A nanoscale Cu-metal organic framework with Schiff base ligand: Synthesis, characterization and investigation catalytic activity in the oxidation of alcohols

Article abstract of DOI:10.1016/j.inoche.2017.04.015

Nanostructures of a new copper-based metal-organic framework with a Schiff base ligand as an organic linker, Cu₂ (bdda) (OAc)₂·1H₂O (H₂bdda?=?4,4′-[benzene-1,4-diylbis (methylylidenenitrilo)] dibenzoic acid), wa

Full text of DOI:10.1016/j.inoche.2017.04.015

Accepted Manuscript
A nanoscale Cu-metal organic framework with Schiff base ligand:
Synthesis, characterization and investigation catalytic activity in
the oxidation of alcohols
Sima Aryanejad, Ghodsieh Bagherzade, Alireza Farrokhi
PII:
S1387-7003(17)30189-2
doi: 10.1016/j.inoche.2017.04.015
INOCHE 6620
DOI:
Reference:
To appear in:
Inorganic Chemistry Communications
Received date:
Revised date:
Accepted date:
7 March 2017
10 April 2017
14 April 2017
Please cite this article as: Sima Aryanejad, Ghodsieh Bagherzade, Alireza Farrokhi ,
A nanoscale Cu-metal organic framework with Schiff base ligand: Synthesis,
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ACCEPTED MANUSCRIPT
A nanoscale Cu-Metal organic framework with Schiff base ligand:
Synthesis, characterization and investigation catalytic activity in the
oxidation of alcohols
a
a
a
Sima Aryanejad , Ghodsieh Bagherzade * , Alireza Farrokhi
Department of Chemistry, Faculty of Sciences, University of Birjand, P.O. Box 97175-615, Birjand,
Iran
Email: bagherzadeh@birjand.ac.ir, gbagherzade@gmail.com
Abstract
Nanostructures of a new copper-based metal-organic framework with a Schiff base ligand as
an organic linker, Cu2 (bdda) (OAc) . 1H O (H bdda= 4,4'-[benzene-1,4-diylbis
2
2
2
(methylylidenenitrilo)] dibenzoic acid), was prepared via Ultrasound assisted synthesis and
characterized by X-ray powder diffraction (XRD), thermogravimetric analysis (TGA),
Brunauer–Emmett–Teller (BET), inductively coupled plasma atomic emission spectroscopy
(
ICP-AES), transmission electron microscope (TEM), elemental analysis (CHN) and FT-IR
spectroscopy. Catalytic proficiency of this MOF in the oxidation of alcohols was investigated
that exhibited efficient and selective activity for the transformation of alcohols to the
corresponding carbonyl compounds under the absence of organic solvents. The reusability of
the catalyst also was examined, in which the catalyst was reused six times without significant
loss of its catalytic efficiency.
Keywords: MOF, Schiff base, Oxidation, TBHP, Alcohols
Metal–organic frameworks (MOFs) are crystalline organic–inorganic hybrid porous
coordination polymers which construct from metal centers as nodes and organic bridging
blocks linking them in conjunction[1]. MOFs, compared to common crystalline materials,
would represent very benefits due to obvious structure, extensive surface areas, high porosity,
structural variability, the potential of adjusting surface hydrophobicity/ hydrophilicity.
Because of the specific intrinsic properties of MOFs, they have achieved abundant attention
in the recent decade. Also, MOFs have been utilized in gas storage/separation[2–8],
adsorption[9], optical sensing[10,11] and drug delivery[12,13]. As well as, MOFs have been
recently noticed as a heterogenous catalyst in organic reactions[14]. In reaction conditions,
the frameworks of MOFs are stable that the percentage of metal leaching in organic solvents

