A stable metal cluster-metalloporphyrin MOF with high capacity for cationic dye removal

Article abstract of DOI:10.1039/c8ta06249h

A metalloporphyrin Cu₅-cluster based MOF (metal-organic framework), [Cu_4.5((H₄TZPP)(TZPP)Cl₂)(H₂O)_0.5]·CH₃NH₂CH₃·7EtOH·8H₂O (LIFM-WZ-3) was synthesized from the tetrapodal ligand 5,10,15,20-tetrakis[4-(2,3,4,5-tetrazolyl)phenyl]porphyrin (H₆TZPP) and copper chloride. LIFM-WZ-3 exhibits a rare 2D + 3D → 3D interpenetration topology, of which the frl-type 3D MOF and a layered 2D HOF (hydrogen bond organic framework) are intertwined, leading to an anionic framework with 1D spindle-like channels. Powder X-ray diffraction analysis reveals that the framework is stable in acid, base and various organic solvent environments. LIFM-WZ-3 exhibits moderately high separation performances for CO₂/CH₄, CO₂/N₂, C₃H₆/CH₄, C₂H₆/CH₄, and C₂H₄/CH₄ at room temperature. Specifically, the anionic framework in LIFM-WZ-3 containing dimethylamine cations can selectively adsorb cationic organic dyes from aqueous pollutants for recycle purpose. The high adsorption capacity for methylene-blue (MB⁺, 983 mg g^-1) and crystal violet (CV⁺, 713.5 mg g^-1) ranks the highest among those MOFs ever reported.

Full text of DOI:10.1039/c8ta06249h

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ISSN 2050-7488
PAPER
Kun Chang, Zhaorong Chang et al.
Bubble-template-assisted synthesis of hollow fullerene-like
MoS2 nanocages as a lithium ion battery anode material
rsc.li/materials-a

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A stable metal clusterꢀmetalloporphyrin MOF with high
capacity for cationic dye removal
Received 00th January 20xx,
Accepted 00th January 20xx
Zheng Wang,a,b JianꢀHua Zhang,a JiꢀJun Jiang,a HaiꢀPing Wang,a ZhangꢀWen Wei,a
Xunjin Zhu,*b Mei Pan,*a and ChengꢀYong Sua
DOI: 10.1039/x0xx00000x
www.rsc.org/
A
metalloporphyrin
Cu5ꢀcluster
based
MOF
(metalꢀorganic
framework),
[Cu4.5(H4TZPP)(TZPP)Cl2)(H2O)0.5]·CH3NH2CH3·7EtOH·8H2O (LIFMꢀWZꢀ3) was synthesized from the
tetrapodal ligand {5,10,15,20ꢀtetrakis[4ꢀ(2,3,4,5ꢀtetrazolyl)phenyl]porphyrin (H6TZPP) and copper chloride.
LIFMꢀWZꢀ3 exhibits a rare 2D+3D→3D interpenetration topology, of which frlꢀtype 3D MOF and layered
2D HOF (hydrogen bond organic framework) are intertwined, leading to an anionic framework with 1D
spindleꢀlike channels. Powder Xꢀray diffraction analysis reveals that the framework is stable in acid, base and
various organic solvent environment. LIFMꢀWZꢀ3 exhibits moderately high separation performances for
CO2/CH4, CO2/N2 and C3H6/CH4, C2H6/CH4, C2H4/CH4 at room temperature. Specifically, the anionic
framework in LIFMꢀWZꢀ3 containing dimethylamine cations can selectively adsorb cationic organic dyes
from aqueous pollutants for recycle purpose. The high adsorption capacity for methyleneꢀblue (MB+, 983 mg
gꢀ1) and crystal violet (CV+, 713.5 mg gꢀ1) ranks the highest among those MOFs ever reported.
