Ag-NPs embedded in two novel Zn3/Zn5-cluster-based metal-organic frameworks for catalytic reduction of 2/3/4-nitrophenol

Article abstract of DOI:10.1039/c7dt00024c

By utilizing symmetrical pentacarboxylate ligands, 3,5-di(2′,5′-dicarboxylphenyl)benzoic acid (H₅L1) and 3,5-di(2′,4′-dicarboxylphenyl)benzoic acid (H₅L2), two novel porous Zn-MOFs, [Zn₅(μ₃-H₂O)₂(L1)₂]·3DMA·4H₂O (CTGU-3) and [Zn₃(μ₃-OH)L2(H₂O)₃]·H₂O (CTGU-4) have been synthesized under solvothermal conditions. CTGU-3 and CTGU-4 exhibit 3D microporous frameworks with flu and dia topologies and possess unique secondary building units [Zn₅(μ₃-H₂O)₂(RCO₂)₆] and [Zn₃(μ₃-OH)(RCO₂)₃], respectively. Such porous systems create a unique space or surface to accommodate Ag nanoparticles (Ag NPs), which could efficiently prevent Ag NPs from aggregation and leaching. In this work, two new Ag@Zn-MOF composites, denoted as Ag@CTGU, have been successfully fabricated through solution infiltration, for the reduction of nitrophenol. Compared with CTGU-4, CTGU-3 shows enhanced catalytic efficiency toward the reaction when it is used as a catalyst support of Ag NPs. Moreover, gas sorption and luminescence properties of two compounds were also investigated.

Full text of DOI:10.1039/c7dt00024c

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ISSN 1477-9226
PAPER
Joseph T. Hupp, Omar K. Farha et al.
Efficient extraction of sulfate from water using
framework
a Zr-metal–organic
rsc.li/dalton

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ARTICLE
Ag-NPs embedded in two novel Zn /Zn -cluster-based metal-
3
5
organic frameworks for catalytic reduction of 2/3/4-nitrophenol
a
a
a
a
a
a
Xue-Qian Wu, Dan-Dan Huang, Zhi-Hang Zhou, Wen-Wen Dong, Ya-Pan Wu, Jun Zhao,
a
b
c
Dong-Sheng Li, * Qi-Chun Zhang * and Xianhui Bu
Received 00th January 20xx,
Accepted 00th January 20xx
By utilizing symmetrical pentacarboxylate ligands, 3,5-di(2',5'-dicarboxylphenyl) benozoic acid (H L1) and 3,5-di(2',4'-
5
dicarboxylphenyl) benozoic acid (H
OH)L2(H O) ]·H O (CTGU-4) have been synthesized under solvothermal condition. CTGU-3 and CTGU-4 exhibit 3D
microporous frameworks with flu and dia topologies and possess unique secondary building units [Zn (µ -H O) (RCO ) ]
5 5 3 2 2 2 2 3 3
L2), two novel porous Zn-MOFs, [Zn (µ -H O) (L1) ]·3DMA·4H O (CTGU-3) and [Zn (µ -
DOI: 10.1039/x0xx00000x
2
3
2
www.rsc.org/
5
3
2
2
2 6
3 3 2 3
and [Zn (µ -OH)(RCO ) ], respectively. Such porous systems create a unique space or surface to accommodate Ag
nanoparticles (Ag NPs), which could efficiently prevent Ag NPs from the aggregation and leaching. In this work, two new
Ag@Zn-MOFs composites, denoted as Ag@CTGU, have been successfully fabricated through solution infiltration, for the
reduction of nitrophenol. Compared with CTGU-4, CTGU-3 shows the enhanced catalytic efficiency toward the reaction
when it was used as a catalyst support of Ag NPs. Moreover, gas sorption and luminescent properties of two compounds
were also investigated.
room left for the improvement of their efficiency. In most situations,
the use of Ag NPs is mainly limited by its high cost and conglobation
Introduction
7
in the catalytic process. One possible solution is to reduce the
Nitrophenol and its homologous series have been widely
considered as one of the most prevalent organic pollutants in
usage of Ag via employing porous materials as a support to disperse
particles, More importantly, such arrangement would largely
improve its conglobation phenomenon. Moreover, the porous
structure of the support is beneficial to the separation of substrates
1
industrial liquid wastes. Even at low concentrations, nitrophenol
still causes detrimental effects to the environment and human
2
health. Thus, it is extremely importment to remove these wastes
8
and products. Although traditional porous materials, such as
from surrounding efficiently and timely. Among all traditional
methods(e.g. ozonation, adsorption, biodegradation and catalytic
mesoporous silica, activated carbon and zeolites, have been
9
,10
3
extensively investigated in the field of catalysis, it is very tedious
to prepare these materials with uniform pores and tune the pore
sizes. Thus, developing new suitable supports for preparation of the
metal-in-pore catalysts still faces many challenges.