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decreases[15–17]. Also, the designability features of MOFs by selecting the metal ions and
the regard to the size and shape of the organic linkers result in the variety synthesis of MOFs
with favorite and adequate structural and chemical property for the particular application
[
18,19]. A broad diversity of organic linkers have been embedded in MOFs [20], the organic
linkers can be modified with consideration of the isoreticular principle, nevertheless,
equivalent structural types can be synthesized. With the use of a linear extension of the
organic linkers can be enhanced pore size, high surface area, and high network stability
[
18,19]. Therefore, there is the particular interest to construct porous MOFs of longer linkers.
Among of the synthesized MOFs until now, it was reported that copper-based frameworks
can be employed as favorable heterogeneous catalysts for several organic reactions because
of their unsaturated open copper metal sites[21–23].
In addition, the synthesis of micro/ nano size of MOFs has increased their potential usage for
nanotechnological applications. Nanoscale MOFs have the same rich variety of combinations,
structures, and properties of bulk MOFs with the benefits of nano compounds[24]. In
between of different methods for synthesis of nano MOFs have been reported such as
ultrasound irradiation and microwave-assisted syntheses, microemulsion synthesis,
surfactant-assisted synthesis [25–28], ultrasound irradiation is one of the simplest and
effective methods. Over the past decade, this method has attained much attention because
ultrasound provides the fast, moderate, inexpensive, reproducible, and green method for
synthesis of nano/micro scale of MOFs with unique properties and new morphologies [29–
3
3].
Whereas, Schiff base metal complexes have the excellent properties as the diversity of their
solid state structures, relatively inexpensive, easy preparation and chemical and thermal
stability, there has been considerably growing in the coordination chemistry of these
compounds recently [34–37]. To date, in an effort to the synthesis of MOFs have been not
used from the Schiff base such as an organic linker.
The selective catalytic oxidation of alcohols into the corresponding aldehydes or ketones
without traceable overoxidation products is one of the most considerable functional group
transformations in synthetic chemistry and the chemical industry. This reaction is
traditionally performed by using environmentally undesired stoichiometric oxidation
systems[38]. Also, there are numerous reports of efficient catlysts for these oxidation
reaction. In most reports, the oxidation reaction have been catalyst with homogeneous or
noble-metal based ( e. g., Au, Pd and Ru) catalysts[39–42]. Nevertheless, homogeneous
catalysts associate with the problems such as difficult recovery and reusability of catalyst. In

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addition, the usage of noble-metal based systems is limited due to high price and shortage of
noble metals resources.
To overcome the problems associated with the catalytic systems for alcohol oxidation
reaction, the preparation of a stable and effective heterogeneous catalyst with non-noble
transition-metal-based catalyst systems is a challenging research aim. Thus, synthesis of
novel and efficient MOF-based heterogeneous catalysts with unique properties are desirable.
Todays, the researchers have extensively used Cu-complexes in the field of catalysis due to
its specific properties such as safe, available and inexpensive[43–46].
This work has centralized on the synthesis and characterize the novel copper-based nano
metal organic framework Cu(II)-MOF conveniently under ultrasound irradiation, which
constructed from the Schiff base as a linker. As well as, the application of Cu(II)-MOF as an
appropriate, efficient and a green catalyst for the selective oxidation of alcohols without any
solvent, with good to excellent yields investigated (Scheme 1). To the best of our knowledge,
this is the first report about the utilization of the new Schiff base as an organic linker in the
synthesis of MOFs.
Scheme 1: Oxidation of benzylic alcohols in presence of UoB-1 by TBHP
The new Schiff base building block, 4,4'-[benzene-1,4-diylbis (methylylidenenitrilo)]
dibenzoic acid, was prepared by the condensation reaction of 4-amino benzoic acid and
terephthaldehyde in EtOH at room temperature. Then, the Schiff base synthesized (H bdda)
2
as a linker used to prepare a novel nano Cu-based metal- organic framework (UoB-1) at room
temperature under ultrasonic radiation. (Scheme 2).