As a new class of porous materials, metalꢀorganic frameworks
(MOFs) have aroused great attention in recent years, and widely
Introduction
applied in various fields including chemical sensing,5 light emitting,6
proton conductivity,7 catalysis,8 magnets,9 drug delivery and medical
materials,10 energy storage,11 and so on.12 Compared with other
porous materials such as activated carbons, zeolites and polymers,
MOFs manifest controllable porosity (sometimes tunable by
interpenetration), high surface areas, and ability to be functionalized
for better interactions with certain kinds of guest molecules
including organic dyes.13ꢀ17 Meanwhile, MOFs with charged
frameworks may have unique advantages in adsorption, selection
and separation by hostꢀguest interactions.18,19 For example, cationic
MOFs can selectively adsorb anionic dyes through ionꢀion exchange
processes, and vice versa. Besides electrostatic interactions, the
driving forces might also include other kinds of intermolecular
interactions between the active sites of host MOFs and guest dyes,
such as hydrogen bonds, hydrophobic interactions, van der Waals
interactions, and so on.20
Accompanying the rapid development of industries, organic dyes
have been widely applied as eluent and colorant in different fields
and enriched our lives.1,2 However, some dye molecules are toxic,
carcinogenic, and very resistant to degradation under sunlight, heat,
and oxidant in nature, which might cause serious water pollutions.
Therefore, it is urgent to find efficient ways to remove dye pollutants
from water before they are released for consumption. So far, various
methods including physical, chemical and biological technologies
have been developed. Among them, adsorption by porous materials
is considered the most common technique to remove organic dyes
from aqueous solution, characteristic of low cost and high
efficiency.3 Currently, different kinds of porous adsorbents like
zeolites, activated carbons, molecular sieves and polymeric materials
have been used for removal of organic dyes.4 However, these
materials encounter problems such as less selectivity and low
capacity, which hinders the efficient removal, recovery and reuse of
specific dyes.
On the other hand, the application of MOFs in selective
adsorption and separation of gases and hydrocarbons has been
widely recognized in the past decades.21 If the confined channels of
MOFs are with suitable sizes and specific interacting sites for certain
guest molecules, effective adsorption and separation might be
resulted for selective ingredients in mixed gases. For such purposes,
a.Lehn Institute of Functional materials, MOE Laboratory of Bioinorganic and
Synthetic Chemistry, School of Chemistry, Sun Yat-Sen University, Guangzhou
510275, China.
b.Department of Chemistry, Hong Kong Baptist University, Waterloo Road, Kowloon
Tong, Hong Kong, China.
Electronic Supplementary Information (ESI) available: [Crystal structure, formula abundant MOFs from carboxyl, pyridine, imidazole, pyrazole and
and size of dyes, TG, gas and dye adsorption, etc]. See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
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triazole ligands have been designed by researchers. Compared with and were anisotropically dealed with occupancy of part 10.5. The
these, 5ꢀsubstituted tetrazolyl ligands are much less used for crystal for LIFMꢀWZꢀ3 has no diffraction point at high angles, so we
constructing MOFs, and 5ꢀsubstituted tetrazolyl porphyrin ligands only collect half
a
degree to 52.99. The LIFMꢀWZꢀ3
are even less developed.22 As a matter of fact, the multiple nitrogen crystallographic data were listed in Table S1. The selected bonds
atoms in 5ꢀsubstituted tetrazolyl porphyrins will bring versatile distance and bonds angles are displayed in Table S2. The single
coordination abilities and charged states by adopting different crystal data have been deposited in the Cambridge Crystallographic
bridging or chelating modes, as well as unique framework stability Data Center (CCDC No: 1812995).
with permanent channels due to the porphyrin core, and might find
Synthesis of ligand
potential applications in MOF chemistry. In addition, more nitrogen
sites within the frameworks can increase the specific adsorption
capacity for gases, hydrocarbons or organic dyes.23 Based on the
above considerations, we designed herein an anionic MOF from
5,10,15,20ꢀtetrakis(4ꢀcyanophenyl)porphyrin
(H2TCNPP).
H2TCNPP was synthesized according to a modified literature
method. 4ꢀformyl benzonitrile (6.55 g, 50.00 mmol) and propionic
acid (200 ml) were added to the flask and heated to 110 , then
pyrrole (3.35 g, 50.00 mmol) was added dropwisely to the mixture
solvent through a period of one hour and heated to reflux for
overnight. After the reaction, the propionic acid was removed under
reduced pressure. The resulting dark residue was washed with cold
ethanol and acetone until the purple solid appeared. And then, it was
dried in vacuum to obtain H2TCNPP (1.71 g) as a pure violet solid
with 20 % yield. 1H NMR (CDCl3) δ 8.85 (s, 8H), 8.38 (d, 8H), 8.12
(d, 8H) ppm.
