Design and development of novel Co-MOF nanostructures as an excellent catalyst for alcohol oxidation and Henry reaction, with a potential antibacterial activity

Article abstract of DOI:10.1002/aoc.4820

The novel metal–organic framework Co₂(bdda)_1.5(OAc)₁·5H₂O (UoB-3) was synthesized via a simple method at room temperature. UoB-3 was characterized by the different methods, including X-ray diffraction (XRD), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR), N₂-adsorption/desorption and elemental analysis. The catalytic ability of UoB-3 was detected to be excellent for primary and secondary alcohols oxidation reaction with high yields under solvent-free conditions. Moreover, UoB-3 was highly active for Henry reaction of different aldehydes with nitromethane in water as a green solvent. The nanocatalyst can be recycled for five consecutive cycles without losing its activity and structural rigidity. The antibacterial activity of UoB-3 nanostructures towards Gram-negative bacteria, Escherichia coli and Gram-positive bacteria, Bacillus cereus was also evaluated by using an inhibition zone test. These nanostructures exhibited strong antibacterial effect against both of them. The purpose of this study was the developing metal–organic framework materials with the enhanced activity in various fields.

Full text of DOI:10.1002/aoc.4820

Received: 14 September 2018
DOI: 10.1002/aoc.4820
Revised: 3 January 2019
Accepted: 7 January 2019
F U L L P A P E R
Design and development of novel Co‐MOF nanostructures
as an excellent catalyst for alcohol oxidation and Henry
reaction, with a potential antibacterial activity
Sima Aryanejad1
| Ghodsieh Bagherzade1
| Maryam Moudi2
1 Department of Chemistry, Faculty of
Sciences, University of Birjand, Birjand,
97175‐615, Iran
2 Department of Biology, Faculty of
Sciences, University of Birjand, Birjand,
97175‐615, Iran
The novel metal–organic framework Co2(bdda)1.5(OAc)1·5H2O (UoB‐3) was
synthesized via a simple method at room temperature. UoB‐3 was character-
ized by the different methods, including X‐ray diffraction (XRD), transmission
electron microscopy (TEM), thermogravimetric analysis (TGA), Fourier trans-
form infrared spectroscopy (FT‐IR), N2‐adsorption/desorption and elemental
analysis. The catalytic ability of UoB‐3 was detected to be excellent for primary
and secondary alcohols oxidation reaction with high yields under solvent‐free
conditions. Moreover, UoB‐3 was highly active for Henry reaction of different
aldehydes with nitromethane in water as a green solvent. The nanocatalyst
can be recycled for five consecutive cycles without losing its activity and struc-
tural rigidity. The antibacterial activity of UoB‐3 nanostructures towards
Gram‐negative bacteria, Escherichia coli and Gram‐positive bacteria, Bacillus
cereus was also evaluated by using an inhibition zone test. These nanostruc-
tures exhibited strong antibacterial effect against both of them. The purpose
of this study was the developing metal–organic framework materials with the
enhanced activity in various fields.
Correspondence
Ghodsieh Bagherzade, Department of
Chemistry, Faculty of Sciences, University
of Birjand, Birjand, 97175‐615, Iran.
Email: bagherzadeh@birjand.ac.ir;
gbagherzade@gmail.com
Funding information
University of Birjand Research Council;
Iran National Science Foundation, Grant/
Award Number: 96008530
KEYWORDS
alcohol oxidation, antibacterial activity, Henry reaction, MOF, Schiff base
1 | INTRODUCTION
compound that can be provided some of the green chem-
istry goals. In the last years, the researchers have
The green chemistry revolution has provided a large
number of challenges in practical and industrial chemis-
try fields. Some of the challenges for chemist include
the finding and developing of new synthetic pathways
by using alternative feedstocks and more selective. In
addition, overcoming to these problems can be possible
by changing reaction conditions and solvents for increas-
ing selectivity, minimizing energy, designing less toxic
and intrinsically safer chemicals.[1] A chemical synthesis
will be ideal by a combination of a number of environ-
mental, health, safety and economic purposes.[2–8]
Metal–organic frameworks (MOFs) are one of chemical
observed the unprecedented explosion of a new class of
porous metal–organic frameworks (MOFs).[9,10] The com-
bination of organic and inorganic building blocks into
highly ordered, crystalline structures offers an almost
infinite number of compositions, enormous flexibility in
pore size, shape, structure, and plenty opportunities for
functionalization, grafting and encapsulation.[11] Because
of these properties, MOFs have the numerous potential
application in the areas of gas storage,[12] sensing,[13] sep-
arations,[14] catalysis,[15,16] drug delivery[17] and health
science.[18] In spite of the many reported catalytic applica-
tions of MOFs, there is a challenge to develop truly
Appl Organometal Chem. 2019;e4820.