degradation ) to treat such these wastes, catalytic degradation has
been demonstrated to be as a more effective and economical
approach not only because this method is feasible, but also because
this method could produce many important industrial raw materials
such as 4-aminophenol (4-AP) and its homologous series, 2-
aminophenol (2-AP) and 3-aminophenol (3-AP) via the reduction of
Recently, metal-organic frameworks (MOFs) have been
demonstrated to represent
a new class of permanently
4
microporous materials, which are unique in terms of their
extraordinarily high porosities, tunable pores, and diverse
nitrophenol over noble metal NPs in the presence of KBH4.
However, developing novel noble metal catalysts to realize this type
of reactions with high efficiency, convenient operation and
1
1
functional sites. Such unique features have enable MOFs to exhibit
great potentials for a broad range of applications, including gas
storage, chemical separation, chemical sensing, and heterogeneous
5
economical rewards is extremely important. Although previous
studies have reported that silver nanoparticles (Ag NPs) can be
12-14
catalysis.
6
Over the past years, porous MOFs materials usually
used as catalyst to carry out above reactions, there is still much
come to be known as a potential candidate for gas separation and
1
5
storage. Moreover, MOFs have been actively employed as host
matrices because the incorporation of functional species into their
pores can add new properties to MOFs due to the guest-host
a.
College of Materials and Chemical Engineering, Collaborative Innovation Center
for Microgrid of New Energy of Hubei Province, Key Laboratory of Inorganic
Nonmetallic Crystalline and Energy Conversion Materials,China Three Gorges
University, Yichang 443002, P. R. China. Tel./Fax: +86-717- 6397506; E-mail
address: lidongsheng1@126.com (D.-S. Li).
School of Materials Science and Engineering, Nanyang Technological University,
Singapore 639798, Singapore. E-mail address: qczhang@ntu.edu.sgc.(Q. C. Zhang)
Department of Chemistry and Biochemistry, California State University, Long
Beach, 1250 Bellflower Boulevard, Long Beach, CA 90840, USA.
1
6
synergistic effect. Given these advantages, MOFs have been
proved to be ideal candidates as host-materials to capture noble
b.
c.
metal nanoparticles to limit their migration and aggregation, due to
17,18
the rigid porous structures of MOFs.
Clearly, continuing to work
on this direction would not only help to promote the development
of this field but also develop new strategies to prepare these
†
Electronic Supplementary Information (ESI) available: bond length/angle tables, ,
additional figures and tables. Adsorption isotherm, fluorogram, TGA, FT-IR, UV-Vis
spectra and PXRD patterns. See DOI: 10.1039/x0xx00000x
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composite materials as well as the fundamental researches analysis (%): calcd for CTGU-3 (C58
including the growth mechanism of nanoparticles in the confined 2.65; found: C 43.12, H 3.46, N 2.40. FT-IR (KBr, cm ) (Fig. S1, ESI†):
space and synergetic effect between subject and object.
3440 (s), 1620 (s), 1600 (s), 1490 (s), 1410 (s), 1270 (m), 1020 (w),
In this work, we successfully prepared two microporous MOFs, 910 (m), 775 (m).
(µ -H O) (L1) ]·3DMA·4H O (CTGU-3, CTGU = China Three
Gorges University) and [Zn (µ -OH)L2(H O)
O (CTGU-4) by Synthesis of [Zn
choosing 3,5-di(2',5'-dicarboxylphenyl) benozoic acid (H L1) and
,5-di(2',4'-dicarboxylphenyl) benozoic acid (H L2) as symmetrical
pentacarboxylate ligands (Scheme 1) and Zn salt as metal sources. 3 by using H
Structural analysis reveals that two compounds consist of two obtained in 56% based on H
57 3 5
H N O29Zn ): C 43.89, H 3.62, N
-1
[Zn
5
3
2
2
2
2
(µ -OH)L2(H O) ]·2H O (CTGU-4)
3 3 2 3 2
3
3
2
3
]·H
2
5
The preparation of CTGU-4 product was similar to that of CTGU-
L2 in place of H L1. Colorless crystals of CTGU-4 were
L2. Elemental analysis (%): calcd for
3
5
5
5
5
different unequal SBUs: [Zn
OH)(RCO
5
(µ
3
-H
2
O)
2
(RCO
2
)
6
] SBUs and [Zn
3
(µ
3
-
CTGU-4 (C23
H
20
O
15Zn
3
): C 37.70, H 2.75; found: C 36.90, H 2.72. FT-
-1
†
2
)
3
] SBUs, and possess multiple pores, which have been IR (KBr, cm ) (Fig. S2, ESI ): 3450 (s), 1620 (s), 1410 (s), 1390 (s),
used to embed Ag NPs through solution infiltration.The as-prepared 1360 (s), 1280 (m), 1170 (w), 1020 (w), 914 (m), 781 (s).
