A bifunctional cationic metal-organic framework based on unprecedented nonanuclear copper(ii) cluster for high dichromate and chromate trapping and highly efficient photocatalytic degradation of organic dyes under visible light irradiation

Article abstract of DOI:10.1039/c8dt01685b

A bifunctional cationic metal-organic framework {[Cu₉(OH)₆Cl₂(itp)₆(1,4-bdc)₃](NO₃)₂(OH)₂·20H₂O}_n (1-NO₃-OH·20H₂O) was synt

Full text of DOI:10.1039/c8dt01685b

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M. Li, Z. Wang, K. Li, Y. Zhang, B. Li and B. Wu, Dalton Trans., 2018, DOI: 10.1039/C8DT01685B.
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January 2016 Pages 1–398
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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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A bifunctional cationic metal-organic framework based on
unprecedented nonanuclear copper(II) cluster for high
dichromate and chromate trapping and highly efficient
photocatalytic degradation of organic dyes under visible light
irradiation†
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
*
Tian-Rui Zheng, Lin-Lu Qian, Min Li, Zhi-Xiang Wang, Ke Li, Ya-Qian Zhang, Bao-Long Li and Bing
Wu
A bifunctional cationic metal-organic framework {[Cu
synthesized and characterized (itp = 1-imidazol-1-yl-3-(1,2,4-triazol-4-yl)propane, 1,4-bdc = 1,4-benzenedicarboxylate). In 1-NO
OH·20H O, three [Cu (ꢀ -OH)(ꢀ -OH)] trimeric clusters are bridged by two ꢀ -Cl and form [Cu (ꢀ -OH) (ꢀ -OH) (ꢀ -Cl) ] cluster.
Such nonanuclear copper(II) cluster [Cu (ꢀ -OH) (ꢀ -OH) (ꢀ -Cl) ] is not reported until now, as to our best knowledge. 1-NO
O shows a 6-connected 2D 3 -hxl net based on nonanuclear copper(II) cluster [Cu (ꢀ -OH) (ꢀ -OH) (ꢀ -Cl) ]. 1-NO
-OH (guest-free phase) shows fast and high efficient
9 6 2 6 3 3 2 2 2 n 3 2
(OH) Cl (itp) (1,4-bdc) ](NO ) (OH) ·20H O} (1-NO -OH·20H O) was
3
-
2
3
3
2
3
9
3
3
2
3
3
2
9
3
3
2
3
3
2
3
-
6
OH·20H
OH·20H
2
9
3
3
2
3
3
2
3
-
6
2
O is also the first 2D 3 -hxl net based nonanuclear cluster. 1-NO
3
2
-
2-
2-
2-
4
Cr
capture Cr
NO
mixture of Cr
NO -OH can capture 87.9% dilute Cr
OH·20H O exhibits highly efficient photocatalytic degradation of the cationic organic dyes methylene blue (MB) and rhodamine B
RhB) under visible light irradiation, and is a good photocatalyst for photocatalytic degradation of the cationic organic dyes.
2
O
7
and CrO
4
trapping, and good recyclability for capturing of Cr
2
O
7
and CrO
. The adsorption capacities of 1-NO
3
-OH to
2
-
2-
-1
-1
-1
-1
2
O
7
and CrO
4
are 1.762 mol mol (154.8 mg g ) and 1.896 mol mol (89.5 mg g ), respectively at molar ratio 1:2 (1-
−3
2-
2-
2-
2-
3
-OH to 2.5 × 10 mol/L Cr
2
O
7
or CrO
4
). 1-NO
3
-OH exhibits selective sorption of Cr
2
O
7
or CrO
4
from the solution containing
2
-
2-
-
-
-
-
2-
2
O
7
or CrO
4
and tenfold the molar amount of ClO
4
, NO
3
, Cl , BF
4
or fivefold the molar amount of mol/L SO
4
. 1-
3
. 1-NO -
2
-
2-
2-
7
2-
3
2
O
7
or 91.8% dilute CrO
4
at equimolar 1-NO
3
-OH to 20 ppm Cr
2
O
or CrO
4
2
(
6
photocatalytic degradation of organic dyes. TiO
likely the most important semiconductors for photocatalysis. But
the relative high band gaps (E ) of TiO (3.2 eV), ZnO (3.4 eV) and
2
, ZnO and CdO are
Introduction
g
2
CdO (2.5 eV) make them absorbing mere a small amount of
ultraviolet light from visible or sunlight and therefore, limit their
Water pollution has been becoming a serious global environmental
pollution issue with the development of modern industry and
7
1
fast development and wide applications. The research and
living. Hexavalent chromium Cr(VI) was classified as Group “A”
development of the high efficient photocatalysts under visible light
or sunlight irradiation is greatly valuable.
human carcinogen by U.S. Environment Protection Agency (EPA)
2,3
because it causes serious damages to human health.
The
2
-
2-
Metal-organic frameworks (MOFs) have attracted great
attention because of their diverse topologies and widely potential
applications as functional materials in catalysis, gas adsorption,
elimination of Cr
2
O
7
and CrO
4
from wastewater is very urgently
desirable. But conventional technologies such as adsorbents, resin
and membranes are poor selectivity, low adsorption capacities and
8
,9
4
magnetism, chemical sensors, separation and so on. Cationic
MOFs contain substitutable uncoordinated anions in their cavity,
and therefore, could serve as the anion-exchange hosts for capture
slow process kinetics. Therefore, the research and development of
2
-
2-
advanced technologies and new materials for Cr
treatment is quite essential.
2
O
7
and CrO
4
1
0
anions and contaminant removal. Until to now, only few cationic
Organic dyes which are widely used in dyeing, dyestuffs and
the textile industry, are main contamination of wastewater due to
2
7
-
2-
MOFs have been reported for the removal of Cr
2
O
or CrO
4
from
1
1-14
5
aqueous media.
a 2D cationic Ag-MOF (SLUG-21) as an adsorbent of CrO
For example, Olive and co-workers synthesized
their poor biodegradability. Currently, semiconductor compounds
2
-
through
anion exchange. Ghost and co-workers reported a water-stable
such as metal oxides TiO
their composites are usually employed as photocatalysts for
2
, ZnO, CdO, metal sulfides ZnS, CdS and
4
1
1a
.
2-
2-
cationic MOF (1 SO
4
) as an adsorbent of Cr
2
O
7
through anion
(ꢀ
2 2 n
6H O} (1-Br) which shows fast and highly
1
2b
exchange.