5,10,15,20ꢀtetrakis[4ꢀ(2,3,4,5ꢀtetrazolyl)phenyl]porphyrin
ligand,
which presents rare example of 2D+3D→3D framework
a
containing interpenetrated 2D metalloporphyrin HOF and 3D MOF
elements simultaneously. The stable anionic framework with 1D
spindleꢀlike channels manifests rather good gas and hydrocarbon
separation abilities, and can selectively adsorb cationic organic dyes
from aqueous solution.
Experimental
Materials and Physical Measurements
5,10,15,20ꢀtetrakis[4ꢀ(2,3,4,5ꢀtetrazolylphenyl]porphyrin
(H6TZPP). H2TCNPP (3.00 g, 4.20 mmol), NH4Cl (3.60 g, 33.71
mmol), NaN3 (4.81 g, 36.72 mmol), and DMF (200 ml) were mixed
and heated to reflux for 3 days. Additional NaN3 (1.71 g, 25.92
mmol) and NH4Cl (1.11 g, 20.52 mmol) were added to the mixture
and continued to react for 2 days. After the reaction, a small part of
DMF was removed under reduced pressure and cold water (500 ml),
6 mol lꢀ1 HCl were added with quickly stirring. The precipitate was
filtered and washed several times with cool water and cool ethanol,
and dried in vacuum to get H6TZPP as a green solid with 92 % yield.
1H NMR (DMSOꢀd6) δ 8.98 (s, 8H), 8.52 (d, 8H), 8.46 (d, 8H) ppm.
IR (KBr, cmꢀ1): 3420 (b), 2926 (w), 2857 (w), 1654 (s), 1615 (m),
1574 (w), 1563 (w), 1496 (w), 1472 (w), 1435 (w), 1415 (m), 1385
(m), 1348 (w), 1270 (w), 1253 (w), 1224 (w), 1187 (w), 1151 (w),
1100 (w), 1061 (w), 1021 (w), 1012 (w), 993 (w), 981 (w), 966 (m),
858 (m), 800 (m), 751 (w), 729 (m), 663 (w), 633 (w), 561 (w), 474
(w), 456 (w).
All reagents of analytical grades were purchased from the
Dieckmann company and used without further purification process.
IR spectrum was recorded from KBr pellet on
a FTSꢀ40
spectrophotometer in the range of 4000ꢀ400 cmꢀ1. Elementary
analysis was performed on a Vario EL element analyzer. NMR
spectra were recorded on a JEOL EX270 spectrometer. Chemical
shifts of 1H NMR spectra were referenced to internal deuterated
solvents and then recalculated to SiMe4. Powder Xꢀray diffraction
(PXRD) was carried out with a Rigaku Smart Lab diffractometer
(BraggꢀBrentano geometry, Cu Kα1 radiation, λ = 1.54056 Å).
Thermogravimetric analyses (TGA) were performed on a NETZSCH
TG209 system in nitrogen and under 1 atm of pressure at a heating
rate of 10 °C per min. Brunauer–Emmett–Teller (BET) surface area
was measured using Quadrasorb SIꢀMP instrument. Gas adsorption
isotherms with the pressures in the range of 0ꢀ1.0 bar were obtained
by a volumetric method using a quantachrome autosorbꢀiQ2ꢀMP gas
adsorption analyzer. Gas adsorption measurements were performed
using ultraꢀhigh purity N2, CH4, CO2 and hydrocarbon gases.
Synthesis of MOF
[Cu4.5(H4TZPP)(TZPP)Cl2)(H2O)0.5]·CH3NH2CH3·7EtOH·8H2O
(LIFMꢀWZꢀ3). A mixture of CuCl2·2H2O (5.30 mg, 0.03 mmol),
HCl (4 ml, 1 mol lꢀ1) and H6TZPP (8.86 mg, 0.01 mmol) dissolved in
2 ml of H2O, 2 ml of DMF and 2 ml of ethanol were sealed in a
Teflon vessel in a steel autoclave, and heated at 110 for three days
and then slowly cooled a period of 48 hours to room temperature.