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Scheme 2: Synthesis of UoB-1 nanostructures from Schiff base as organic linker
UoB-1 was characterized by X-ray powder diffraction, N adsorption–desorption isotherms,
2
thermogravimetry, FT-IR, inductively coupled plasma-MASS (ICP-MS), and CHN elemental
analysis.
At the first, the molecular formula of UoB-1 was determined by CHN, ICP, and TG analyses.
Cu (bdda) (OAc) . 1H O is calculated to obtain C (49.29%), H (3.50%), N (4.42%), Cu
2
2
2
(
20.06%) which reasonably agrees with the real amounts of C (50.34%), H (5.17%), N
3.23%), Cu (20.68%).
(
The TGA curve of the synthesized UoB-1 nanostructures has been shown in figure 1. It can
be seen that the TGA data expose a weight loss of 2.016 % (calculated: 2.8 %) from room
temperature to 180 °C, which can be ascribed to the loss of H O molecules. Thereafter, a
2
small weight loss (7 % at 272 °C) was observed, which corresponds to the decomposition of
UoB-1 nanostructures. Also, the most considerable weight loss (30.54 % at 343 °C) can be
seen because of the more decomposition of the structure. The results of obtained from TGA
have confirmed the molecular formula of UoB-1.

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Tempreture(°C)
Fig. 1: TGA curves of UoB-1 catalyst
To gain a further perception into the structure of UoB-1, transmission electron microscopy
(TEM) was employed to investigate the morphology and size distribution of nano UoB-1.
The images TEM of the UoB-1 nanostructures were demonstrated in Fig. 2a. It is obvious
that the most of the nanostructures were spherical in shape. As well as, the particle size
distribution of UoB-1 nanostructures is estimated by using TEM and display that the average
diameter of the particles was 51 nm (Fig. 2b).
a
b
30
25
20
15
10
5
0
47
48
49
50
51
52
Particle Size (nm)
Fig. 2: (a) TEM image and (b) particle size distribution histogram of UoB-1
−
1
The IR spectra were recorded as KBr pellets in the range 4000–400 cm . Strong bands in the
−
1
region of 1300-1800 cm correspond to ν (COO), νs(COO), and ν(C–C) vibrations,
as
implying the presence of dicarboxylate linker in the UoB-1 framework. The significant
spectral shift of the carboxylate group compared with legend confirms that the carboxylate
group coordinated. It should be noted that the values of Δν (Δν = ν (COO) -ν (COO)) for
as
s
the metal carboxylates can be utilized to distinguish the coordination modes of the
carboxylate group. However, the carboxyl group in the ligand has exhibited the ν (COO) and
as
−
1
−1
ν (COO) at 1680 and 1291 cm , respectively (Δν= 389 cm ), whereas these vibrations in
s
−
1
−1
UoB-1 have represented at 1591 and 1299 cm , respectively (Δν= 292 cm ). With regard to
the Δν of UoB-1 was approximately close to the Δν of the ligand, it can be concluded that the

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carboxylate group coordinated to metal in the form of bridging [47]. Also, the broadband at
-1
3
414 cm is attributed to vibration of coordinated water molecules (Fig. S1).
The permanent porosity of UoB-1 was confirmed by nitrogen adsorption/desorption isotherm
and pore size distribution measurement (Fig. 3), and total pore volume was also determined
using the adsorption branch of N isotherm curve at the P/P0 = 0.99 single point. The sample
2
adsorbs N gas at 77 K, displaying a reversible typical IV isotherms characteristic of
2
mesoporous materials[48]. The pore size distribution derived from adsorption data and
calculated by the BJH method, the results indicate that the sample exhibits an average pore
3
-1
diameter at 29.34 nm(Fig. 3, inset). The total pore volume is 0.55 cm g and the apparent
2
-1
BET surface area 75 m g . The formation of mesoporosity in the sample can possibly be
attributed to 3D structure of UoB-1. The low surface area and broad pore size distribution of
UoB-1 can be due to framework interpenetration because of the length and flexibility of the
linker or pores of UoB-1 might be closed during the degassing process of N sorption and
2
desorption measurement.
ADS
0
.018
.009
0
3
00
50
0
0
1
1
10
rp/nm
100
ADS
DES
0
0.5
1
p/p0
Fig. 3: Experimental N adsorption/ desorption isotherm at 77 K for UoB-1
2
The size of the crystallites was too small for single-crystal structure determination. The
powder X-ray diffraction pattern of this material indicates the presence of a crystalline
structure and is very similar to the simulated pattern reported for IRMOF-74-IV[49],
confirming the formation of isostructure metal-organic framework (Fig S2).
The catalytic performance of UoB-1 nanostructures was subsequently assessed in the
oxidation reactions of the alcohols. For optimizing the oxidation reaction conditions, the
oxidation of benzyl alcohol (1 mmol) to benzaldehyde (2 mmol) with TBHP in the presence