wileyonlinelibrary.com/journal/aoc
© 2019 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.4820

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ARYANEJAD ET AL.
efficient and selective catalytic processes using MOFs. On
the other hand, ability to access monodisperse nano‐sized
MOFs is very important for prospective applications in
heterogeneous catalysis and biomedicine.[19,20]
free condition and Henry reaction in water as a green
solvent. The results exhibited that UoB‐3 would be a
heterogeneous catalyst with highly efficiency and stable
performance. The nano‐catalyst can be easily recovered
and reused due to its heterogeneous catalytic nature. In
the following study of MOF applications, we have sought
to use UoB‐3 nanostructures as antibacterial agent. The
evaluation of test towards both Gram‐negative bacteria
and Gram‐positive bacteria revealed good potency for
the bactericidal activity.
Among the synthetic methods of aldehyde and
ketones, the alcohol oxidation is very interesting in mod-
ern organic chemistry.[21–24] Hence, the development of
alcohol oxidation methods directs toward achieving
highly selective, efficient, and environmentally friendly
catalytic systems. Also, it is important that the stoichio-
metric amount of inorganic oxidant is being substituted
with green oxidant such as O2 or peroxides or peroxides
[H2O2, tert‐butyl hydroperoxide (TBHP)] to overcome
the formation of harmful wastes.[25,26] There are some
reports on MOFs which are catalytically active for the
alcohol oxidation reaction.[27–33] Despite of available
reports, the search for new, environmentally friendly,
and efficient alcohol oxidation protocols, as well as the
improvement of the known ones, is of current interest.
On the other hand, the one of important methods for
C‐C formation is the nitro aldol or Henry reaction in
modern organic chemistry.[34,35] The product of Henry
reaction, β‐nitroalkanols, could be readily transformed
into beneficial synthons for the development of various
natural products and pharmaceutically urgent structural
scaffolds.[36,37] Additionally, the oxidation, dehydration,
reduction and Nef reaction of β‐nitroalkanols lead to a
diverse of significant building blocks. These building
blocks have many applications in synthetic chemistry
for the complex molecules construction.[38–40] Therefore,
for developing of the Henry reaction have made consider-
able efforts using homogeneous[41–43] and heteroge-
neous[44–47] catalysts. Among the studies have reported
for heterogeneous‐catalyzed Henty reaction until now,
few reports exist about MOFs that catalyse this reac-
tion.[48–50] It is not common that the metal catalysts act
effective in environmentally water solvent.[51,52] There-
fore, the replacing an organic solvent with this green
solvent in both synthesis and catalysis has achieved
advantages not only in the laboratory scale but also in
the industrial scale.[53]
2 | EXPERIMENTAL
2.1 | Materials and instruments
All of the reagents and solvents employed were from the
commercial sources and were used without further purifi-
cation. TEM investigations were performed using a
Philips CM120 Transmission Electron Microscope. XRD
was conducted on a X'Pert Pro MPD diffractometer
with Cu‐Kα (λ = 1.54060 Å) radiation source. The
Brunauer–Emmett–Teller (BET) surface area and pore
sizes of the UoB‐3 were measured using from N2
adsorption/desorption isotherms at 77 K with a Belsorp
mini II instrument after degassing UoB‐3. The FT‐IR
spectra were recorded on a NICOLET system 800 beam
splitter KBr SCAL = 800 using a resolution in the range
of 400–4000 cm −1. The C, H, and N contents were deter-
mined using
a Perkin Elmer CHNS‐O Elemental
Analyzer. Inductively coupled plasma atomic emission
spectroscopy (ICP‐AES) analysis was conducted on
OPTIMA 7300DV. Thermoanalyzer Shimadzu was used
for thermogravimetric analysis (TGA) between 30 and
710 °C with a heating rate of 10 °C/min under a N2 flow.
Ultrasonic generation was performed in an ultrasonic
bath Bandelin electronic (frequency: 35 KHz). The reac-
tion progress and product purity were released by TLC
on silica gel polygram SILG/UV254 plates. NMR experi-
ments were performed on a Bruker UltraShield™
spectrometer operating for proton‐1 and carbon‐13,
respectively. The chemical shifts were expressed in ppm
relative to tetramethylsilane as the internal reference.