Purple red flake single crystal of LIFMꢀWZꢀ3 were collected. The
yield is 90% based on the ligand. Analysis calcd. for
Xꢀray single crystal structural analysis
The Xꢀray diffraction intensity data for LIFMꢀWZꢀ3 were performed
on a Bruker Apex II CCD diffractometer graphiteꢀmonochromatic
enhanced ultra Cuꢀradiation (λ = 1.54178 Å) at 100 K. The structure
was solved by direct methods, and refined by fullꢀmatrix leastꢀsquare
methods with the SHELXLꢀ1997 program package. All hydrogen
atoms were located in calculated positions and refined
anisotropically. The solvent molecules in LIFMꢀWZꢀ3 are
disordered. The SQUEEZE routine of PLATON was applied to
remove the highly disorder solvent molecules, and the final
molecular formulas of LIFMꢀWZꢀ3 was determined by the
combination of TGA (Fig. S1) and elemental analysis data. The 2D
HOF layers within LIFMꢀWZꢀ3 are all disordered over two sites
which form a rotate disorder angles by two occupied components
C
112H114N41Cl2O15.5Cu4.5: C 53.33, H 4.42, N 22.78%; found: C,
53.76, H, 4.97, N, 23.22%. IR (KBr, cmꢀ1): 3356 (b), 1615 (s), 1537
(w), 1495 (w), 1447 (w), 1421 (w), 1378 (s), 1345 (m), 1270 (w),
1247 (w), 1207 (w), 1157 (w), 1126 (w), 1100 (w), 1076 (w), 999
(s), 886 (w), 860 (w), 818 (w), 802 (w), 761 (w), 751 (w), 718 (w),
561 (w), 498 (w). The MOF samples were activated by soaking in
MeOH and CH2Cl2 for 7 days and then heated at 120℃ for 10 hours.
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Results and discussion
two TZPP6ꢀ ligands, one chloride ion and one water molecule. The
CuꢀN bond lengths change from 1.938(16) to 2.049(17) Å, and the
CuꢀCl and CuꢀO bond lengths vary in a reasonable range from
2.590(13) to 2.343(5) Å, which are in accordance with typical Cu
complexes.24, 25
Crystal structure
It is interesting that in the framework of LIFMꢀWZꢀ3, there are
two discrete elements, a 2D hydrogen bonded framework (HOF),
and a 3D MOF (Fig. 1b). The 2D HOF is formed by intermolecular
hydrogen bonding and πꢀπ stacking linked CuH4TZPP moieties (Fig.
1c), in which Cu5 ions are located in the porphyrin cores, and the
tetrazolyl ends are not coordinated. In comparison, the 3D MOF is
composed of {Cu5} clusters and Cu1ꢀresided metalloporphyrins,
showing an aperture of ~1.1
× 1.1 nm (Fig. 1d). The porphyrin
ligands containing Cu1 centers are extended via coordination of
tetrazolyl ends with other Cu2+ ions (Cu2, Cu3, and Cu4). Further
analysis reveals that, in the 3D MOF structure, Cu2, Cu3, Cu3A,
Cu4 and Cu4A are connected by eight tetrazolyl groups and four Clꢀ
ions into a fiveꢀnuclear {Cu5} cluster with Cu···Cu distance of 3.448
and 3.526 Å (Fig. 1e). The {Cu5} clusters are further linked by the
bridge of water molecules to form 1D zigzag metal ladders, as
termed by Yaghi et al. to be rodꢀshaped secondary building units,26
and are connected by [CuTZPP]4− ligands to produce a 3D anionic
framework.
Topologically, simplifying [CuTZPP]4ꢀ metalloporphyrin as 4ꢀ
connected points to link the zigzag ladders composed of {Cu5}
clusters, a rare 3D frl structure with the Schläfli symbol of
(42·64)4(64·82) is formed, presenting the first frl network in
porphyrinꢀbased MOFs, as far as we know. Furthermore, the 3D
MOF is interpenetrated by the 2D HOF via H…Cl interactions and
the whole LIFMꢀWZꢀ3 can be seen as an interpenetrated
2D+3D→3D network. Although the interpenetration of 2D HOF
blocks half of the pores in the original 3D frl framework, the
Fig.