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of the UoB-1 was selected as a model reaction. In initial studies were investigated the effect
of the various solvents as ethanol, ethylacetate, acetonitrile, dichloromthane, n-hexane and
the absence of any organic solvent using 3 mol % of the UoB-1 nanostructures catalyst for
the reaction conversion. The results indicated that solvent free condition was the best
selection, providing the desired product with higher yield (Fig. S3).
The model oxidation reaction was accomplished in ethanol for 120 min, in the presence of 3
mol% UoB-1 catalyst, at room temperature, 45 °C, 65 °C and 85 °C, respectively (Fig. S4).
As the results show, the reaction did not proceed at room temperature with good yields but
increasing the temperature to 45 °C led to a significant enhancement in the yield of product.
Increasing the reaction temperature to more than 45 °C was found to be undesirable for the
enhancing reaction time and the product yield. In fact, the performance of reaction at 65 °C
and 85 °C was led to producing benzoic acid besides benzaldehyde and therefore was
decreased the corresponding product yield.
In addition, the influence of the amount of catalyst on the proceed of the reaction was studied
(Fig. S5). The model reaction was performed at 45 °C under the absence of solvent for 120
min, in the presence of 1 mol%, 2 mol% and 3 mol% UoB-1 and TBHP (tert-Butyl
hydroperoxide) such as catalyst and oxidant, respectively. It was observed that increasing the
amount of catalyst led to a considerable enhancement in the product yield. The model
experiment confirmed that the desired product was not formed in the absence of the catalyst,
and it gave a moderate yield in the presence of TBHP.
In order to understand the amount of TBHP on the oxidation of benzyl alcohol, the model
reaction was examined at 45 °C without solvent in presence 3 mol 5% UoB-1 nanostructures
and the different amounts of TBHP (Fig. S6). The results of this study demonstrated the yield
of benzaldehyde enhanced simultaneously by the increasing of amounts of TBHP to 2 mmol.
The value higher than 2 mmol of TBHP did not improve the product yield due to over
oxidation and reduce selectivity.
Benzyl alcohol was subjected to the oxidation protocol using H O , NaIO and Oxone under
2
2
4
the catalytic influence of UoB-1 nanostructures in the solvent free condition at 45 °C, to
evaluate the oxidizing potential of other common oxidants (Fig. S7). Only small amounts of
the oxidation products were observed.
As a result, controlled experiments announced that the optimized reaction conditions were
recognized as using UoB-1 nanostructures (3 mol %), TBHP (2 mmol) at 45 °C without any
organic solvent. To explore the extent of the presented catalyst system, the oxidation reaction
of various alcohols was investigated under optimal reaction conditions. The obtained results