composite catalysts (Ag@CTGU-3 and Ag@CTGU-4) show
outstanding catalytic activities toward the reduction of nitrophenol. Synthesis of Ag@CTGU
The composite catalysts were prepared according to
a
1
9
previously reported method. To load Ag precursors into the
channel/surface of CTGU-3, polycrystalline samples (20 mg) were
immersed into an aqueous solution of AgNO (20 mg/3 mL) for 24h
3
and vacuum-dried at 273 K. During the period of preparation,
AgNO solution was refreshed three times. After filtration, Ag-
3
CTGU-3 was rinsed and soaked in distilled water to remove
dissociative AgNO . Then, 3 ml ethanol was added into the system
3
as a reducing agent. This mixed solution was kept for another 10h.
Eventually, the composite material Ag@CTGU-3 was obtained and
confirmed by XPS and HRTEM measurements. Ag@CTGU-4 was
prepared by replacing CTGU-3 with CTGU-4.
Scheme 1. Chemical structures of ligands
Gas sorption measurements
Experimental section
2 2
N and CO isotherms were collected using an ASAP 2020
Materials and general methods
surface area and pore size analyzer in a clean ultra-high-vacuum
system. Approximately 120 mg of solvent-exchanged sample was
loaded into the sample basket within the adsorption instrument
All reagent used in the experiment were commercially available
without further purification. Powder X-ray diffraction (PXRD) was
studied on a Rigaku Ultima IV diffractometer (Cu Kα radiation, λ =
o
and then degassed under dynamic vacuum at 100 C for 6h to obtain
the fully desolvated sample. Volumetric N
measurements were performed over the pressure range 0-1 bar at
7K and 298K, respectively.
2 2
and CO sorption
1
.5406 Å). Thermogravimetric (TG) curves were operated on a
o
−
1
NETZSCH449C thermal analyzer with a heating rate of 10 C min
7
under air atmosphere. FT-IR spectra (KBr pellets) were conducted
on a Thermo Electron NEXUS 670 FTIR spectrometer. Elemental
analyses were performed on a PerkinElmer2400 Series II analyzer.
The solid state luminescent spectra and emission lifetime were
recorded by the Edinburgh FLS55 luminescence spectrometer at
ambient temperature. The UV−vis spectra for samples were
obtained on a Shimadzu UV 2550 spectrometer. X-rayphotoelectron
spectrometry (XPS) was carried out on an ESCALABMKLL X-ray
photoelectron spectrometer by using an Al Kα source. High-
resolution Transmission electron microscope (HRTEM) images were
taken by a JEOL JEM 2010F at an accelerating voltage of 200 kV.
Catalytic measurements
In the reduction of nitrophenol, a desired amount of Ag@CTGU
powder (1 mg) was added to 3 ml nitrophenol aqueous solution, in
which the concentration was 14 mg/L (4-NP), 60 mg/L (2-NP) and 60
mg/L (3-NP), separately. The reaction was started by adding 3 mg
4
KBH into the reactor. At desired time intervals, the absorbance at
concerted wavelength was measure by utilizing the UV-vis
20
spectrophotometer.
