the heating rate of 5 C min-1 in the air atmosphere.
problem is the catalytic reduction of nitro compounds to
the corresponding amines which are valuable chemicals
X-ray photoelectron spectroscopy (XPS) measurements
were recorded using a Kα spectrometer.
[24–26]
in synthetic organic chemistry.
For instance,
obtained aminophenols from reduction of nitrophenols
are non-toxic and used in the synthesis of drugs, rubber
materials, photographic resources and industrial
2.2 | Synthesis of Co-Cu precursors
[27,28]
dyes.
Other type of pollutants which usually found
PVP (3 g), Co(OAc) .4H O (0.91 g) and Cu(OAc) .4H O
2
2
2
2
in groundwater and causes allergic dramatic, skin irradia-
(0.37 g) were added to 500 ml flask containing ethanol
(200 ml) and the resulting solution was stirred under
refluxing conditions for 8 hr. Afterwards, the obtained
precipitate was separated by centrifugation (4000 rpm)
and the resulting light pink solid was washed with etha-
[29,30]
tion and cancer in human, are dyes.
Toxic and
extremely colored sewerages of dyeing industries which
penetrated in groundwater are a serious threat to both
human health and the environment. Therefore, it is still
great challenges to develop new efficient and eco-friendly
methods and catalysts for the reduction of pollutants
such as nitro compounds and dyes. Herein, we report
synthesis and characterization of new Co-Cu/ZIF and
investigate its catalytic performance in the reduction of
nitro compounds and organic dyes.
ꢀ
nol (10 × 20 ml) and dried in oven at 60 C.
2.3 | Synthesis of Co-Cu/ZIF
2-Methylimidazole (3 g) was dissolved in ethanol
ꢀ
The synthetic strategy for the Co-Cu/ZIF is shown in
scheme 1.
(150 ml) and the solution was stirred at 90 C under
reflux condition. Then, 50 mg of Co-Cu precursors were
dispersed in ethanol (20 ml) and the mixture was added
to the solution of 2-methylimidazole. Afterwards, the
reaction mixture was stirred under reflux conditions for
2
2
| EXPERIMENTAL SECTION
.1 | Materials and methods
1
hr. Finally, the purple precipitate was separated by cen-
trifugation, washed with ethanol (5 × 20 ml) and finally
ꢀ
dried in oven at 60 C.
Cobalt acetate tetrahydrate ( Co(OAc) .4H O), copper
2
2
acetate
vinylpyrrolidone (PVP, MW~10000), EtOH (99.86%),
-methylimidazole, nitro compounds, methyl orange
tetrahydrate
(
Cu(OAc) .4H O),
poly-
2
2
2.4 | General procedure for the
reduction of nitro compounds to amines
2
(
(
MO), rhodamine B (RhB), and sodium borohydride
NaBH ) were purchased from Sigma-Aldrich, Acros and
In a 5 ml glass flask, ArNO (0.5 mmol), NaBH (2 mmol),
4
2
4
Merck MilliporeSigma. Reactions were monitored by thin
layer chromatography (TLC) using Merck silica gel
catalyst (12.5 mg), and H O/ethanol (2 ml, 1:1) were
added and reaction mixture was stirred continuously at
2
SCHEME 1 Schematic illustration of the
formation process of Co-Cu/ZIF cubic via a two-
step strategy

CO/CU ZIF WAS PREPARED AND USED AS A CATALYST
3 of 10
room temperature for the desired time. The progresses of
the reactions were monitored by GC and TLC. After com-
pletion of the reaction, distilled water (2 ml) was added
to the reaction mixture and the crude product was
extracted with ethyl acetate (3 × 5 ml). The crude product
was further purified by column or plate chromatography
using n-hexane and ethyl acetate as eluents.