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summarized in Table 1 displayed that UoB-1 nanostructures was extremely active and highly
selective for the oxidation of a large variety substrates. In total, the results illustrated that
benzyl alcohols substituted with electron donating groups show higher reactivity than ones
substituted with electron-withdrawing groups. Benzyl alcohols containing hydroxyl,
methoxy, and nitro substituents could all be easily oxidized the corresponding benzaldehyde
with more than 80% conversion yield (Table 1, Entries 2-6). Gratifyingly, excellent yield was
maintained for the oxidation of halogen-substituted benzyl alcohols, while the relative
reactivity of halogen substituents was in the order: Br- > Cl- (Table 1, Entries 7- 10). It is
notable that the para positions of substituted on the phenyl ring were found to be a little more
active than the ortho positions. In addition to the primary benzylic alcohols, the secondary
alcohols such as 1-phenylethanol were also investigated in the current catalytic system and
good yields of the desired ketone were exclusively obtained. As expected, the secondary
alcohols, because of the more steric effects, were recognized to be moderate compared to the
primary benzylic alcohols (Table 1, Entries 11- 13).
a
Table 1: UoB-1 nanostructures catalyzed the oxidation reaction of various alcohols
b
Entry
1
Substrate
Product
Time (h)
2
Yield (%)
95
CHO
OH
OH
CHO
OH
2
3
4
2.5
2
90
93
80
OH
CHO
OH
HO
HO
CHO
NO2
OH
2.5
NO2
CHO
OH
5
6
7
8
9
2.5
1.5
1.5
2
85
93
90
91
90
O2N
MeO
O2N
CHO
OH
MeO
CHO
OH
Cl
Cl
CHO
OH
Cl
Cl
CHO
Br
OH
2
Br

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CHO
OH
1
1
0
1
2
85
80
Br
Br
OH
O
3
3
OH
O
1
1
2
3
75
78
OH
O
3
O
O
a
Reaction conditions: Alcohols (1 mmol), TBHP (2 mmol), UoB-1 (3 mol %) at 45 ° C and the absence of any
solvent
For commercial and industrial applications, recovery from the reaction medium and the
reusability of the catalyst is an imperative property of heterogeneous catalysts. Therefore, the
recovery and reusability of UoB-1 nanostructures were investigated in the multiple
successive oxidations of benzyl alcohol with TBHP under the present reaction conditions.
After the completion of the reaction, UoB-1 nanostructures were centrifuged and easily
separated from the reaction mixture, washed with EtOH, dried 1 h at 100 °C before using it in
the subsequent run under the same reaction conditions. The recovered catalyst was
successfully used for 6 consecutive reactions without significant loss of its activity. The
average isolated yield of benzaldehyde after 6 subsequent runs was 93.5, which clearly
represents practical reusability of the catalyst (Fig. S8a). The TEM image of UoB-1
nanostructures after being reused 6 runs displayed that the UoB-1 nanostructures remained
substantially unchanged, were still well dispersed. Also, no obvious aggregation of UoB-1
nanostructures was observed (Fig. S8b).
In order to investigate the heterogeneity of UoB-1 nanostructures, it was decided that the hot
filtration test was performed by taking benzyl alcohol under optimized reaction conditions.
For this reason, the oxidation reaction was stopped at 45% yield of benzaldehyde, and the
solid catalyst was separated from the mixture at the reaction temperature. Then, the filtrated
solution was retained for oxidation under the identical conditions. The results detected no
increasing product yield after the removal of catalyst from the reaction mixture. Inductively
coupled plasma-atomic emission spectrometer (ICP-AES) analysis of the liquid phase was
performed to find the amount of metal leached from the catalyst. The obtained results of ICP