Crystal structure
Synthesis of [Zn
5
(µ
3
-H
2
O)
2
(L1)
2
] (CTGU-3)
The diffraction data for CTGU-3/4 was collected on a RigakuXtaLAB
A mixture of Zn(NO
3
)
2
ꢁ6H
2
5
O (0.04 mmol, 11.9 mg), H L1 (0.04
mini diffractometer with graphite monochromated Mo Kα radiation
mmol, 18.0 mg) and DMA/H O (4 ml/4 ml) was sealed in a 25 ml
2
(
λ = 0.71073 Å). The structures were solved by direct method and
o
Teflon-lined stainless steel vessel, heated to 120 C for 72h, and
2
refined by a full-matrix least-squares refinement on F with SHELXTL
then cooled to room temperature over 24h. Colorless crystals of
21
and Olex2. All non-H atoms were refined anisotropically. In the
CTGU-3 were obtained. Yield: 75% based on H L1. Elemental
5
two structures, solvent molecules are highly disordered, therefore,
2
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the SQUEEZE routine of PLATON is used to remove the diffused to four carboxylato-O atoms from two independent ligands and two
electron densities resulting from solvent molecules. The final oxygen atoms from water ligands, while Zn2 and Zn3 are linked with
formulation of CTGU-3 and CTGU-4 were calculated from the three carboxylato-O atoms from three different ligands and one
SQUEEZE results combined with TGA analysis. Detailed oxygen atom from water ligand. Therefore, Zn1 atom adopts a six-
crystallographic data are summarized in Table 1. Selected angles coordinated mode to form a octahedron geometry, while, Zn2 and
Zn3 bond to four oxygen atoms to form a tetrahedron. More
and bond lengths are listed in Table S1 (ESI†). The crystal structures
5
-
Interestingly, through the linkage of six carboxylates of L1 and two
central O atoms, five Zn ions are bonded together to generate a
of two compounds have been deposited and CCDC numbers are
510773 and 1510774. These data can be obtained free of charge
1
poly [Zn
5
(µ
3
-H
2
O)
2
(RCO
2
)
6
] cluster, acting as secondary building unit
L1 ligand adopts
4
–(η )-(η )-(η )-(η )-(η ) coordination mode to connect metal
via Http://www.ccdc.cam.ac.un/conts/retrieving.html.
(
SBU) in this the structure (fig. 1a). Notably, each H
5
2
1
1
2
2
a ꢀ
Table 1. Crystal data and structure refinements for CTGU-3 and CTGU-4
clusters (fig. 1d). Every SBU is connected with the surrounding eight
SBUs by the linkage of five ligands, which could be considered as a
Compound
Formula
CTGU-3
CTGU-4
5
-
8
-connected node. Meanwhile, L1 anion could be viewed as a 4-
C
58
H
57
N
3
O
29 Zn
5
23 20 3
C H O15 Zn
connected node. Thus, the overall structure of CTGU-3 is 3D (4,8)-
1
2
12
4
6
Formula mass
1587
731
orthorhombic
Pmn2
2
flu network with the point symbol of (4 ·6 ·8 )(4 ) . It is
noteworthy that the as-obtained (4,8)-connected frameworks are
also relatively rare compared to the classical topologies of diamond,
Crystal system
triclinic
P -1
2
2
NbO, and PtS etc. With the expansion of such SBUs, it can be
speculated that more porous MOFs with novel SBUs and topologies
could be synthesized.
Space group
a/ Å
1
12.194(6)
12.647(6)
12.699(6)
83.837(11)
83.660(13)
77.272(12)
1891.7(16)
2
20.137(11)
10.702(6)
11.418(6)
90.00
90.00
90.00
2461(2)
2
CTGU-4 crystallizes in the orthorhombic system with Pmn2
space group. The asymmetric unit is composed of one and a half Zn
1
b/ Å
5
-
ions, half a L2 ligand, one and a half coordinated water molecule
and a half of hydroxyl specie. In the structure, two Zn cations
including Zn1 and Zn2, occupancy rates are 1 and 0.5, which are
coordinated by carboxylato-O, hydroxyl-O and water-O, show
octahedron and tetrahedron coordination geometries, respectively.
c /Å
α/°
β/°
More importantly, a trimeric [Zn
similar to CTGU-3, serving as SBU in this structure (Fig. 2a). The H
ligand in CTGU-4 is also completely deprotonated, which possesses
one type of coordination mode: H L2 acts as a connector to link
3
(µ
3
-OH)(RCO
2
)
3
] cluster, which is
γ/°
5
L2
3
V/ Å
5
2
Z
1
1
2
2
four metal clusters with the ꢀ
mode. From a topological perspective, every SBU could be defined
as a 4-connected node, and the H L2 could also be corresponded to
4
–(η )-(η )-(η )-(η )-(η ) coordination
-1
D
calcd /g cm
1.100
0.960
1.488
710
5
-1
µ/mm
1.615
a 4-connected vertex, finally, constructing a porous 3D network
with dia topology (Fig. 2f). A synthetic and structural comparison of
CTGU-3 and CTGU-4 demonstrates that the positional
heterogeneity of ligands have a profound impact on the final
structure of MOFs.
F [000]
624
Independent refls.