With respect to significance of the green chemistry
goals and the potential application of MOFs, also our
interest to this field, we focused on the synthesis and
properties of MOFs in catalytic and antibacterial areas.
In our continuing research on synthesis and applica-
tions of MOFs,[54,55] we synthesized the new Co‐MOF
nanostructures from coordination assembly of cobalt ace-
tate with 4,4′‐[benzene‐1,4‐diylbis (methylylidenenitrilo)]
dibenzoic acid (H2bdda) in water under ultrasound irradi-
ation (viewed as UoB‐3).
2.2 | Synthesis of 4,4′‐[benzene‐1,4‐diylbis
(methylylidenenitrilo)] dibenzoic acid
(H2bdda)
4‐amino benzoic acid (2 mmol, 137 mg) was dissolved in
EtOH (10 ml) and added gradually to a solution of
terephthaldehyde (1 mmol, 268 mg) in EtOH (5 ml).
The mixture was magnetically stirred for one hour at
the room temperature. After completion of the reaction,
Hereby, we investigated the potential catalytic activity
in primary/secondary alcohol oxidation under solvent‐

ARYANEJAD ET AL.
3 of 11
the resulting yellow crystalline solid was filtered,
washed with EtOH three times and then dried in the
oven under vacuum.[55]
were purified on a silica gel plate (petroleum ether/ethyl
acetate; 5:1) that were characterized with 1HNMR. In
addition, the recycling experiments were carried out after
washing and drying the used catalyst. The rest of the pro-
cess was followed as the same condition.
2.3 | Synthesis of nanoscaled co‐MOF
(UoB‐3)
2.6 | Anti‐bacterial activity
The Co‐MOF nanostructures were synthesized according
to a facile one‐pot procedure. First, the linker H2bdda
(0.372 g, 1 mmol) were dissolved by adding NaOH 10%
(1 ml) in deionized water (20 ml) under magnetic stirring
for 5 mins at room temperature to obtain a clear yellow
solution. Then, a solution of Co (OAc)2 (0.342 g, 2 mmol)
in deionized water (10 ml) was added dropwise to above
mixture under ultrasonic irradiation at room temperature
for 15 mins and stay in the same condition for 30 mins.
The resulting green precipitation was collected by centri-
fugation and washed with EtOH three times by disper-
sion. The resulting Co2(bdda)1.5(OAc)1·5H2O were dried
in an oven at 100 °C. Elemental analysis and ICP (calc.%):
C (49.91%), N (4.85%), H (3.98%) and Co (15.25%);
(exp.%): C (50.43%), N (5.00%), H (3.56%) and Co
(13.68%).
Staphylococcus aureus (Gram‐positive) and Escherichia
coli (Gram‐negative) as the model microorganisms were
used to assess the antibacterial activity of UoB‐3 nano-
structures. Experiments were performed with fresh bacte-
ria previously incubated on Nutrient Agar plates at 37 °C
for 24 hours. Agar plates were provided by dissolving agar
powder (15.0 g L‐1), tryptone (5.0 g L−1), yeast extract
(2.5 g L−1), glucose (1.0 g L−1) in deionized water. The
above mixture was heated and stirred until the agar dis-
solved. In the following, the pH of solution was adjusted
to 7.0 0.1 with sodium hydroxide or hydrochloric acid
and the plates were sterilized by autoclaving.
The biocidal effect of UoB‐3 was investigated by
means of the diffusion method (Bauer et al., 1966). There-
fore, the bacterial suspension (200 ml, containing 5·107
colony‐forming units (CFU)/ml) was spread on the pre-
pared agar plates. After drying plates, the holes (7 mm
diameter) were punched by using the sterile tip over the
agar plates. Then, UoB‐3 (1 mg) was disposed directly
onto the holes of agar plates, after which the plates were
incubated at 37 °C for 48 hrs. The antibacterial activity
was evaluated based on the standard zone of inhibition
test. A qualitative test was performed under static condi-
tions that the diameters of the growth inhibition zones
were measured with the scale and reported in centimeter.
The experiments were performed in two replicates.
2.4 | Typical catalytic procedure for
alcohol oxidation
Typically, a mixture of UoB‐3 (2 mol%) as catalyst, alco-
hol (1 mmol) and TBHP (1.5 mmol) was stirred at 65 °C
for appropriate time. The progress of the reaction was
determined by thin layer chromatography (TLC). After
completion, the reaction mixture was cooled to room
temperature. The catalyst was separated by centrifuga-
tion, thoroughly washed with EtOAc and after drying,
used in the next run. The products were purified on a
silica gel plate to give pure products. For identification
of the final products, their physical data were compared
with those of authentic samples, because of all of them
are known.