OH) (mtrb)
efficient Cr
cationic MOFs were reported as adsorbents for removal both
Our group synthesized a cationic MOF {[Cu
4
3
-
.
2
2
(1,4-bda)
2
]Br
2
-
13c
2 7
O
trapping through the SC-SC process. Scare
2
-
2-
2 7 4
Cr O and CrO . For example, Lazarides and co-workers reported
a Zr cationic MOF (MOR-2) structural characterized via power X-
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o
ray crystallography and its composite form (MOR-2-HA) as were heated under vacuum at 75 C for one day to obtain the quest
2
-
2- 14
4
adsorbents of removal both Cr
2
O
7
and CrO
.
3
free phase dark teal crystals 1-NO -OH.
Garcia and co-workers reported MOF-5 as the first MOF
1
5
X-ray Crystallography
semiconductor photocatalyst for the degradation of phenol.
Although, some MOF photocatalysts for the degradation of organic
The measurement of 1-NO
3 2
-OH·20H O was made by using a Rigaku
1
6-18
dyes under UV or visible light irradiation were reported.
Saturn CCD diffractometer with an enhanced X-ray source Mo Kα (λ
However, relative few MOFs exhibit effective photocatalytic activity
under visible light irradiation due to most of MOFs with poor
=
0.71073 Å). The single crystal was mounted on a glass fiber at 293
2
0
K. The structure was solved and refined with SHELXTL package.
1
7,18
photoresponse in the visible region.
In previous work, we
The disordered hydroxy anions and water molecules in 1-NO
3
-
synthesized some Cu-MOFs using flexible N-donor ligands and
multicarboxylate ligands which show good photocatalytic activity in
the degradation of organic dyes under UV or visible light
OH 20H O were removed with the SQUEEZE procedure in PLATON.
·
2
The positions of the hydrogen atoms of itp and 1,4-bdc ligands were
determined with theoretical calculations. The parameters of the
1
9
irradiation.
In the present work,
[Cu (OH) Cl (itp) (1,4-bdc) ](NO
OH·20H
bdc
hydrothermal method. 1-NO
3 2
crystal data collection and refinement of 1-NO -OH·20H O are
given in Table S1 (in the ESI†). Selected bond lengths and angles are
a
bifunctional
·20H O}
Cu-MOF
3
(1-NO -
{
9
6
2
6
3
3
)
2
(OH)
2
2
n
listed in Table S2 (in the ESI†).
O) (itp = 1-imidazol-1-yl-3-(1,2,4-triazol-4-yl)propane, 1,4-
1,4-benzenedicarboxylate) was synthesized by the Anion Exchange Studies
2
=
3
-OH·20H
2
O shows a 6-connected 2D General procedure
6
3
-hxl net based on unprecedented nonanuclear copper(II) cluster
2-
2-
Molar ratio 1:1 (1-NO
3
-OH to 20 ppm Cr
, Selective capture of CrO
experiment are shown in the ESI†.
2 7 4
O or CrO ), Selective
[
Cu
fast and high efficient Cr
recyclability for capturing of Cr
9
(ꢀ
3
-OH)
3
(ꢀ
2
-OH)
3
(ꢀ
3
-Cl)
2
]. 1-NO
3
-OH (guest-free phase) shows
2-
2-
2
-
2-
capture of Cr
2
O
7
4
, Release and cycle
2
O
7
and CrO
4
trapping, and good
2
-
2-
2
O
7
and CrO
4
. 1-NO
3
-OH·20H
2
O
−3
2-
2-
(
a) Molar ratio 1:2 (1-NO
)
3
-OH to 2.5 × 10 mol/L Cr
2
O
7
or CrO
4
exhibits highly efficient photocatalytic degradation of the cationic
organic dyes methylene blue (MB) and rhodamine B (RhB) under
visible light irradiation.
{
[Cu
9
(OH)
6
Cl
2
(itp)
6
(1,4-bdc)
3
](NO
3
)
2
(OH)
2
}
n
3
(1-NO -OH) (20 mg,
−3
2-
0
.00814 mmol) was immersed in a 6.5 mL 2.5 × 10 mol/L Cr O
2 7
2
-
or CrO
4
aqueous solution and the mixture was mildly shaken at
Experimental
room temperature. The anion exchange process was monitored by
2
-
Materials and methods.
liquid UV-vis spectroscopy based on typical absorption of Cr
2
O
7
at
2
-
2-
2-
2
57 nm or CrO
4
at 372 nm. 0.10 mL Cr
2
O
7
or CrO
4
aqueous
All reagents were purchased and used without further purification.
Elemental analyses for C, H and N were performed on a Perkin-
Elmer 240C analyzer. FT-IR spectra were obtained on a Bruker
solution was pipetted at different time interval and was diluted
using 1.9 mL deionized water to measure the UV-vis adsorption
intensity.
-
1
VERTEX 70 FT-IR spectrophotometer in the 4000−600 cm region.
Powder X-ray diffraction (PXRD) were performed on a D/MAX-3C
diffractometer with the Cu-Kα radiation (λ = 1.5406 Å) at room
temperature. The UV-vis spectra were measured on a Varian Cary
The equilibrium adsorption capacity q (mg/g) is calculated by
e
the following equation.
(
C - C )V
i e
qe
(1)
=
5
00 UV-vis spectrophotometer. UV-vis diffuse reflectance spectra
of the solid samples were collected using Cary 500
spectrophotometer using barium sulfate (BaSO ) as a reflectance of Cr O7 , respectively. V (L) was the volume of the solution, and W
W
a
i e
Where C and C (mg/L) were the initial and final concentrations
2
-
4
2
standard. The X-ray photoelectron spectra (XPS) were recorded on (g) was the mass of sorbent.
an ESCALAB250XI spectrometer (Thermo-VG Scientific) and the
−3
2-
2-
(
b) Molar ratio 1:1 (1-NO
The procedure is similar to that of the experiment of molar ratio
:2, except that 1-NO -OH (40 mg, 0.0163 mmol) was used in this
(1- experiment.
3 2 7 4
-OH to 2.5 × 10 mol/L Cr O or CrO )
binding energy values were calibrated with respect to the C (1s)
peak (284.6 eV).