1 Crystal structure of LIFMꢀWZꢀ3. a) Coordination
environment of copper ions and porphyrin ligands. b) Selfꢀassembly
formation of 2D+3D→3D nets; c) 2D metalloporphyrin HOF layers
formed via CꢀH···N and πꢀπ stacking interactions; d) 3D metal
clusterꢀmetalloporphyrin MOF nets with 1D square channels; e)
{Cu5} metal cluster.
remaining 1D spindleꢀlike channels along
c axis (Fig. S3) afford
LIFMꢀWZꢀ3 with selective adsorption abilities for certain gases and
dyes. Meanwhile, the whole frameworks are anionic in nature and
charge balanced by dimethylamine cations originated from the
decomposition of DMF under hydrothermal conditions, leading to
further adsorption selectivity.
Purple red flake crystals of LIFMꢀWZꢀ3 with sizes of 0.1 × 0.5 ×
0.5 mm3 were obtained under solvothermal reaction by heating the
mixture of CuCl2·2H2O and H6TZPP at 110 for 3 days. Single
crystal Xꢀray diffraction reveals that LIFMꢀWZꢀ3 is crystallized in
the monoclinic P2/m space group. In the asymmetric unit of LIFMꢀ
WZꢀ3, there are a half of H4TZPP2ꢀ porphyrin ligand, a half of
TZPP6ꢀ, one chlorine ion, two and one quarter of Cu2+ ions, one
quarter of water molecules, a half of dimethylamine cation, and
solvent molecules. There are altogether five kinds of Cu2+
coordination centers (Fig. 1a). Cu1 and Cu5 are located in respective
porphyrin core and exhibit square planar geometry. To prove the
occupancy of Cu at porphyrin center, LIFMꢀWZꢀ3 and H6TzPP
The purity of LIFMꢀWZꢀ3 bulk samples were confirmed by
PXRD tests (Fig. 2a). The diffraction patterns for asꢀsynthesized
sample are slightly shifted comparing with the simulated one, which
might be due to small difference of the solvent inclusion states
between the asꢀobtained bulk samples and single crystals. After
activation, all of the measured peaks are closely matched with the
simulated pattern.27,28 The PXRD peaks keep almost the same after
N2 and dye adsorption experiment, manifesting the permanent pore
structure. Furthermore, the chemical stability of LIFMꢀWZꢀ3 was
tested by treating its samples in HCl, HNO3, H2SO4, glacial acetic
acid and NaOH aqueous solutions with variant pH values, and
different organic solvents (CH3CN, MeOH, deionized water and
DMF) for 72 h at room temperature, respectively. The PXRD peaks
of the treated samples remained unchanged, indicating the original
crystal phase was maintained after the treatments (Fig. 2b). The
ligand were dissolved in NaOH aqueous solution (1×
10ꢀ5 mol Lꢀ1)
for UVꢀVis test. As can be seen in Fig. S2, the UV absorption of
LIFMꢀWZꢀ3 is obviously different from that of the pure ligand, in
which the Q band changes from four peaks to two peaks, proving
that the porphyrin center is completely occupied by Cu ions. Cu2
and Cu4 display octahedral coordination environment, which are
coordinated with four nitrogen atoms derived from four tetrazolyl
rings of different TZPP6ꢀ ligands and two chloride ions coming from
metallic salt. Cu3 forms a tetrahedral coordination surrounding and
coordinated with two nitrogen atoms coming from tetrazolyl rings of
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super stability of the LIFMꢀWZꢀ3 framework warrants its sites and dimethylamine cations in the framework induced by the
application in gas and dye adsorption purposes.
quadrupole moment of CO2. Further analysis affords the isosteric
heat of LIFMꢀWZꢀ3 for CO2 adsorption to be 46.8 kJ·molꢀ1 (Fig.
S11).