3 | RESULT AND DISCUSSION
3.1 | Syntheses and characterization
The synthesis of UoB‐3 nanostructures was performed
under ultrasound irradiation conditions, by reacting the
H2bdda with Co (OAc)2 in the presence of deionized
water at room temperature (Scheme 1).
2.5 | Typical catalytic procedure for
Henry reaction
TEM technique was used to get a further insight into
the structure of UOB‐3 nanostructures. Monodispersed
nanoparticles with relatively uniform morphology were
detected (Figure 1a). The average diameter of nanostruc-
tures was obtained 32 nm based on the particle size distri-
bution histogram (Figure 1b).
Many efforts were made to gain the appropriate
crystals for single‐crystal structure determination.
Unfortunately, the crystal size was very small which be
In a typical experiment, aldehyde (1.0 mmol), nitrometh-
ane (5.0 mmol) and UoB‐3 (3 mol%) were added to water
(1 ml) in a glass vessel. Afterwards, the capped reaction
system was stirred for 24 hrs at 70 °C. The solid catalyst
was removed by centrifugation from the reaction mixture
and the organic phase was extracted with CH2Cl2 and
dehydrated with Na2SO4 to determine the conversion.
After the evaporation of the solvent, the crude products

4 of 11
ARYANEJAD ET AL.
indicated a narrow pore diameter distribution at 16 nm
(Figure 1e). The pore size distribution curve confirmed
that the surface area of UoB‐3 was mainly derived from
the mesopore.
In the FT‐IR spectrum of UoB‐3 nanostructures
(Figure 2, a), the corresponding v(C–O) stretching was
observed in the 1244 cm−1, whereas v (OH) of the coordi-
nated water molecules was in the 3450 cm−1. The band at
1695 cm−1 established the presence of a coordinated
acetate ligand. In addition, the characteristic strong bands
of the coordinated carboxylate groups appear at 1594 cm
SCHEME 1 Synthesis of UoB‐3 nanostructures from Schiff base
as organic linker
unsuitable for X‐ray diffraction. However, the PXRD
pattern of UoB‐3 was used to investigate the structural
properties (Figure 1c). It was clear that the most promi-
nent of pecks can be seen in area of 2θ < 10. However,
the presence of pecks in this area was exhibited that
UoB‐3 had porous structural. In addition, the pattern of
UoB‐3 was similar to the simulated pattern reported of
IRMOF‐74.[47] This observation confirmed that the both
of structure (UoB‐3 & IRMOF‐74) were isostructural.
The N2 adsorption/desorption at 77 K was used to
investigate the porosity of synthesized nanostructures.
The N2 sorptometry results showed a typical type IV
nitrogen sorption curve according to the IUPAC classifi-
cation (Figure 1d). This observation indicated that UoB‐
3 was a mesoporous material. In addition to, the hystere-
sis loop of curve was type HI that released UoB‐3 had
narrow distributions of pore size. The analysis of the
sorption curve using the Brunauer–Emmett–Teller
(BET) method demonstrated that the specific area was
approximately 50 m2 g−1 and the pore volume was
0.18 cm3 g−1. Moreover, the mesopore size distribution
curve, calculated from Barrett–Joyner–Halenda analysis,
−1
for the asymmetric stretching and 1401 cm−1 for the
symmetric v(C=O) one. These values confirmed that
−
CO2 groups were coordinated to cobalt. The coordina-
tion modes of carboxylate to metal could be determined
by the values of Δν (Δν = νas (COO) − νs (COO)) for metal
carboxylates.[56] The observed Δν values for UoB‐3 indi-
cated a bridging coordination mode for the carboxylate
groups; according to these observations, the geometric
structure the cobalt was proposed. (Figure 2, b).
According to the obtained data from Elemental CHN
and ICP analyses, the molecular formula of UoB‐3 nano-
structures was suggested as Co2(bdda)1.5(OAc)1·5H2O.
The calculated elemental content based on its molecular
formula is C (49.91%), N (4.85%), H (3.98%) and Co
(15.25%) that appropriately agrees with the real amounts
of C (50.43%), N (5.00%), H (3.56%) and Co (13.68%).