1
3
Synthesis of {[Cu
NO -OH·20H O)
A mixture of itp (0.035 g, 0.2 mmol), 1,4
9
(OH)
6
Cl
2
(itp)
6
(1,4-bdc)
3
](NO
3
)
2
(OH)
2
·20H
2
O}
n
3
2
-H
2
bdc (0.017 g, 0.1 mmol), Photocatalytic experiment
O (0.034 g, 0.2 mmol), The experiment was carried out a PCR-I multipurpose photoreactor
O (6.5 mL) were added to a (Beijing China Education Au-Light Company Limited, China)
Teflon-lined stainless autoclave and this was sealed and heated to equipped a CEL-HXF300 Xe lamp with UV cut-off filter (providing
0°C for 2 days and then cooled to room temperature. The blue visible light with λ > 400 nm). 1-NO -OH·20H O (40 mg) and 0.50
crystals 1-NO -OH·20H
O were obtained in 31% yield based on itp mL 30% H were added into a 100 mL of methylene blue (MB)
0.029 g). Anal. Calc. for C78 Cu 46 (1-NO -OH·20H
O): C, solution (10 mg/L), or a 100 mL of rhodamine B (RhB) solution (10
3.24%; H, 4.51%; N, 15.90%. Found: C, 33.15%; H, 4.45%; N, mg/L). The suspension solution was stirred in the dark for about 30
.
Cu(NO
3 2 2 2 2
) 3H O (0.048 g, 0.2 mmol), CuCl .2H
NaOH (0.008 g, 0.20 mmol) and H
2
9
3
2
2 2
O
3
2
(
H
126Cl
2
9
N
32
O
3
2
3
1
1
8
-
1
5.78%. IR data (cm ): 3402m, 3123w, 1636w, 1570s, 1452w, min. Then, the mixture was stirred continuously under visible light
373s, 1288w, 1259w, 1229w, 1200w, 1099m, 964w, 885w, 864w, irradiation. At a given interval, aliquots of the reaction mixture were
25w, 758m, 663w, 629m. These blue crystals 1-NO
3
-OH·20H
2
O
periodically taken and analyzed with a UV-vis spectrophotometer at
2
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ARTICLE
an absorption wavelength of 664 nm for MB and 552 nm for RhB. photocatalyst 1-NO
The blank experiment in the presence of H and absence of
3 2
-OH·20H O was also measured.
2 2
O
Fig.1 (a) The [Cu
-NO -OH·20H O; (c) The 2D cationic network in 1-NO
connected 2D network in 1-NO -OH·20H O. The brown balls show the 6-connected [Cu
-connected 1,4-bdc ligands.
9
(OH)
6
Cl
2
] nonanuclear copper(II) cluster in 1-NO
-OH·20H O, showing nitrate anions in the cavity; (d) Schematic depiction of the 6-
(OH) Cl (itp) ] clusters. The pink sticks exhibit the
3 2 9 6 2 6
-OH·20H O; (b) The [Cu (OH) Cl (itp) ] nonanuclear copper(II) cluster in
1
3
2
3
2
3
2
9
6
2
6
2
oxygen atom from one 1,4-bdc ligand in the apical position (O3) in
the distorted square-pyramidal configuration. The structural
Results and Discussion
distortion index τ for Cu2 atom is 0.172, indicating that the
Crystal
structure
of
{[Cu (OH) Cl (itp) (1,4- coordination environment of the metal atom is closer to square-
9
6
2
6
2
1
bdc) ](NO ) (OH) ·20H O} (1-NO -OH·20H O)
pyramidal geometry than trigonal-bipyramidal configuration.
The ꢀ -OH hydroxy (O1) acts as 3-connected bridge and
3
3 2
2
2
n
3
2
6
3
1
-NO
3
-OH
·
20H
2
O shows a 6-connected 2D 3 -hxl net based on
(ꢀ -OH) (ꢀ
20H O consists of
connects three Cu(II) atoms (Cu1, Cu1A, Cu2) (Fig. 1a). The ꢀ -OH
hydroxy (O2) acts as 2-connected bridge and connects two Cu(II)
2
unprecedented nonanuclear copper(II) cluster [Cu
9
3
3
2
-
OH) (ꢀ -Cl) ]. The asymmetric unit of 1-NO -OH
·
3
3
2
3
2
atoms (Cu1, Cu1A). Three Cu(II) atoms (Cu1, Cu1A, Cu2) are linked
one and half Cu(II) atoms, one itp ligands, half 1,4-bdc, two halves
of coordination hydroxyl (OH ), disordered nitrate. The Cu1 atom is
together by one ꢀ
OH)(ꢀ -OH)] trimeric cluster. Each Cl acts as bridge and connects
three [Cu (ꢀ -OH) (ꢀ -OH) (ꢀ -Cl) ] trimeric cluster trimeric clusters.
3
-OH (O1) and one ꢀ
2
-OH (O2), and form [Cu
3
(ꢀ
3
-
-
-
2
coordinated by two OH oxygen atoms (O1/O2), and two nitrogan
atoms from two itp ligands in the equation positions (N1/N4B) and
9
3
3
2
3
3
2
Three [Cu (ꢀ -OH)(ꢀ -OH)] trimeric cluster trimeric clusters are
-
3
3
2
one Cl in the apical position in the distorted square-pyramidal
joined by double ꢀ
3
-Cl and construct [Cu
9
(ꢀ
3
-OH)
3
(ꢀ
2
-OH)
3
3 2
(ꢀ -Cl) ]
configuration (Fig. S1 in the ESI†). The structural distortion index τ
for Cu1 atom is 0.017, indicating that the coordination environment
of the metal atom is closer to square-pyramidal geometry than
nonanuclear copper(II) cluster (Fig. 1a).
Although few nonanuclear copper(II) clusters were
2
2
reported.
For
example,
(
2
1
II
II
trigonal-bipyramidal configuration. The Cu2 atom is coordinated [{Cu (oxamate) }{Cu (pmdien)} ](ClO ) ·12H O
3
2
6
4 6
2
by one OH oxygen atoms (O1), one carboxylate oxygen atom from oxamate = N,N’,N’’-1,3,5-benzenetris, pmdien = N,N,N’,N’’,N’’-
one 1,4-bdc ligands (O5C) and two nitrogan atoms from two itp pentamethyldiethylenetriamine) exhibits the anticipated pattern
2
of six external [Cu(pmdien)] subunits ligated to a central
+
ligands (N2/N2A) in the equation positions and one carboxylate
This journal is © The Royal Society of Chemistry 20xx
II
6-
22a
[
{Cu
3
(oxamate)
2
}]
unit.