6492
4084
No. of parameters
331
193
Previous research has been confirmed that SBUs can be used as
building units instead of single metal ions in the MOFs
a
R
1
(I >2σ(I))
)(I >2σ(I))
0.0496
0.1341
2
0.0410
0.1131
1/2
23
engineering. As an effective strategy, SBUs undoubtedly help to
b
shed light on the prediction, design, and synthesis of the target
product, in which, SBUs are established under the appropriate
chemical conditions. Up to now, many famous framework materials
such as MOF-5, UIO-66, MIL-101, and HKUST-1 have been
synthesized base on SBUs and usually consist of two, three or more
metal centers. In this work, two distinct SBUs, consisting of three
and five metal centers, have been successfully directed to generate
two novel Zn-MOFs. Note that both SBUs were assembled under
the same temperature, solvent, ration of reactant and pH value,
indicating that the ligand with carboxyl group in a different location
is the main reason for the structure differences between CTGU-3
and CTGU-4.
wR(F
2
a
b
2
2
2 2
1 o c o 2 o c o
R =∑||F |-|F ||/∑|F |. wR =[∑w(F -F ) /∑w(F ) ] .
Results and discussion
Crystal structure description for CTGU-3 and CTGU-4
Single-crystal X-ray diffraction analysis revealed that CTGU-3
crystallizes in the triclinic system with P-1 space group. The
minimum asymmetric unit contains two and
a
half
5
-
crystallographically independent Zn centers, one complete L1
Actually, several microporous metal-organic frameworks
ligand and one coordinated water molecule. Zn1 ion is coordinated
(
MMOFs) have been reported in previous literature, in which the
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1
1
5 5
ligand is isometric with H L1 and H L2. Liu et al. utilized a similar property of gas mixture (The coordination mode of ligand is (η :η -
1
1
1
1
1
1
25
).
pentacarboxylate ligand to prepare two anionic MMOFs, JLU-Liu5
ꢀ
2
)-(η :η -ꢀ
2
)-(η :η -ꢀ
2
)-(η :η -ꢀ
2
)-ꢀ
8
Combined with above
and JLU-Liu6, based on rare ternary SBU (The coordination mode of examples, it is clear that the location of functional groups in similar
1
2
1
1
1
1
1
1
1
2
24
ligand is (η :η -ꢀ
Qian groups also prepared a novel MMOF, ZJU-72, which possesses structure.
paddle-wheel Cu (CO SBU and shows prominent separating
3
)-(η :η -ꢀ
2
)-(η :η -ꢀ
2
)-(η :η -ꢀ
2
)-(η :η -ꢀ
3
)-ꢀ12).
ligands can produce profound influence on the final SBU and MOF
2
2 4
)
Fig. 1 (a) Coordination environments of the Zn ions and [Zn
-z; #4 = x, y, 1+z. The hydrogen atoms are omitted for clarity. (b), (e) View of the novel 3D frameworks of CTGU-3 along the a axis. (d) Defined a 4-
connected node based on SBUs. (c), (f) Schematic representation and natural tiling of the (4,8)-connected flu network of CTGU-3.
5 3 2 2 2 6
(µ -H O) (RCO ) ] SBU in CTGU-3. Symmetry code: #1 = 2-x, 1-y, 1-z; #2 = x, 1+y, z; #3 = 1-x, 1-y,
1
3 3 2 3
Fig. 2 (a) Coordination environments of the Zn ions and [Zn (µ -OH)(RCO ) ] SBU in CTGU-4. Symmetry code: #1 = -x, y, z; #2 = -x+1/2, 2-y, 1/2+z; #3 = x, 1+y,
z. The hydrogen atoms are omitted for clarity. (b), (e) View of the novel 3D frameworks of CTGU-4 along the a axis. (c), (f) Schematic representation and
natural tiling of the (4,4)-connected dia network of CTGU-4.
4
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o
o
Sorption properties
(calcd: 16.40%). The third step is from 315 C to 500 C, where the
L1 began to decompose with the weight loss of 46.8% (calcd:
H
5
o
o
It is noteworthy that CTGU-3 has one dimensional (1D)
rectangle shape channels with dimensions of approximately 18.9 Å
5
0.18%). For the latter, the weight loss between 60 C and 140 C
corresponds to the release of lattice water and coordinated water
molecules (obsd: 12.20% and calcd: 12.30%). The removal of
×
16.9 Å along the a axis (Fig. 1e) and two other channels along
o
the b and c axis. Whereas, there are only one kind of channel
belongs to CTGU-4 with dimensions of around 16.9 Å × 11.7 Å
along the a axis (Fig. 2e).
organic components occurs at 310 C.