The thermal stability of UoB‐3 nanostructures was
studied by TGA under nitrogen gas over a range of
20–700 °C. The TGA curve indicated two recognizable
weight loss steps (Figure 3). The first weight loss (9.69%)
from room temperature to 260 °C was attributed to the
FIGURE 1 (a) TEM images; (b) Particle size distribution histogram; (c) XRD pattern; (d) Isotherm adsorption–desorption; (e) Pore width
of UoB‐3

ARYANEJAD ET AL.
5 of 11
FIGURE 2 (a) FTIR spectrum of UoB‐
3; (b) The suggested geometry around of
the Co center
loss of water molecules. This observation was in good
agreement with the number of water molecules in the
proposed molecular formula. Another weight loss
(41.77%) in the range of 260–660 °C can be derived from
the decomposition of the coordinated organic ligands.
Actually, acetate and the part of Schiff base linker
decomposed that compatible with the results of CHN
and ICP analyses.
the usage of effective catalyst for the promotion of given
reaction was reasonable. In order to the investigation of
solvent nature, the model reaction was performed in dif-
ferent solvents and solvent‐free conditions (Figure S1).
As seen, the best result was given in solvent‐free condi-
tions in the presence of UoB‐2 as catalyst (Figure S1). It
is suggested that open catalytic sites in solvent‐free
medium is the reason of this observation. After that, the
catalytic performance of UoB‐3 was evaluated at different
temperature (Figure S2). With increasing temperature,
the reaction was improved based on yield and rate, grad-
ually. The maximum yield was observed at 65 °C. More
increasing in the temperature had no positive effect on
the yield and rate of the reaction. Then, the catalyst
(Figure S3) and oxidant amount (Figure S4) was opti-
mized. Best yield was obtained in the presence of
2 mol% of UoB‐3 and 1.5 mmol of TBHP. The effect of
oxidant type was also evaluated with TBHP, NaIO4,
H2O2 and Oxone under the catalytic influence of UoB‐3
in the solvent‐free conditions at 65 °C (Figure S5). After
the optimization of reaction, the activity of Co (OAc)2 as
the precursor salt of UoB‐3 was evaluated, 40% yield
was obtained after 60 minutes (Figure S3). Therefore, it
can be concluded that the ligand H2bdda have an impor-
tant role in this catalytic system.
3.2 | Catalytic studies
UoB‐3 nanostructures were exhibited considerable activ-
ity for the primary and secondary alcohols oxidation to
the corresponding aldehydes or ketones; and Henry reac-
tion between several benzaldehydes and nitromethane in
water (Scheme 2).
3.2.1 | Alcohol oxidation
Benzyl alcohol oxidation was chosen as a model substrate
in more detail to optimize the reaction variables such as
solvent, temperature, the molar ratio of alcohol/oxidant
and alcohol/catalyst. Initially, the model reaction was
conducted under neat conditions. However, reaction did
not proceed in the absence of the catalyst. Therefore,
With the optimized reaction conditions in hand, we
next evaluated the oxidation reaction of primary and sec-
ondary alcohols in the presence of UoB‐3 nanostructures.
The number of available aromatic alcohols bearing
electron‐donating or electron‐withdrawing groups were
SCHEME 2 Catalytic activity of UoB‐3 in primary/secondary
FIGURE 3 TGA curve of UoB‐3 nanostructures
alcohol oxidation and Henry reaction

6 of 11
ARYANEJAD ET AL.
tested which their results are summarized in Table 1. A
slight difference in the yield of the reactions is probably
due to the presence of electron‐donating/withdrawing
functional groups on the benzene ring, which cause the
alcohols to be slightly active or inactive.
The mechanism of alcohol oxidation with TBHP in
the presence of UoB‐3 was investigated. For this reason,
the benzyl alcohol oxidation catalyzed by UoB‐3 was cho-
sen. PhNH2 and CBrCl3 were added to the reaction
medium as the oxygen and carbon traps, respectively.
The reaction yield decreased after adding PhNH2 or
CBrCl3 from 95% (Table 1, Entry 1) to 2% and 4%, respec-
tively. The results confirmed that the mechanism of alco-
hol oxidation occurs via the radical mechanism, and it is
similar to the proposed mechanism in other cases.[26,57]
Based on obtained results, it was proposed that the oxida-
tion mechanism may start with the metal‐assisted gener-
t
t
ation of BuOO• (upon reduction of BuOOH by Co (II)
t
center), and continue by the generation of BuO• (upon
t
oxidation of BuOOH by the formed Co (III) center).