9 6 6
[Cu (cpida) (MeOH) ]·6(MeOH)
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cpida = 2-(carboxyphenyl)iminodiacetic acid) is made up of
units that are linked through a
Journal Name
(H
3
two carboxylate-bridged Cu
was almost identical to that of 1-NO
1-NO -OH maintains the framework (Fig. S4 in the ESI†). 1-NO
is a porous cationic framework. The NO
in the voids of the framework. The anion exchange properties of 1-
NO -OH were investigated. The crystals of 1-NO -OH were
immersed in an aqueous solution of double molar amount of 2.5 ×
3
-OH
·
20H
2
O which exhibits that
-OH
3
and OH anions are located
II
4
II
central Cu to give a Cu
22b
core. [Cu
3
3
9
9
(L)
4
(
ꢀ
N,N -(2-hydroxypropane-1,3-
3
-OH)
4
(MeOH)
2
](ClO
4
)
2
-
-
/
(
H
3
L
=
+
diyl)bis(benzoylacetoneimine)) consists of four dinuclear [Cu
units linked covalently to a central copper atom by four -OH,
CN·1-
O (L = 10 mol/L Cr
3] exchange process was monitored by UV/Vis spectroscopy at
cluster in intervals based on the intensity variation of the maximum
} (bte = 1,2-bis(1,2,4-
triazol-1yl)ethane, sip = 5-sulfoisophthalate) can be described as
consisting of two [Cu -OH) ] moieties connected to a centrally
placed CU(II) ion through two
2
L]
3
3
ꢀ
3
2
2c
II
thus yielding the nonacopper core. [Cu
9
(L)
CN· 2CH
,6-bis[5-(2-pyridinyl)-1H-pyrazol-3-yl]pyridin) show [3
6
](BF
4 6 3
) ·3CH
I
II
-3
2-
-
-
2-
PrOH·13H
2
O and [Cu
2
Cu
7
(L)
6
](PF
6
)
4
·4CH
3
3
OH·2H
2
2 7 3 2 7
O (equal charge of NO and OH , and Cr O ). The
2
×
2
2d
copper grid structures.
[Cu
9 3 4 2 2
(ꢀ -OH) (ꢀ -OH) ]
{
[Cu
9
(OH)
6
(bte)
2
(sip)
4
(H
2
O)
3
]·6H O
2
adsorption peak of in solution (257 nm). The concentration of
2-
Cr
2
O
7
in solution decreased by 46.9%, 56.1%, 64.2%, 71.6% and
4
(
ꢀ
3
2
2
2e
83.4% after 1h, 2h, 4h, 6h and 12h, respectively (Fig. 2),
corresponding to capture capacities of 0.938, 1.122, 1.284, 1.432
ꢀ
2
-OH groups.
(OH) ]·(ClO ·0.25CH
2,2’-(((5-methyl-1,3-
In the cation
5
]
+
[Cu
9
(L)
3
(OH)
7
of [Cu
=
9
(L)
3
7
4
)
5
3
OH·1.15H
2
O
-
1
2-
2 7
and 1.668 mol mol , respectively. Then the concentration of Cr O
(
2
H L
2
-
was slowly decreased, and the concentration of Cr
2 7
O and solution
phenylene)bis(methylene))bis((pyridine-2-ylmethyl)azane-
diyl)bis(methyl))bis(4-methylphenol)), a tricopper core is an
incomplete cubane with one missing, constructed by three hexa- Cr
color were no obvious changes from 24 h to 48 h. The total 88.1%
2
-
2
O
7
3
was captured by 1-NO -OH after 48 h. The overall capacity
2
-
-1
-1
coordinated copper atoms and four
3
3 2 7
ꢀ -OH group and then is of 1-NO -OH to capture Cr O is 1.762 mol mol (154.8 mg g )
2
2f
surrounded by two layers. [(MeSiO1.5
observation of nonanuclear metallasilsesquioxane ever.
However, In , three [Cu -OH)( -OH)] trimeric cluster
trimeric clusters are joined by double -Cl and construct
Cu -OH) -OH) -Cl) nonanuclear copper(II) cluster.
Such nonanuclear copper(II) cluster [Cu -OH) -OH)
Cl) ] is not reported until now, as to our best knowledge.
)18(CuO) ] is the first after 48 h. As compare, the the theoretic adsorption capacity of 1-
9
22g
2
-
-1
-1
NO
dark teal crystals 1-NO
2 7
after 1-NO -OH capturing Cr O anions (Fig. 3).
3
-OH to capture Cr
2
O
7
is 2.000 mol mol (175.7 mg g ). The
1
3
(
ꢀ
3
ꢀ
2
3
-OH were transfer to green crystals 1-Cr
2 7
O
ꢀ
3
2-
3
[
9
(ꢀ
3
3
(
ꢀ
2
3
(
ꢀ
3
2
]
Adsorption capacities for chromate or dichromate on various
porous materials are listed in Table S3 in the ESI† for comparison.
9
(ꢀ
3
3
(ꢀ
2
3 3
(ꢀ -
2
2
-
Each itp ligand coordinates three Cu(II) atoms via its two triazole For adsorption capacities for dichromate (Cr
nitrogen atoms (N1/N2) and one imidazole nitrogen atom (N4) (Fig. porous materials which were characterized by X-ray diffractometer,
2 7
O ) on cationic MOF
1
3b
S2 in the ESI†). The Cu(II) atoms in [Cu (OH) Cl ] nonanuclear
9
6
2
the capture capacities of Fir-53, Fir-54, a 3D MOF tetranuclear
1
3c
12c
,
copper(II) cluster are linked by six itp ligands and stabilize the
Cu (ꢀ -OH) (ꢀ -OH) (ꢀ -Cl) ] cluster, and form [Cu (ꢀ -OH) (ꢀ
OH) (ꢀ -Cl) (itp) ] cluster (Fig. 1b).
copper(II) cluster (1-Br), {[Ag(L
1
)
2
](BF
4
)}
n
and a 2D Cd based
[
9
3
3
2
3
3
2
9
3
3
2
-
12d
MOF were 74.2, 103.1, 128, 81.9 and 116.6 mg/g, respectively.