2.6 | Typical procedures for the
reduction of MO and RhB
2.5 ml of MO or RhB solution (0.06 mM), 0.5 ml of
NaBH aqueous solution (0.5 M) and catalyst (1 mg) were
4
added to a quartz cuvette and mixture was stirred at
room temperature. The progress of the reaction was mon-
itored with UV–Visible spectroscopy
2
.5 | Typical procedures for the
reduction of nitrophenol isomers
3 | RESULTS AND DISCUSSIONS
3.1 | Characterization
Typically, 2 ml of a 0.15 mM aqueous solution of the
nitrophenol isomers, 0.5 ml of NaBH aqueous solution
4
(
0.5 M) and 100 μl of the catalyst (1 mg/ml) were trans-
Content of Co and Cu in the Co-Cu/ZIF were determined
by atomic absorption spectroscopy to be 2.5 and
1.57 mmol/g, respectively. The morphology of the as-
prepared Co-Cu precursor and Co-Cu/ZIF were investi-
gated by different techniques. The scanning electron
microscopy (SEM) and transmission electron microscopy
(TEM) images of Co-Cu precursor showed amorphous
ferred into a quartz cuvette and the mixture was stirred
at room temperature. The conversion of nitrophenol iso-
mers to corresponding aminophenol isomers were
recorded by UV–Visible spectroscopy. The intensity of
absorptions were centered at 415, 393 and 400 nm for the
2
-NP, 3-NP and 4-NP, respectively.
FIGURE 1 SEM images of Co-Cu/ZIF
a) low and (b, c, d) high magnification. (e, f)
TEM images of Co-Cu/ZIF
(

4
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GHOLINEJAD ET AL.
sheets (Figure S1 in ESI). While, SEM and TEM images
of Co-Cu/ZIF showed that the structure consists entirely
of uniform cubic particles (Figure 1). Also, elemental
mapping and energy dispersive X-ray spectroscopy (EDX)
were carried out and proved the existence of C, Co, O,
and Cu in Co-Cu precursor as well as uniform distribu-
tion of C, N, Co, O, and Cu elements in Co-Cu/ZIF struc-
ture (Figures S2-S4 in ESI).
In order to find more information about oxidation
states of elements, X-ray photoelectron spectroscopy
(XPS) of Co-Cu/ZIF in Co 2p, Cu 2p, C 1 s, and N 1 s
regions were studied (Figure 2). From the XPS spectra it
can be realized that peaks centered at 932.8 and 935.08
are related to Cu 2p3/2 and peak at 953.0 eV is related to
Cu 2p1/2 of Cu (II) (Figure 2a). It should be noted that
three small peaks at 941.2, 943.8 and 955.2 are shake-up
FIGURE 3 XRD spectrum of Co-Cu/ZIF
[31]
satellites related to Cu (II) (Figure 2a).
Also, peaks
centered at 284.78 and 285 eV were attributed to C-C and
[32,33]
C-N bonds in Co/Cu-ZIF (Figure 2b).
The Co 2p
spectra exhibited four peaks at a binding energy of 780.8,
3
+
7
2
82.5, 796.7 and 798.3 eV, which are assigned to Co
2+
3+
2+
p3/2, Co 2p , Co 2p1/2 and Co 2p1/2, respectively
3/2
34–37]
[
(Figure 2c).
It should be noted that two peaks at
7
86.78 and 804.28 eV are ascribed to shake-up satellite
2
+ [38–40]
peaks of Co .
Also, the peak located at 398.7 eV
represented the tertiary N bonded to carbon atoms
[41]
(Figure 2d).
It is worth mentioning that presence of N
1
s of imidazole peak in Co-Cu/ZIF compared to Co-Cu
precursor confirm successful formation of ZIF framework
(Figure S5 in ESI).
The crystal structure and phase composition of Co-
Cu/ZIF were characterized by X-ray diffraction (XRD).