These radicals act as hydrogen atom abstractors from
the alcohols. In the proposed mechanism, the proton
transfer steps are the fundamental steps of the above
reaction. These steps can be assisted by the linker Schiff
base that increase the catalytic activity of UoB‐3.
The merit of this operationally catalytic protocol was
compared with the previously reported methods
(Table 2), in terms of catalyst loading, conversion rate,
conversion yield and used conditions in the oxidation of
benzyl alcohol as model substrate. Inspection of the
results was revealed clearly the superiority of the pre-
sented methodology for oxidation of alcohols. Actually,
the low amount of used catalyst, the reduced reaction
time and the absence of solvent were common advan-
tages of our system.
TABLE 1 Substrate scope for oxidation of primary and secondary
benzyl alcohol by UoB‐3a
Time
(min)
Yield
(%)b
Entry
Substrate
Product
1
60
95
2
3
4
5
45
93
60
60
75
83
87
81
3.2.2 | Henry reaction
The good performance of UoB‐3 as heterogeneous cata-
lyst in alcohol oxidation reaction encouraged us to check
the catalytic activity of this catalyst in the different reac-
tion. Therefore, the potential catalytic activity of UoB‐3
nanostructures was investigated in Henry (or nitroaldol)
reaction of nitromethane with various aldehydes. To
search for the optimal conditions, benzaldehyde
(0.50 mmol) and nitromethane (2.5 mmol) were taken
as model substrates with UoB‐3 nanostructures as cata-
lyst. The factors that affect reaction including the nature
of solvent, amount of catalyst and temperature were
screened. Initially, control reactions were examined in
the absence of UoB‐3 nanostructures but in the presence
of Co (OAc)2 and free linker. No remarkable reaction
between benzaldehyde and nitromethane was observed
in the absence of nanocatalyst. Actually, the nitroaldol
reaction was proceed after an extended reaction time of
24 hours in the presence of Co (OAc)2 and free linker
18% and 20%, respectively (Figure S7). The model reac-
tion was carried out at 70 °C in different solvents such
as water, ethanol, ethyl acetate, acetonitrile and solvent‐
free condition (Figure S6). Surprisingly, the best result
was obtained in water. Thus; water was selected as the
sole solvent for further studies. Then, the effect of catalyst
6
75
45
45
60
60
90
84
82
84
90
85
82
7
8
9
10
11
12
13
90
90
75
78
aReaction conditions: Alcohols (1 mmol), TBHP (1.5 mmol), UoB‐3 (2 mol%),
Solvent free, 65 °C.
bIsolated yield.

ARYANEJAD ET AL.
7 of 11
TABLE 2 Comparison of activities of catalysts towards the alcohol oxidation reaction
Catalyst
amount
Time
(h)
Catalyst
Conditions
yield
ref
[27]
[28]
[29]
[30]
[31]
[32]
[33]
MOF‐HPW
50 mg
CTAB/H2O2/80 °C
CH3CN/O2/75 °C
Tuloene/O2/105 °C
Tuloene/O2/130 °C
MW/TBHP/100 °C
CH3CN/TBHP/60 °C
CCl4/visible‐light
S.F./TBHP/65 °C
98
50
95
71
81
88
80
95
3
Fe‐MIL‐101
1 mol
14
6
Hf‐MOF‐808‐V
7.5 mol%
100 mg
0.2 mol
2 mol %
15 mg
CuPd‐MOF
7
[{Cu(L1)‐ (DMF)}·DMF·H2O]nb
[Co3L(PTA)2.5(OAc)]a
MIL‐53(Fe)‐graphene
UoB‐3
0.5
24
9
2 mol%
1
This work
aPTA: p‐phthalic acid.
bL:5‐{(pyridin‐4‐ylmethyl)amino} isophthalic acid.
amount was studied. An increase of the catalyst amount
from 1.0 to 3.0 mol% was enhanced the reaction yield
from 18% to 83%, respectively; but a further rise of that
amount was not improved the product yield (Figure S7).
Afterwards, the investigation of the temperature effect
was revealed that varying the temperature from room
temperature to 70 °C improved the yield of β‐nitroalkanol
from 20 to 83%, however, a further temperature increase
had not the positive effect (Figure S8).