2-
-1
3
3
2
6
The capture capacity of 1-NO
better than these of above of cationic MOFs, but lower than
66mg/g for a 3D Ni based MOF12b and 207 mg/g for a 3D Ag
3 2 7
-OH to capture Cr O 154.8 mg g is
Two carboxylate groups of one 1,4-bdc lignads (O3O4, O5O6)
show monodentate mode. Each 1,4-bdc ligand acts as 2-connected
1
bridge (Fig. S3 in the ESI†). Each [Cu
nonanuclear copper(II) cluster connects six [Cu
OH) (ꢀ -Cl) (itp)
bridges and construct a 2D cationic network with the cage-like voids
9
(ꢀ
3
-OH)
3
(ꢀ
2
-OH)
3
(ꢀ
3
-Cl)
2
(itp)
6
]
1
3d
12a
based MOF. A post-synthesized Zr-MOF (ZJU-101), a Zr-MOF
MOR-2 via power X-ray crystallography) and its composite MOR-2-
9
(ꢀ
3
-OH)
3
(ꢀ
2
-
(
3
3
2
6
] nonanuclear copper(II) clusters via six 1,4-bdc
1
4
HA exhibit the high adsorption capacity for dichromat 245, 193.7
and 162.8 mg/g respectively. For other types adsorbents, the
adsorption capacities for Cr(VI) of amino starch, β-CD and
-
(
diameter ca. 6.5 Å) (Fig. 1c). The nitrate anions, disordered OH and
water molecules are located in the voids.
To simplify the topology, the nonanuclear copper(II) cluster quaternary
(ꢀ -OH) (ꢀ -OH) (ꢀ -Cl) (itp) ] is simplified as one node, and hexadecylpyridinium bromide modified natural zeolites, modified
,4-bdc ligand is the linker. Thus, the structure of 1-NO
ammonium
groups
modified
cellulose,
[Cu
9
3
3
2
3
3
2
6
1
3
-OH·20H
2
O
magnetic chitosan chelating resin and amino-functionalized titanate
nanotubes were 12.12, 61.05, 14.31, 58.48 and 153.85 mg/g,
6
23
is simplified as a 6-connected 2D 3 -hxl net. The distances
between nodes are 18.438(3) Å (Fig. 1d). Although the 3 tiling or
6
2
6
respectively.
When using equimolar amount of 1-NO
tessellation is common in face- and hexagonal-close packed
structures of many elements, it is unusual in coordination polymers
or metal-organic frameworks (MOFs) due to the requirement for a
3
-OH for absorb
2 7
O ) under the same conditions, 22.4%, 44.3%, 52.6%
2
-
dichromate (Cr
and 62.5% of Cr
0min, respectively (Fig. 4). The UV/Vis adsorption intensity of
2
-
2
7
O were exchanged after 5min, 15min, 30min and
o
24
six-connecting planar node with a 60 inter-contact angle. Only
6
6
few 3 tessellated 2D net coordination polymers were reported so
remained almost constant after 6h, thus indicating completion of
the exchange process. During exchange, the solution changed from
2
5
6
far. The first example of 3 tessellated 2D net coordination
polymer should be a Co(II) coordination polymer [CoL ](ClO (L =
,4-bis(benzimidazole-1-ylmethyl)-2,3,5,6-tetramethylbenzene)
2
-
3
4
)
2
yellow to colourless. The total 96.2% Cr
NO -OH after 12 h. The absorb procedure using equimolar amount
of 1-NO
using 1-NO
O
7
was captured by 1-
2
1
3
2
5a
2
-
reported by Su and co-workers. Yang and co-workers synthesized
a hexanuclear heterometal cluster coordination polymer showing 3
3
-OH and dichromate (Cr
2 7
O ) is obviously faster than that
6
2
-
3
-OH and double molar amount of dichromate (Cr O ).
2 7
25b
6
2D net. 3 tessellated 2D net coordination polymers contain the
metal atoms in the unit do not exceed six, to the best of our
2
4,25
6
knowledge.
3 2
1-NO -OH·20H O is also the first 2D 3 -hxl net based
nonanuclear cluster.
2
-
Anion Exchange Studies with Cr
The measured and simulated PXRDs confirm the purity of 1-NO
OH 20H O. The PXRD pattern of 1-NO -OH (the quest free phase)
2 7
O
3
-
·
2
3
4
| J. Name., 2018, 00, 1-3
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DOI: 10.1039/C8DT01685B
Journal Name
ARTICLE
examined for mixtures of anions. When equimolar amount of
crystals 1-NO -OH were immersed in the mixed aqueous solution
containing 2.5 × 10 mol/L Cr
3
1
0
0
0
0
0
.0
.8
.6
.4
.2
.0
0
-3
2-
2
-
2 7
O and tenfold the molar amount of
Cr O
5min
-2
-
-
-
-
2
7
2
.5 × 10 mol/L ClO , or NO , Cl , BF or fivefold the molar amount
4
3
4
15min
30min
1h
-2 2-
of 1.25 × 10 mol/L SO
4
. The UV/Vis spectroscopy, PXRD (Fig. S5 in
the ESI†) and FTIR spectroscopy were employed to study the
2-
2h
preferential anion uptake. The total Cr
2
O
7
3
captured by 1-NO -OH
4
6
1
2
3
4
h
h
2h
4h
6h
8h
after 24 h were 63.0%, 78.5%, 80.0%, 81.0% and 85.0% for the
2-
7
-
2-
-
2-
-
2-
-
mixtures of Cr
2
O
/ClO
4 2 7 3 2 7 2 7 4
, Cr O /NO , Cr O /Cl , Cr O /BF and
2
-
2-
Cr
2
O
7
/SO
anion at 940 cm were observed in the FTIR spectra of 1-
) in the presence
of interfere anions (Fig. S6 in the ESI†). The bands corresponding to
4
, respectively (Fig. 5). The bands corresponding to
2
-
-1
Cr
2
O
7
3 2 7
NO -OH after anion exchange (change to 1-Cr O
-
-
2-
250
300
350
400
450
500
550
the competing anions BF , Cl and SO were absent. The band
4
4
Wavelength (nm)
-
-1
corresponding to NO
in the FTIR spectra of 1-NO
presence of different interfere anions ClO
The characteristic adsorption band arising from ClO
cm was observed. The experiment measurements indicated that
3
anion at 1373 cm were obviously reduced
3
-OH after anion exchange in the
2
-
-
-
-
-
2-
Fig. 2 UV/Vis spectra of Cr
2
O
7
aqueous solution during exchange with 1-NO
3
-OH
4
, NO
3
, Cl , BF
4
and SO
4
.
-3
2-
-
and double molar amount of 2.5 × 10 mol/L Cr
2
O
7
aqueous solution.
4
at about 1084
-1
-
-
-
2-
the uptake is almost not disturbed by NO , Cl , BF and SO4 . The
tenfold the molar amount of ClO anion has some competitor to
4
3
4
-
2
-
Cr O anion.