FIGURE 4 FT-IR spectra of the Co-Cu/ZIF
FIGURE 2 High resolution XPS spectra of
a) Cu 2p, (b) C 1s, (c) Co 2p and (d) N 1s for
Co-Cu/ZIF
(

CO/CU ZIF WAS PREPARED AND USED AS A CATALYST
5 of 10
addition, peaks in the region between 900–1350 cm−
indicated to the in-plane bending of the ring and the
peaks at 600–800 cm− exhibited the out-of-plane bend-
1
1
−
1
ing. Finally, the band at 420 cm shows the metal-N
[
14,43]
stretching mode.
The thermogravimetric analysis (TGA) indicates that
Co-Cu/ZIF has high thermal stability and negligible
ꢀ
organic compounds leaching up to 360 C (Figure 5).
3.2 | Catalytic performance
To investigate the catalytic activity of the Co-Cu/ZIF, ini-
tially the reduction of 4-nitrophenol (4-NP) to
FIGURE 5 TGA curve of the Co-Cu/ZIF
4
-aminophenol in the presence of NaBH was selected as
4
a model reaction and progress of the reaction was moni-
tored by UV–visible spectroscopy (Figure 6). Results indi-
cated that after the addition of catalyst and NaBH4,
absorption spectra of 4-NP which is centered at 317 nm,
was shifted to 400 nm, indicating formation of
4-nitrophenolate ion. Then, the peak intensity at 400 nm
was remarkably decreased and new absorption peak was
appeared at 300 nm denoting the formation of
ꢀ
Results showed the stronger peaks at 2θ = 7.35 and
1
ꢀ
2.8 corresponding to (011) and (112) planes indicating
high crystallinity of synthesized Co-Cu/ZIF and con-
firmed the crystalline phases of prepared ZIF
[6,42]
(Figure 3).
FT-IR spectrum of Co-Cu/ZIF showed two peaks
located at 3130 and 2927 cm−1 distinguishing the
stretching vibrations of C-H bonds in the imidazole ring
and the methyl group, respectively (Figure 4). Also, the
[
44,45]
4-aminophenol.
The complete reduction of
4-nitrophenols to 4-aminophenol was achieved within
4 min. To ensure the accuracy of the results, yield of reac-
tion was checked by gas chromatography (GC). Result
indicated that obtained GC yield is in line with UV–
visible spectroscopy results.
−1
−1
absorption bands at 1610 cm and 1580 cm can be
attributed to stretching vibration of C=C and C=N
respectively. The peaks in the range of 1350–1500 cm−
are correspond to the entire imidazole ring stretching. In
1
FIGURE 6 UV–Vis absorption spectra of
nitrophenol compounds reduction in the
4
presence of NaBH . Spectra showing the
reduction of nitrophenol catalyzed by Co-
Cu/ZIF

6
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GHOLINEJAD ET AL.
The reduction of 2-NP and 3-NP was also per-
peak was decreased and the new peak became visible
at the 291 nm indicating formation of corresponding
formed under the same reaction conditions and investi-
gated by the similar methodology (Figure 6). Results
showed that the absorption peak of 2-NP was emerging
at 417 nm in the UV–visible spectrum. With the addi-
[
46,47]
amine product.
Similarly, 3-NP shows the peak
absorption at 368 nm in UV–visible spectrum and the
new peak absorption appeared at 288 nm confirming
the formation of 3-AP.
tion of the catalyst and NaBH , the intensity of this
4
a,b
TABLE 1 The reduction of structurally different nitro compounds using Co-Cu/ZIF as the catalyst
a
Reaction conditions: ArNO
2
(0.5 mmol), NaBH
4
(2 mmol), catalyst (12.5 mg) in H
2
O/ethanol (1:1) at room temperature.
b
Yields determined by GC.
c
Reduction of 4-nitrophenol in the absence of NaBH
4
using Co-Cu/ZIF under optimized reaction conditions.
d
e
Reaction performed using Co/ZIF.
2
Reaction performed using Cu(OAc) .