With having the optimized conditions of reaction, the
catalytic activity of UoB‐3 was examined the reaction of
different substituted aromatic aldehydes with nitrometh-
ane, producing the corresponding β‐nitroalkanols
with yields from 62 to 88%. The results revealed that aryl
aldehydes bearing an electron‐withdrawing group were
exhibited higher reactivity (Table 3, entries 2 and 7)
as compared to those having electron‐donating moieties
(Table 3, entries 5 and 10). It may be related to an
increase of the electrophilicity of the substrate in the
former case.
Furthermore, the catalytic activity of UoB‐3 was
extended to the reaction of benzaldehyde and nitoalkanes
with various molecular size including nitromethane
(2.0 Å × 3.3 Å), nitroethane (2.2 Å × 3.9 Å) and
nitropropane (2.2 Å × 5.6 Å)]. The obtained results
released that the yield of reaction was systematically
depended on the molecular size of nitroalkanes
(Table 4). Actually, the reaction yield decreased as
the molecular size of nitroalkanes increased. These obser-
vations can help to get a comprehensive the reaction
mechanism and reaction center. Based on the selective‐
size behavior of UoB‐3, it can be concluded that the
reaction catalyst in the interior sites and not only by
the exterior ones.
nitronate species, the linker assisted the deprotonation
of the methylene group of nitromethane. Then, benzalde-
hyde was activated by metal center towards its electro-
philic attack. Finally, the formation of C − C bond
upon nucleophilic was performed by addition of the
nitronate to the carbonyl group of aldehyde to give
the β‐nitroalkanol. The abstraction of proton from
nitroalkane and the protonation of the C − C coupled
species can be assisted by the linker (with an azomethine
group) and by water (amphoteric behavior), thus this
probably accounts for the good activity of our catalysts
in the presence of water Scheme 3.
The catalytic efficiency of UoB‐3 nanostructures in
comparison with various MOFs that had catalyzed
Henry reaction was presented in Table 5. UoB‐3 nano-
structures had the advantages of being rather cheap
and easy‐to‐prepare. Moreover, organic solvents have
been utilized in the some of the reported cases for the
Henry reaction, and there were only very few examples
where water has been applied. In this work, interest-
ingly, the best results were obtained in aqueous medium
compared with the organic solvents. Using of water as
solvent had many advantages such as non‐toxic, safe,
and environmentally benign.
3.2.3 | Recyclability and heterogeneity
tests
The recyclability and the heterogeneous nature of UoB‐3
nanostructures were investigated in the both of alcohol
oxidation and Henry reactions. The nanostructures were
recovered from the reaction mixture after appropriate
time for the next reaction run by centrifugation, washing
with ethanol, and then drying in the oven. As shown in
Figure 4 (right), the significant changes were not
observed in the activity of UoB‐3 after five runs. FT‐IR
The reaction mechanism for the Henry reaction cata-
lyzed by UoB‐3 should be similar to the reported cases
with the related catalytic systems.[58,59] For giving a

8 of 11
ARYANEJAD ET AL.
TABLE 3 Henry reaction of various aldehydes and nitromethane
with UoB‐3a
The hot filtration test was carried out for Henry
reaction in order to clarify if the catalytic process was
heterogeneous or homogeneous. For this purpose, a con-
trolled experiment with UoB‐3 was performed until an
intermediate yield (ca. 45%) was observed (12 hr). Then,
the catalyst was removed, kept the catalyst free reaction
solution under the same conditions and was stirred for
additional 36 hrs. The results indicated that the yield of
β‐nitroalkanole did not increase appreciably after
removal of the solid catalyst (Figure 4, left). Additionally,
the amount of cobalt was determined in the filtrated
solution, after the separation of the catalyst, was only
0.01% of the amount used in the reaction thus ruling
out any significant leaching of the catalyst. These
observations demonstrated that the catalysis was hetero-
geneous in nature.
Entry
Substrate
Product
Yield (%)b
1
83
2
88
85
83
78
74
78
75
72
65
62
68
80
3
4
3.3 | Antibacterial activity
5
The advantages of MOFs as new, highly functional com-
pounds with biological activity might come from their
composition, structure, and very high internal volume.
In addition to, the benefits to using MOFs over natural
and synthetic polymers is their uniformity of the specia-
tion and distribution of metal active sites. As regards,
medicinal applications of MOFs might be limited because
of their low solubility.[60] Accordingly, the developing
novel MOFs with therapeutic activity is very important.
Therefore, the antibacterial activity of UoB‐3 nanostruc-
tures was evaluated in this work. Gram‐negative bacteria,
Escherichia coli and Gram‐positive bacteria, Bacillus
cereus were chosen as model microorganisms at the con-
centration of 80 μl by the Agar well diffusion method.