2
7
2-
Cr O
2
7
1
.0
.8
2
7
-
Cr O
before anion exchange
2
-
2-
7
ClO /Cr O
0
4
2
-
NO /Cr O
3
2
7
1
-NO -OH
3
1
-Cr O
0.6
2
7
-
2-
7
Cl /Cr O
2
Fig. 3 Colour change of 1-NO
3
-OH crystals to 1-Cr
2
O
7
crystals.
-
2-
BF /Cr O
2 7
0
0
0
.4
.2
.0
4
2
-
2-
7
SO /Cr O
4
2
2-
7
Cr O
2
1
0
0
0
0
0
.0
.8
.6
.4
.2
.0
2-
Cr O
2
0min
7
5
1
3
min
5min
0min
250
300
350
400
450
500
550
Wavelength (nm)
60min
Fig. 5 UV-vis spectra of the mixed aqueous solution during anion exchange.
2
3
4
6
1
h
h
h
h
The trapping and release experiments were carried out to
evaluate the regeneration ability of the anion exchange. When 200-
was used as the triggers, 95.7% of
Cr O was released from 1-Cr O7 after 48 h at first cycle. The
trapping and releasing process was performed five continuous
cycles. The trapping efficiency was approximate 83.6% at fifth cycle.
The release efficiency was approximate 86.8% at fifth cycle.
-
fold molar amount of NO
3
2-
2h
2
7
2
2
50
300
350
400
450
500
550
Wavelength (nm)
2
-
Anion Exchange Studies with CrO
The crystals of 1-NO -OH were immersed in an aqueous solution of
double molar amount of 2.5 × 10 mol/L CrO
4
2
-
Fig. 4 UV-vis spectra of Cr
2
O
7
aqueous solution during anion exchange with
3
-3
2-
equimolar 1-NO -OH and 2.5 × 10 mol/L Cr
3
2
O
7
aqueous solution.
-3
2-
4
(equal charge of
-
-
2-
2-
2
-
The Cr
dilute Cr
immersed in an equimolar 20ppm Cr O aqueous solution. The and 6h, respectively (Fig. 6), corresponding to the capture
2
O
7
capture ability of 1-NO
3
-OH was further studied in NO
were decreased by 72.2%, 76.9%, 82.7% and 85.6% after 1h, 2h, 4h
3
aqueous solution. The crystals of 1-NO -OH were
3
and OH , and CrO
4
). The concentrations of CrO
4
in solution
2
-
2
O
7
2
-
2
7
-1
2
-
capacities of 1.444, 1.538, 1.654 and 1.712 mol mol , respectively.
7.0%, 60.0% and 79.0% after 1h, 2h, 4h and 9h, respectively, as Then, the concentrations of CrO
concentrations of Cr
2
O
7
in the solution were decreased by 26.0%,
2
-
3
4
were slowly decreased, and the
and solution color were no obvious
2
-
2
-
concentrations of CrO
4
2 7
shown in Fig. S4 in the ESI†. Then, the concentrations of the Cr O
2
-
were no obvious changes between 36 h and 48 h. The total 87.9% changes from 24 h to 36 h. The total 94.8% CrO
4
was captured by
-OH after 36 h. The overall capacity of 1-NO -OH to capture
is 1.896 mol mol (89.5 mg g ) after 36 h. As compare, the
2
-
Cr
In comparison with anion exchange, anion selectivity should be CrO
more important and challenging. To test the selectivity of the theoretic adsorption capacity of 1-NO
2
O
7
was captured by 1-NO
3
-OH after 48 h.
1-NO2
3
3
-
-1
-1
4
2
-
3
-OH to capture CrO
system for Cr O capture, selective exchange experiments were 2.000 mol mol (94.4 mg g ). The dark teal crystals 1-NO -OH were
4
is
-1
-1
2
-
3
2
7
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ARTICLE
Journal Name
2
-
transfer to bright green crystals 1-CrO after 1-NO -OH capturing of CrO4 were exchanged after 30min, 1h, 2h and 4h, respectively
4
3
2
-
4
CrO anions (Fig. 7).
(
Fig. 8). The UV/Vis adsorption intensity of remained almost
constant after 6h, thus indicating completion of the exchange
1
0
0
0
0
0
.0
.8
.6
.4
.2
.0
process. During exchange, the solution changed from yellow to
0
min
2
-
2-
CrO
4
5min
15min
colourless. The total 96.7% CrO
2 h.
was captured by 1-NO
-OH after
4
3
1
3
1
2
4
6
1
0min
h
h
h
h
2
-
2-
T
h
e
C
r
O
c
a
p
t
u
r
e
a
b
i
l
i
t
y
w
a
s
f
u
r
t
h
e
r
i
n
v
e
s
t
i
g
a
t
e
d
i
n
d
i
l
u
t
e
C
r
O
4
4
aqueous solution. The crystals of 1-NO
3
-OH were immersed in an
2-
aqueous solution of equimolar 20ppm CrO4 . The concentration of
2-
CrO
4
in the solution decreased by 44.0%, 62.4%, 78.2% and 89.7%
2h
24h
6h
after 1h, 2h, 4h and 8h, respectively, as shown in Fig. S7 in the ESI†.
2
-
3
Then, the concentrations of the CrO
between 12 h and 24 h. The total 91.8% CrO4 was captured by 1-
NO -OH after 24 h.
4
were no obvious changes
2-
250
300
350
400
450
500
550
3
Wavelength (nm)
When equimolar amount of crystals 1-NO -OH were immersed
3
-3
2-
in the mixed aqueous solution containing 2.5 × 10 mol/L CrO
4
2
-
Fig. 6 UV/Vis spectra of CrO
4
aqueous solution during exchange with 1-NO
3
-OH
-2
-
-
-
and tenfold the molar amount of 2.5 × 10 mol/L ClO
4
, or NO
3
, Cl ,
-3
2-
and double molar amount of 2.5 × 10 mol/L CrO
4
aqueous solution.
-
-2
2-
BF
4
4
or fivefold the molar amount of 1.25 × 10 mol/L SO . The
UV/Vis spectroscopy, PXRD (Fig. S8 in the ESI†) and FTIR
spectroscopy were employed to study the preferential anion
2
-
uptake. The total CrO
4
captured by 1-NO
3
-OH after 24 h were
2
-
6
5.4%, 90.0%, 89.1%, 91.0% and 53.0% for the mixtures of CrO
/ClO , CrO4 /NO , CrO4 /Cl , CrO4 /BF4 and CrO4 /SO4
4 3
4
2-
CrO 2-
-
2-
-
2-
-
2-
-
2-
4
,
2
-
respectively (Fig. S9 in the ESI†). The bands corresponding to CrO
4
-1
anion at about 895 cm were observed in the FTIR spectra of 1-
NO -OH after anion exchange (change to 1-CrO ) in the presence of
3
4
1
1c
interfere anions (Fig. S10 in the ESI†). The bands corresponding
-
-1
to NO3 anions at 1373 cm were obviously reduced in the FTIR
spectra 1-NO -OH after anion exchange (change to 1-CrO ) in the
presence of different interfere anions ClO , NO , Cl , BF and SO4
1
-NO -OH
3
1
-CrO4
3
4
-
-
-
-
2-
.