CO/CU ZIF WAS PREPARED AND USED AS A CATALYST
7 of 10
We also studied application of the Co-Cu/ZIF catalyst
in the reduction of structurally different aromatic nitro
compounds (Table 1). Results indicated that nitroarenes
having electron donating and electron withdrawing
groups were reduced very efficiently and produced
amines in excellent yields. For highlighting advantage of
using bimetallic Co-Cu/ZIF in the reduction of
[59]
nitroarenes, reduction of 4-nitrotoluene using Co/ZIF
under optimized reaction conditions was studied. How-
ever, results showed formation of desired amine in very
low yield (Table 1, entry 7). Furthermore, reduction of
SCHEME 2 The reduction of 2,5-dichloro-N-(3-nitrophenyl)
pyrimidin-4-amine and 3-bromo-4-(4-(pyrrolidin-1-yl)piperidin-
4
-nitrotoluene using Cu(OAc) afforded very low yield
2
demonstrating advantage of using bimetallic Co-Cu/ZIF
in this reaction (Table 1, entry 7). These results con-
firmed presences of synergetic effect in bimetallic Co-Cu/
ZIF catalysts compared to monometallic analogies. We
have also studied reduction of 4-nitrophenol in the
absence of NaBH4 using Co-Cu/ZIF under optimized
reaction conditions. In this case result showed that reac-
tion did not proceed and starting material was intact
(Table 1, entry 5).
1
-yl)aniline
Using the UV–visible spectra, the percentage of con-
version for reduction of three nitrophenol isomers was
calculated [Equation (1)].
Ct
At
Ln = Ln
C0
= −kappt
ð1Þ
A0
We also studied reduction of pharmaceutical type
nitroarenes such as 2,5-dichloro-N-(3-nitrophenyl)
pyrimidin-4-amine and 3-bromo-4-(4-(pyrrolidin-1-yl)
In addition, the apparent rate constants (kapp) for the
reduction of 2-NP, 3-NP and 4-NP are computed
[
Equation (2)].
piperidin-1-yl)aniline
Scheme 2). Results showed desired amine products were
obtained in 87–90 isolated yields.
to
corresponding
amines
(
A −A
A0
0
t
%
Conversion =
× 100
ð2Þ
Recovery and recyclability of the catalyst is important
from industrial and economical standpoints. Therefore,
we investigated the reusability of Co-Cu/ZIF catalyst in a
reduction of 4-nitrophenol. Result of this study showed
that the Co-Cu/ZIF reused for ten successive reaction
cycles with small decrease in activity (Figure S6 in ESI).
Structure of reused catalyst was studied by SEM and FT-
IR in which SEM images (Figures S7a and S7b in ESI)
and FT-IR spectrum (Figure S8 in ESI) of reused catalyst
after 3 and 5 runs showed that structure of Co-Cu/ZIF is
almost preserved with partial destruction. However, SEM
image (Figure S7c in ESI) after 10 runs showed complete
distortion of the ZIF structure. This result was confirmed
by FT-IR study in which spectrum after 10 run showed
absence of related peaks to imidazole moiety confirming
destruction of the ZIF structure (Figure S8 in ESI).
Where A and A are the absorbance of nitrophenol at
t
0
time (t) and the time of initial absorbance, respectively.
The conversion percentage, completion time of reactions
and the apparent rate constant (Kapp) for the reduction of
all three nitrophenol isomers to aminophenol using Co-
Cu/ZIF as a catalyst are exhibited (Table S1 in ESI).