The both of the bacteria are commonly found in water.
The standard zone of inhibition test, a qualitative test
6
7
8
9
10
11
12
13
TABLE 4 Henry reaction of benzaldehydes and various
nitroalkanes with UoB‐3a
Entry
Substrate
Nitroalkane
Yield (%)b
1
CH3NO2
83
aCondition reaction: Benzaldehyde (1 mmol), Nitromethane (5 mmol), UoB‐
3 (3 mol%), H2O (1 ml), 70 °C, 24 hr;
bIsolated yield.
2
3
71
46
spectra of reused UoB‐3 compared with its fresh were
revealed that the internal structure of it was maintained
intact even after the five cycles of the reaction (Figure S9).
aCondition reaction: Benzaldehyde (1 mmol), Nitroalkane (5 mmol), UoB‐3
(3 mol%), H2O (1 ml), 70 °C, 24 h;
bIsolated yield.

ARYANEJAD ET AL.
9 of 11
SCHEME 3 Proposed catalytic cycle for
the Henry reaction catalyzed by UoB‐3
TABLE 5 Comparison of activities of catalysts towards the Henry reaction using aldehyde and nitromethane
Catalyst
Aldehyde
solvent/temp/time
yield
ref
[49]
[61]
Cu(L)(H2O)4](L = 2‐propionamidoterephthalate)
Benzaldehyde
Benzaldehyde
H2O/70 °C/30 h
71
50
[Cu3(pdtc)L2(H2O)3].2DMF.10H2O (HL: 4‐(2‐(pyridin‐4‐yl)vinyl)
1,4‐dioxane/70 °C/36 h
benzoic acid)
[50]
[31]
NH2‐Tb‐MOF
Benzaldehyde
Benzaldehyde
EtOAc/90 °C/24 h
H2O/75 °C/40 h
87
84
[Cu(L)‐(DMF)] ·DMF·H2O (H2L: 5‐{(Pyridin‐4‐ylmethyl)amino}
isophthalic acid)
[31]
[48]
[59]
[Cd‐(L)]n (H2L: 5‐{(Pyridin‐4‐ylmethyl)amino}isophthalic acid)
[{Cd2(L‐glu)2(bpe)3(H2O)}·2H2O]
Benzaldehyde
Benzaldehyde
Benzaldehyde
H2O/75 °C/40 h
MeOH/R.T./72 h
MeOH/70 °C/24 h
69
89
89
[Cu4(HL)2(H2O)4(MeO)4]n (H3L: (2S,2'S,2"S)‐2,2′,2″‐
(benzenetricarbonyltris (azanediyl)) tripropanoic acid)
UoB‐3
Benzaldehyde
H2O/70 °C/24 h
83
This work
performed under static conditions, was used for investiga-
tion of anti‐bacterial activity. Its results for individual
bacterial culture was shown in Figure 5. The bacterial
growth below the contact area between the E. coli/B.
cereus and the UoB‐3 was highly inhibited. The diameter
of inhibition zones (cm) around UoB‐3 nanostructures
were for E. coli and B. cereus 2.3 1 and 3.5 1, respec-
tively. The differences in the diameter of zone of
FIGURE 4 (left) The hot leaching test for Henry reaction based on UoB‐3 nanostructures; (right) Catalyst recycling test for alcohol
oxidation and Henry reaction.

10 of 11
ARYANEJAD ET AL.
FIGURE 5 Inhibition areas for UoB‐3
nanostructures (a) B. Cereus, (b) E. Coli
inhibition for E. coli/B. cereus might be due to the differ-
ence in the susceptibility of different bacteria to UoB‐3.
The difference in cell structure, physiology and metabo-
lism of Gram‐positive and Gram‐negative bacteria might
be effect on their sensitivity toward UoB‐3 nanostruc-
tures. However, the present study clearly was exhibited
that UoB‐3 nanostructures indicated good activity against
both Gram‐negative and positive organism.
ORCID
Sima Aryanejad https://orcid.org/0000-0002-5145-3734
Ghodsieh Bagherzade
https://orcid.org/0000-0002-7417-
2214
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How to cite this article: Aryanejad S,
Bagherzade G, Moudi M. Design and development
of novel Co‐MOF nanostructures as an excellent
catalyst for alcohol oxidation and Henry reaction,
with a potential antibacterial activity. Appl
Organometal Chem. 2019;e4820. https://doi.org/
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