4
3
4
-
-
3 4
Fig. 7 Colour change of 1-NO -OH crystals to 1-CrO crystals.
The bands corresponding to the competing anions BF
4
and Cl were
absent in the FTIR spectra. The characteristic adsorption bands
2
-
-
-1
2-
-1
The adsorption capacities for capturing CrO
MOF (SLUG-21), a 3D Dy-MOF (1-ClO
) and Zn0.5Co0.5SLUG-35 are were observed. The measurements indicated that the uptake of is
4
of a 2D Ag based- arising from ClO4 at about 1084 cm and SO4 at about 1103 cm
4
-
-
-
-
1
11
almost not disturbed by NO
3
, Cl and BF
4
. The tenfold the molar
6
0, 62.88 and 68.5 mg g , respectively (Table S3 in the ESI†). The
-
2-
-
1
2-
amount of ClO4 anion and fivefold the molar amount of SO anion
capture capacity 89.5 mg g for capturing CrO
better than these of above cationic MOF. Recently, Lazarides and
co-workers reported Zr MOF (MOR-2) via power X-ray
crystallography and its composite form MOR-2-HA which exhibit
4
of 1-NO
3
-OH is
4
2
-
have some competitor to CrO
4
anion.
-
When 200-fold molar amount of NO was used as the triggers,
3
a
2
-
9
6.3% of Cr
2
O
7
4
was released from 1-CrO after 48 h at first cycle.
The trapping and releasing process was performed five continuous
cycles. The trapping efficiency was approximate 84.3% at fifth cycle.
The release efficiency was approximate 88.2% at fifth cycle.
-
1
high adsorption capacities of 118.3 and 109 mg g , respectively, for
2
- 14
4
capturing CrO .
2
-
2-
1
-NO
3 2 7 4
-OH shows the selectivity capture for Cr O or CrO . The
-
-
1.0
0.8
0.6
0.4
0.2
0.0
anions NO3 and OH located in the the cage-like voids (diameter ca.
6.5 Å) of 1-NO -OH were exchanged by Cr O or CrO because the
3 2 7 4
shape and size of relative big Cr O7 and tetrahedral CrO4 anions
2-
2-
2-
CrO
0min
4
5min
2-
2-
2
15min
30min
are more suitable for the big cage-like voids than other small
-
-
-
-
2-
1h
competing anions ClO , NO , Cl , BF and SO4 . Moreover, the
4
3
4
2h
…
probable O-H O hydrogen bonding interactions between the
coordinated hydroxyl groups and Cr O or CrO4 can support the
2 7
3h
2
-
2-
4
8
1
h
h
2h
2
-
2-
2 7 4
MOF’ selectivity capture for Cr O or CrO .
Catalytic activity for the degradation of methylene blue and
rhodamine B
2
50
300
350
400
450
500
550
Wavelength (nm)
3 2
The UV-vis spectrum (Fig. S11 in the ESI†) of 1-NO -OH·20H O
2
-
sample shows the absorption peak at 480 nm, which should be
caused by the optical transitions of the ligand-to-metal charge
transfer (LMCT). The band gap energy (Eg) is estimated to be 2.06
Fig. 8 UV-vis spectra of Cr
2
O
7
aqueous solution during anion exchange with
-3
2-
equimolar 1-NO -OH and 2.5 × 10 mol/L CrO
3
4
aqueous solution.
When using equimolar amount of 1-NO
3
-OH for absorb chromate eV by the extraction of the linear portion of the absorption edge,
2
-
(
CrO ) under the same conditions, 71.9%, 85.5%, 92.9% and 95.0% indicating its semiconductor nature.
4
6
| J. Name., 2018, 00, 1-3
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DOI: 10.1039/C8DT01685B
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ARTICLE
3 2
To study the photocatalytic activity of 1-NO -OH·20H O, we
selected the cationic organic dyes methylene blue (MB), and
rhodamine B (RhB) as the model dye contaminants to evaluate the
photocatalytic effectiveness under visible light irradiation in the
2.0
0
min
1
1
0
.5
.0
.5
15 min
1
6-19
30 min
45 min
60 min
purification of wastewater.
The photocatalytic behaviors of 1-NO
degradation of MB under visible light irradiation were shown in Fig.
and Fig. 10. After 90 min, the degradation efficiency of MB
reached 92.5% in the presence of catalyst 1-NO -OH·20H O.
3
2
-OH·20H O for the
75 min
90 min
9
105 min
3
2
120 min
However, the degradation efficiency of MB was reduced to 19.8%
after 90 min when the experiment was conducted in the presence
0.0
of only H
OH·20H O is a good catalyst for the degradation of MB.
The photocatalytic behaviors of 1-NO -OH·20H
degradation of RhB under visible light irradiation were shown in Fig.
1 and Fig. 12. After 120 min, the degradation efficiency of RhB
reached 92.1% in the presence of catalyst 1-NO -OH·20H O.
2
O
2
and in the absence of catalyst. Therefore, 1-NO
3
-
400
500
600
700
Wavelength (nm)
Fig. 11 The UV-vis absorption spectra of RhB solution during
photocatalytic degradation of the MB solution using catalyst 1-NO
2
3
2
O for the
3
-
1
2 2 2
OH·20H O in the presence of H O under visible light irradiation.
3
2
However, the degradation efficiency of RhB was reduced to 14.0%
after 120 min when the experiment was conducted in the presence
1
.00
.75
of only H
2 2 3 2
O . Therefore, 1-NO -OH·20H O is also a good catalyst for
the degradation of RhB.
0
1.5
1.0
0.5
0.0
0
1
3
4
6
7
9
min
0.50
5 min
0 min
5 min
0 min
5 min
0 min
Blank
0
.25
.00
.
-NO -OH 20H O
3 2
1
.
1
-NO -OH 20H O+mannitol
3
2
0
0
20
40
60
80
100
120
Irradiation time (min)
400
500
600
700
800
Wavelength (nm)
Fig. 9 The UV-vis absorption spectra of MB solution during
photocatalytic degradation of the MB solution using catalyst 1 in mannitol, and only H O under visible light irradiation.