Results showed that the complete reduction of 4-NP,
3
-NP and 2-NP were achieved in 4 min, 2 min and 8 min,
respectively and reduction rates of nitrophenols follow
-NP > 4-NP > 2-NP order. This order can be explained
3
by conjugation, inductive and steric effects. The 2-NP
and 4-NP can be stabilized under the conjugation effect
and the negative charge in the phenoxide ion delocalizes
onto the nitro group resulted their lower reactivity than
3
4
-NP. Also, the inductive effect of 2-NP is higher than
-NP, that produced more positively charged nitrogen
Finally, the catalytic activity of Co-Cu/ZIF was inves-
tigated in the reduction of dyes, including methyl orange
(MO) and rhodamine B (RhB). These reactions were
monitored using UV–visible spectra in which in the pres-
ence of Co-Cu/ZIF the absorbance of MO (λmax = 467 nm)
and RhB (λmax = 556 nm) decrease with time (Figure 7).
The Kapp values of MO and RhB dyes are calculated to be
atom expecting higher reactivity of 2-NP. However, lower
reactivity of 2-NP than 4-NP indicated that the steric
effect plays an important role and reduce activity.
Activity of Co-Cu/ZIF catalyst is compared with other
catalysts reported previously using the normalized rate
constant (knor = kapp/m, where m is total weight of cata-
lyst) confirming higher efficiency of Co-Cu/ZIF catalyst
−
1
2.52 and 1.34 min , respectively indicating that Co-
Cu/ZIF can be employed as an efficient catalyst for the
[48–58]
[60,61]
(Table S2 in ESI).
reduction of organic dyes.
The proposed mechanism

8
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GHOLINEJAD ET AL.
FIGURE 7 Time-dependent UV–
visible absorption spectra for the
catalytic reduction of (a) RhB and
(
b) MO using Co-Cu/ZIF catalyst
for the Co-Cu/ZIF reduction of MO and RhB is the same
as the known mechanism for the metal catalyzed reduc-
tion reactions of MO and RhB. On the basis of common
analogies, produced H from the reaction of NaBH and
H O in the presence of ZIF catalyst reduce Methyl
2
1
1
Orange to N ,N -dimethylbenzene-1,4-diamine and
sodium 4-aminobenzenesulfonate and Rhodamine B to
[
62–70]
leuco rhodamine B (Figure 8).
2
4
4
| CONCLUSION
In conclusion, we introduced efficient strategy for the
synthesized of cubic Co-Cu/ZIF using mild reaction con-
ditions and characterized by different techniques. The
Co-Cu/ZIF exhibits high catalytic activity in the reduc-
tion of nitro compounds and organic dyes at room tem-
perature. The presence of Cu was proved to be crucial to
obtain excellent yields. This catalyst was recovered and
recycled using simple centrifugation and reused several
times with small decrease in activity. SEM and FT-IR
studies of reused catalyst proved that structure of the cat-
alyst was preserved until three recycling runs.
ASSOCIATED CONTENT
Supporting Information. Further SEM, XPS, Map, EDX,
TGA, FT-IR of Co-Cu precursor and Co-Cu/ZIFs,
recycling diagram, comparison Tables, GC spectra reduc-
tion reactions, and H NMR and C NMR of amine
products.
FIGURE 8 Possible mechanism for the reduction of methyl
orange (MO) and rhodamine B (RhB) by the Co-Cu/ZIF catalyst
1
13
using NaBH
4

CO/CU ZIF WAS PREPARED AND USED AS A CATALYST
9 of 10
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The authors are grateful to Institute for Advanced Studies
in Basic Sciences (IASBS) Research Council and Iran
National Science Foundation (INSF-Grant number of
[
[
9
7021804) for support of this work. José M. Sansano is
also thankful for financial support to the Spanish
Ministerio de Economía y Competitividad (MINECO)
[
23] L. Sun, Y. Yin, F. Wang, W. Su, L. Zhang, Dalton Trans. 2018,
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and the University of Alicante. Special thanks to
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Mohammad Gholinejad https://orcid.org/0000-0003-
0
209-4509
José M. Sansano https://orcid.org/0000-0002-5536-2717
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SUPPORTING INFORMATION
Additional supporting information may be found online
in the Supporting Information section at the end of this
article.
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