Luminescent properties
The total accessible volume of two compounds is ca. 50.2%
and 59.5% respectively, calculated by using the PLATON
Two compounds are assembled from luminescent rigid ligands
26
10
program. In virtue of the high accessible volume, and prominent
pore structure, we investigated their adsorption performance for
and d configuration ions of Zn, therefore, the solid-state
5 5
photoluminescent spectra of two compounds, free H L1 and H L2
N
2
at 77 K and CO
2
at 298 K. The N
2
sorption isotherm of CTGU-3
ligands were measured at room temperature. For CTGU-3, excited
at 325 nm, it gives rise to an emission band at 435 nm (Fig. S10,
ESI†). The emission spectrum of CTGU-4 exhibits an emission band
at 405 nm nearby with excitation maximum at 310 nm (Fig. S11,
reveals typical reversibe type-I sorption behavior, which
represents the characteristic of microporous materials,
2
corresponding to a BET surface area of 639.63 m /g (Langmuir
2
surface area of 928.91 m /g) (Fig. 3). CTGU-4 was also investigated
5 5
ESI†) and the maximal emission peaks of free H L1 and H L2 ligand
by adsorption-desorption isotherm measurements, as expected,
obtaining no appreciable absorption data (Fig. S3, ESI†), which
indicated that CTGU-3 and CTGU-4 have differences within pore
structure.
appear at 437 (λex = 390 nm) and 470 nm (λex = 400 nm),
respectively (Fig. S8,S9, ESI†). Compared with that of free ligands,
the emission bands of CTGU-4 is blue-shift, which should be
27
ascribed to the metal-ligand coordinative interactions. The
emission of CTGU-3 and CTGU-4 can probably be assigned to the
intraligand transfer. Apparently, the spectral differences between
CTGU-3 and CTGU-4 are associated with the structure disparity,
28
which has been reported in previously literature. Besides, the
emission lifetime of two compounds are 4.11 ns and 3.20 ns (Fig.
S12, 13 ESI†).
Catalysis activities
As stated, composite catalysts were produced according to the
1
9
related literature. To get a further insight into the structure of
Ag@CTGU, high-resolution transmission electron microscopy
(HRTEM) was used to investigate the dispersion and size
distribution of the Ag NPs in the channel or on the surface. HRTEM
images revealed that the AgNPs were crystalline and highly
dispersed with an average particle size of 4±2 nm (Ag@CTGU-3)
and 6 ± 2nm (Ag@CTGU-4) (Fig. 4a, 4d). Although the particles
measured by TEM are larger than the pore size of CTGU, the
porous structure may still offer steric restriction to confine and
prevent the growth of Ag NPs. As shown in Fig. 4b and Fig. 4e,
two images clearly display a lattice fringe with an interplanar
distance of 0.23 and 0.20 nm, corresponding to (111) and (200)
lattice plane of face center cubic Ag. Meanwhile, X-ray
photoelectron spectroscopy (XPS) were operated to confirm the
existence of Ag (Fig. 4c, 4f), there are two specific peaks with
binding energies of 369 and 375 eV due to the Ag 3d5/2 and Ag
2 2
Fig. 3 N and CO sorption isotherms for CTGU-3 at 77 K (298 K).
PXRD and thermal analysis
To verify the phase purity of the bulky materials, X-ray power
diffraction (PXRD) experiments have been carried out. The PXRD
experimental and computer-simulated patterns are in good
agreement with each other, indicating phase purity of the as-
synthesized products (Fig. S4 and Fig. S5, ESI†). Additionally,
thermogravimetric analysis of CTGU-3 and CTGU-4 has been
0
o
3d3/2 electrons of Ag .
performed in the temperature range of 30-800 C. The TGA curves
The ease of the synthesis of composite catalysts based on well-
dispersed AgNPs provides opportunities for applications,
especially with respect to the catalytic reduction of nitrophenol.
Meanwhile, the degradation of nitrophenol in aqueous solutions is
often chosen as a model reaction to study the catalytic
performance of composite materials. Thus, in order to research
the catalytic activity of Ag@CTGU-3 and Ag@CTGU-4, the
degradation experiment was conducted in a typical way, in which
of CTGU-3 and CTGU-4 are similar and present two main steps of
weight loss corresponding to the loss of coordinated water
molecule, solvent molecules and decompose of organic ligands.
o
CTGU-3 shows the first mass loss of 6.20% below 149 C due to the
release of the coordinated water and lattice water molecules
(
calcd: 6.80%). The second step displays a weight loss of 16.20%
o
o
from 160 C to 287 C, indicating the departure of DMA molecules
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4
-NP and its isomerides were chosen as reaction substrates.