Fig. 12 Photocatalytic degradation efficiencies of the RhB solution
using catalyst 1-NO -OH·20H O in the presence H or H and
3
2
2
O
2
2 2
O
2
2
the presence of H
2
O
2
under visible light irradiation.
After the photocatalytic experiment, the PXRD patterns of 1-
NO
NO
3
-OH·20H
-OH·20H
2
O are in good agreement with that of the original 1-
O, implying that 1-NO -OH·20H after the
1.00
0.75
0.50
0.25
0.00
3
2
3
2
O
photocatalytic reaction maintains their structural integrity (Fig. S12
in ESI†). The photocatalytic experiment proves that 1-NO3-
2
OH·20H O is a highly efficient photocatalyst for degradation of the
cationic organic dyes MB and RhB.
In order to reveal the photocatalytic mechanism, the
photocatalytic reactions were performed under the same conditions
using catalyst 1-NO -OH·20H O in the presence of mannitol (1.0
Blank
.
1
-NO -OH 20H O
3
2
3
2
1
7,18
.
g).
The experimental results (Fig. 10 and Fig. 12) show that the
-OH·20H O almost completely disappeared
1
-NO -OH 20H O+mannitol
3
2
0
20
40
60
80
catalytic activity of 1-NO
in the presence of mannitol (1.0 g) and reveal that the
photogenerated holes should be the active secrecies for the dye
3
2
Irradiation time (min)
Fig. 10 Photocatalytic degradation efficiencies of the MB solution degradation process. The oxidation ability of the holes is determined
using catalyst 1-NO
mannitol, and only H O under visible light irradiation.
3
-OH·20H
2
O in the presence H
2
O
2
or H
2
O
2
and by the energy position of the valence band. The VB XPS spectrum
2
2
(Fig. S13 in the ESI†) shows that the VB edge of 1-NO -OH·20H O
3
2
17i,18f
locates at 0.62 eV.
-
The holes also can oxidize hydroxyl ions (OH ) to generated the
•
OH radicals. The hydroxyl radicals can directly oxidize the dyes. The
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•
OH radicals can also react with terephthalic acid (TA) in the
solution to generate 2-hydroxyterephthalic acid (TAOH), which
2
3
L. H. Keith and W. A. Teillard, Environ. Sci. Technol., 1979, 13
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,
4
1
7i,18f
emits a unique fluorescence signal with its peak at ca. 426 nm.
(
2
The intensity of the TAOH fluorescence signal can qualitatively
•
identify the amount of the generated OH radicals. As shown in Fig.
4
S14, samples reacting for 10 min were selected as the objects of
photoluminescence spectra. There was a lack of the signal of TAOH
without the photocatalyst and H
was observed when H was added. A relative strong fluorescence
was detected in the presence of only photocatalyst 1-NO
OH·20H O. The remarkably increased TAOH fluorescence intensity
in the presence of 1-NO -OH·20H O and H confirms that the
photocatalyst system in the presence of photoctalyst 1-NO
2 2
O . The TAOH fluorescent peak
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3
2
2 2
O
3
-
1
68, 51; (d) H. Wang, M. Miyauchi, Y. Ishikawa, A. Pyatenko,
•
OH·20H
Therefore, the photocatalytic reaction mechanism could be
assumed. The photoctalyst 1-NO -OH·20H O was irradiated by
2 2 2
O and H O can generate more OH radicals.
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2
7
8
photons with energy equal to or greater than the band gap (2.06
eV), electrons are excited from the valence band (VB) to the
conduction band, leaving the holes in the valence band. The
photogenerated holes have a strong oxidant ability and can directly
oxidize dyes or can react with hydroxyl ions to generate hydroxyl
radicals. The hydroxyl radicals can directly oxidize the dyes to
effectively decompose the organic dyes (MB, RhB) to complete the
photocatalytic process.
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Conclusions
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A bifunctional cationic metal-organic framework 1-NO
was synthesized and characterized. 1-NO -OH·20H O shows a 6-
connected 2D 3 -hxl net based on unprecedented nonanuclear
3 2
-OH·20H O
3
2
6
copper(II) cluster [Cu
9
(ꢀ
3
-OH)
3
(ꢀ
2
-OH)
3
(ꢀ
3
-Cl)
2
]. 1-NO
3
-OH·20H
2
O is
9
6
also the first 2D 3 -hxl net based nonanuclear cluster. 1-NO
3
-OH
2
-
2-
(
guest-free phase) shows fast and high efficient Cr
trapping, and good recyclability for capturing of Cr
-NO -OH·20H exhibits highly efficient photocatalytic
2
O
7
and CrO
4
2
-
2-
2
O
7
4
and CrO .
1
3
2
O
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1
, 4887; (c) Y. Y. Hu, T. T. Zhang, X. Zhang, D. C. Zhao, X. B.
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degradation of the cationic organic dyes methylene blue (MB) and
rhodamine B (RhB) under visible light irradiation.
(
In summary, a stable cationic MOF was synthesized. The present
results could provide a good cationic MOF sorbent for removal of
hexavalent chromium pollutants and a good photocatalyst for
removal of organic dye pollutants in wastewater.
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Conflicts of interest
There are no conflicts to declare.
2
017, 56, 14178.
Acknowledgements
1
0
(a) D. T. Tran, P. Y. Zavalij and S . R. J. Oliver, J. Am. Chem.
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This work is supported by the National Natural Science
Foundation of China (No. 21171126), the Natural Science
Foundation of Jiangsu Province (No. BK20161212), the Priority
Academic Program Development of Jiangsu Higher Education
Institutions, State and Local Joint Engineering Laboratory for
Functional Polymeric Materials, and the project of scientific and
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A Table of Contents
6
A bifunctional cationic metal-organic framework shows a 6-connected 2D 3 -hxl net
2
-
2 7
based on unprecedented nonanuclear copper(II) cluster, fast and high efficient Cr O
2
-
and CrO4 trapping, and highly efficient photocatalytic degradation of the cationic
organic dyes methylene blue and rhodamine B under visible light irradiation, under
visible light irradiation.
2
-
CrO 2-
2 7
Cr O
4
2 7
1-Cr O
1
-CrO
4
1-NO -OH
3
1.5
1.0
0.5
0.0
0
min
1
3
4
6
7
9
5 min
0 min
5 min
0 min
5 min
0 min
4
00
500
600
700
800
Wavelength (nm)