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exhibited no perceptible amount of Cu in the liquid phase. This finding indicated UoB-1
nanostructures are stable under the applied reaction conditions.
A plausible mechanism for the alcohol oxidation catalyzed by UoB-1 is presented in the case
of the primary alcohol dehydrogenation in Scheme 3. In the proposed mechanism, the
radicals t-BuOO• is generated the metal-assisted, which the Cu (II) center is oxidized t-
BuOOH. In addition, the formed Cu (I) center is reduced t-BuOOH and provided the radicals
t-BuO•. The both of formed radicals behave as hydrogen atom abstractors from the alcohols
[
46].
Scheme 3: The plausible mechanism for the alcohol oxidation catalyzed by UoB-1
To establish the catalytic activity of the introduced catalyst in the present work (UoB-1
nanostructures), the oxidation reaction of benzyl alcohol as a model reaction in present UoB-
1
nanostructures was compared with the obtained results of other catalytic systems. As
indicated in Table 2, the reported methods, despite the high yield, suffer from some
disadvantages such as enhanced reaction temperatures, long reaction times and hazardous
organic solvents. On the other hand, the performance of some reported catalytic systems
required the use of specific conditions such as MW. As regards to the oxidation reaction in
the presence of UoB-1 nanostructures was performed at the relatively low temperature and
the absence of any organic solvent with high yield, this method could be more efficient and
more desirable in term of reaction time and conditions than other reported methods.
Table 2. Comparison of catalytic activity on oxidation of benzyl alcohol with previously reported catalysts
Catalyst
amount
Conditions
Time (h)
Yield (%)
Ref
Entry Catalyst
1
2
UiO-66-Sal-CuCl
Cu-MOF-2
2
4 mol %
17 mol %
CH
CH
3
CN/O
CN/O
2
/60 °C
/75 °C
24
16
99
99
[50]
[51]
3
2

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a
3
4
5
6
7
8
9
1
[{Cu(L1)- (DMF)}·DMF·H
2
O]
n
0.2 mol
2 mol %
3 mol %
5 mol %
2.5 mol %
2 mol %
15 mg
MW/TBHP/100 °C
CH CN/TBHP/60 °C
Toluene/air/110 °C
0.5
24
15
9h
12
8
81.1
88
98
94
89
99
80
95
[46]
[52]
[53]
[54]
[55]
[56]
[57]
[16]
This
work
b
[Co
Au@Cu(II)-MOF
Cu (BTC)
L(PTA)2.5(OAc)]
3
3
CH
CH
CH
CN/O
CN/O
CN/O
/70 °C
/70 °C
/75 °C
3
2
3
3
3
2
2
2
Cu-MOF-74
SPS–Cu(II)@Cu
(BTC)
2
3
MIL-53(Fe)-graphene
Pd@Cu(II)- MOF
CCl
/visible-light
9
4
0
1
5 mol %
Xylene/air/130 °C
25
1
UoB-1
3 mol %
SF/TBHP/45 °C
2
95
a
:
PTA: p-phthalic acid,
b
1
L : 5-{(pyridin-4-ylmethyl)amino} isophthalic acid
In summary, the novel porous UoB-1 nanostructure was synthesized using a new Schiff- base
as an organic linker via a simple method under moderate synthesis conditions. The obtained
UoB-1 nanostructures exhibited an excellent catalytic performance in the oxidation of
primary and secondary alcohols to the corresponding aldehydes and ketones under the
absence of any solvent. The solvent-free conditions contrast of using of organic solvent
afforded the some of the advantages because it was safe, economic, environmental and non-
toxic. The nanomorphology of synthesized catalyst increased the dispersion due to enhanced
catalytic reactivity. More importantly, the UoB-1 nanocatalyst could be recycled and reused
for six runs without any significant loss of catalytic performance which confirmed a high
stability of the catalyst. Therefore, the UoB-1 nanostructures can be considered as a
heterogeneous, green and efficient catalyst for the oxidation reaction of alcohols.
Acknowledgements
We are thankful to the University of Birjand Research Council for support of this work.
Appendix A. Supplementary data
Experimental details and additional figures.
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Graphical abstract:
A Nanoscale Cu-Metal organic framework with Schiff base ligand: Synthesis,
characterization and investigation catalytic activity in the oxidation of alcohols
a
a
a
Sima Aryanejad , Ghodsieh Bagherzade * , Alireza Farrokhi
TBHP, Solvent Free

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Highlights



A new Cu- MOF nanostructures were synthesized and fully characterized
Solvent-free oxidation of benzyl alcohol derivatives with t-BuOOH
The reusability of the catalyst was examined