Generally, the aqueous solution of 4-NP, 2-NP and 3-NP shows
a strong absorption peak at 317, 277 and 272 nm. After the
addition of KBH , the absorption peak of nitrophenol red-shifted
Table 2 Catalytic activities of Ag@CTGU for the reduction reaction
4
reaction substrate
Catalysts
to 400, 390 and 414 nm, respectively, which corresponded to a
color change of light yellow to yellow-green due to the formation
4-NP
2-NP
3-NP
2
9
of nitrophenolateion. Besides, each of three nitroaromatics
exhibits a negligible change in the adsorption spectroscopy after
-1 -1
-1 -1
-1 -1
Ag@CTGU-3
Ag@CTGU-4
8.64s g
3.33s g
4.50s g
-
1
-1
-1 -1
8.50×s g
-1 -1
1.58s g
3.03s g
4 4
the addition of KBH , indicating that KBH itself has no catalytic
activity for the reaction. However, when the as-prepared catalysts
were added, the absorption of substrates significantly decreases
at the monitored wavelength. Ultimately, for Ag@CTGU-3,
Fig. 4 (a), (b) are the TEM images of Ag@CTGU-3, (d), (e) for Ag@CTGU-4. (c), (f) X-Ray photoelectron spectroscopic (XPS) analysis of Ag@CTGU.
three nitroaromatics were decomposed completely in the
presence of catalysts and KBH within the time of 8 min to 11 min,
To study the reduction rate of nitrophenol over the different
composite catalysts, the kinetics of each reaction were further
investigated. As shown in Fig. 5, in each case, liner relationship
4
while 20-26 min for Ag@CTGU-4. Interestingly, under normal
circumstances, the absorbance of the reaction mixture at 400 nm
gradually decreased as the reaction proceeded, along with a
concomitant increase of the 300 nm peak corresponding to 4-
aminophenol. Nevertheless, the characteristic peak of 4-
aminophenol did not appear when Ag@CTGU was used as the
catalyst, presumably as a result of the formation of intermediate
t 0
between ln(C /C ) and reaction time is obtained, implying that
such a catalytic reaction could be of pseudo-first-order reaction,
31
which has been observed in several similar catalytic progress.
The related value of k was calculated from the slope as
summarized in Table 2. For a quantitative comparison, the activity
’
32
parameter k =k/M was introduced, where M is the total mass of
30
products in the limited pore space of CTGU. In the control
experiment, the CTGU support shows no catalytic activity towards
the target reaction. Furthermore, to test the recyclability of
Ag@CTGU, catalyst was recovered from the reaction mixture by
filtration, washed with distilled water, and reused directly for the
next run under the same conditions. Finally, the catalyst can be
successfully recycled and reused for up to three times (Fig. S17,
S18 ESI†).
the catalyst added in the reaction. Thus, the reaction rate
-1
-1
g
constants per unit mass were calculated to be 8.64 s
-1 -1
(Ag@CTGU-3) and 3.03 s g (Ag@CTGU-4) for the reduction of 4-
NP, respectively. According to the literature, Au/ZSBA-PL catalyst
and the Ag/POM-2 composites have good activity parameters of
-1
-1
33
about 2.36 and 3.69 s g respectively, which is superior to some
other catalysts measured under similar conditions. (Table. S2,
ESI†). Obviously, in this work Ag@CTGU-3/4 composites show
excellent catalytic activities for the reduction of nitrophenol.
6
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The results revealed that both catalysts exhibited outstanding
catalytic activities due to the pore structure of their support and
highly dispersed Ag NPs, allowing effective mass transfer process.
Compared with Ag@CTGU-4, Ag@CTGU-3 shows the enhanced
catalytic efficiency, which might be attributed to the size-
dependent catalytic property of Ag NPs and the surface area of
support (A smaller Ag NPs would possess faster elector transfer
rate on their surface, a higher surface area would guarantee the
diffusion rate of substrate). Although we have demonstrated that
support could be a key factor in the catalytic processes, there is
still a long way to understand the nature of this effect.
adsorbed by the CTGU support, At meanwhile, borohydride ions
react with the Ag NPs in the Ag@CTGU composite material and
transfer active hydrogen and electrons to them, which result in
-
the electron transfer takes place from BH
4
to 4-NP through
adsorption the nitrophenol molecules onto the catalyst surface at
a later stage. Thus, the catalytic efficiency is highly dependent on
the size of Ag NPs and the contacting opportunity between
catalyst and reactant. Compared to nanoporous substrates, the
permanent porosity of the CTGU can promote the transport of 4-
NP and 4-AP. Besides, the strong interaction between Ag NPs and
the support also can prevent the agglomeration of Ag NPs. This
makes the Ag NPs is more accessible for the substrate.
In accordance with the above experimental results and
traditional theory about the catalytic reduction of nitrophenol by
Ag NPs, we propose a possible catalytic mechanism pathway for
3
4
the reaction (Fig. 6). Taking 4-NP as an example, nitrophenol is
Fig. 5 (a) UV-vis spectra showing gradual reduction of 4-NP, 2-NP (c) and 3-NP (e) over Ag@CTGU-3 and Ag@CTGU-4 (b, d, f). Insert: the relationship
between ln(C /C ) and reaction time (t).
t
0
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H
2
O)
2
(RCO
2
)
6
] SBUs. Similarly, CTGU-4 presents a porous MOF with
3 3 2 3
dia topology, which possesses [Zn (µ -OH)(RCO ) ] SBUs and 1D
channels along a axis. Gas-sorption measurements for two
compounds reveal that CTGU-3 has a considerable surface area
2
(
Langmuir 928.91 m /g) and big differences compared to CTGU-4
within pore system. More importantly, our work demonstrated
that solution infiltration of two different Zn-MOFs with AgNO
3
results in uniformly distribution of AgNPs with size related to the
MOF structure and pore dimensions. Catalytic experiments
indicated that two composite catalysts, Ag@CTGU-3 and
Ag@CTGU-4, show different activities during the progress, which
might be attributed to the wide variations caused by the support.
Therefore, it has been confirmed that MOFs can be elegantly
employed as hosts to provide solid catalysts with NPs size and
catalytic activities regulatable based on their crystalline pore
structure or surface. Currently, further efforts on the synthesis of
porous MOFs based on SBUs and the application in solid catalysts
support are underway.
Fig. 6 Mechanism of the catalytic deduction of nitrophenol with the
Ag@CTGU.
Conclusions
In summary, two novel 3D metal-organic frameworks with Zn
nodes and pentacarboxylate linker have been constructed under
solvothermal conditions and the as-prepared material can be
employed as a catalytic support of Ag NPs. CTGU-3 features a 3D
framework with flu topology based on H L1 ligand and [Zn (µ -
5
5
3
8
(a) N. Wang, Q. M. Sun, R. S. Bai, X. Li, G. Q. Guo and J. H. Yu,
J. Am. Chem. Soc., 2016, 138, 7484; (b) Y. B. Huang, M. Shen,
Acknowledgements
X. S. Wang, P. C. Shi, H. F. Li and R. Cao, J. Catal., 2015, 330
4
Janiak, S. C. Mu, G. Tian, M. Pan, G. V. Tendelood and B. L.
Su, Chem. Commun., 2016, 52, 8219.
,
52; (c) J. Ying, Z. Y. Hu, X. Y. Yang, H. Wei, Y. X. Xiao, C.
This work was financially supported by the NSF of China (Nos:
1373122, 21673127, 21671119, 51572152, 51502155), the NSF
2
of Hubei Province of China (No. 2014CFB277).
9
1
C. Q. Wang, Z. R. Zhang, G. Yang, Q. Chen, Y. D. Yin and M. S.
Jin, Nano Lett., 2016, 16, 5669.
0 A. Srebowata, R. Baran, G. Slowik, D. Lisovytskiy and S.
Dzwigaj, Appl. Catal. B:Environ., 2016, 199, 514.
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Hua and X. H. Bu, Chem. Commun., 2016, 52, 8501; (e) H. X.
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Graphical Abstract
Ag-NPs embedded in two novel Zn /Zn -cluster-based metal-organic frameworks for
3
5
catalytic reduction of 2/3/4-nitrophenol
a
a
a
a
a
a
a
Xue-Qian Wu, Dan-Dan Huang, Zhi-Hang Zhou, Wen-Wen Dong, Ya-Pan Wu, Jun Zhao, Dong-Sheng Li, * Qi-
b
c
Chun Zhang * and Xianhui Bu
Two novel microporous Zn-MOFs consist of two different unequal SBUs: [Zn
5
3 2 2 2 6
(µ -H O) (RCO ) ] SBUs and
[
Zn (µ -OH)(RCO ) ] SBUs and possess multiple pores, which have been used to embed Ag NPs through
3
3
2 3
solution infiltration. The resulted composite catalysts show outstanding catalytic activities toward the
reduction of nitrophenol.
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