Fig. 3 Gas sorption for LIFMꢀWZꢀ3: a) N2 sorption isotherm at 77 K (inset:
pore size distribution analyzed with SF method); b) CO2 sorption isotherms at
different temperature; c) selective uptake of CO2 over CH4 and N2 at 298 K;
d) CH4 and C2H6 sorption isotherms at 298 K and 273 K.
The application of LIFMꢀWZꢀ3 for potential separation of light
hydrocarbons was also investigated through measuring the uptake of
C3H6, C2H4, C2H6, and CH4 at 273 and 298 K, respectively (Fig. 3d).
We can clearly see the trend of adsorption ability with C3>C2>C1 for
LIFMꢀWZꢀ3. IAST calculation was applied to evaluate the multiꢀ
component selectivities. Under 1 atm, the selectivities of C3H6,
C2H6, and C2H4 with respect to CH4 are 202.1, 26.8 and 10.7 at 298
K, and 218.2, 17.3 and 9.8 at 273 K. Meanwhile, the selectivities of
C3H6/C2H6 and C3H6/C2H4 are 9.7, 10.7 at 298 K, and 15.4, 13.1 at
273 K, respectively (Figs. S14ꢀ16). The above results suggest that
LIFMꢀWZꢀ3 can be a potential candidate for the separation of C3
with respect to C2 hydrocarbons and C3/C2 hydrocarbons over CH4.
Fig. 2 PXRD patterns of LIFMꢀWZꢀ3. a) Simulated, asꢀactivated, asꢀ
synthesized, activated product soaked in water again, after dye (RB+)
adsorption, and after gas sorption; b) Asꢀsynthesized, soaked in aqueous
solutions with different pH, acids, and different solvents for 72 h.
Gas adsorption
N2 sorption measurements were carried out at 77 K for LIFMꢀ
WZꢀ3, which manifests a type I adsorption isotherm behavior with
the maximal adsorption amount of 141 cm3 g−1 (Figs. 3a, S4, S5).
The Langmuir and Brunauer−Emmett−Teller (BET) surface area
were estimated to be 457 and 509 m2 gꢀ1, and the total pore volume
and pore size are 0.143 cm3 gꢀ1 and 0.64 Å, respectively. Although
the surface area of LIFMꢀWZꢀ3 is not large, the significant number
of uncoordinated nitrogen sites in the framework might enhance
selective adsorption of CO2 and certain hydrocarbons (Figs. S6ꢀ16).
First, the CO2 sorption isotherms at different temperature were
measured, which show an uptake of 103.6 cm3 gꢀ1 at 195 K and 29.5
cm3 gꢀ1 at 298 K (Fig. 3b). For comparison, the CH4 and N2 uptakes
at 298 K are very low, accounting for 7.1 cm3 gꢀ1 and 1.7 cm3 gꢀ1
only (Fig. 3c), which leads to the calculated CO2/CH4 and CO2/N2
selectivity of 7.6 and 34.4 at 298 K and 1 bar, respectively.
Meanwhile, the gas selectivity for CO2/N2 and CO2/CH4 at 273K
was calculated to be 17.9 and 7.3, respectively (Figs. 3c and S13).
We deduce that the good selectivity for CO2 over CH4 and N2 should
be due to the strong interactions with uncoordinated/open nitrogen
Dye adsorption and desorption
As for the adsorption of organic dyes, in order to get high
selectivity, the sizes, shapes and charges of dye molecules are
several important factors to be considered. Thus, nine kinds of dyes,
namely, cationicꢀtype methylene blue (MB+), crystal violet (CV+),
rhodamine B (RB+) and basic red (BR+), anionicꢀtype methyl orange
(MOꢀ) and acid orange (AOꢀ), and neutralꢀtype dimethyl yellow
(DY), Sudan I (SDꢀI), and Sudan II (SDꢀII) with different attributes
(Table S2) were chosen as adsorbent target dyes. The fresh
crystalline LIFMꢀWZꢀ3 were soaked in aqueous solution of MB+,
CV+, RB+, BR+, MOꢀ, AOꢀ, DY, SDꢀI and SDꢀII, respectively. The
concentration of dye molecules during the adsorption process can be
viewed by direct color change and detected quantitatively by UVꢀ
Vis absorption spectroscopy. As a result, the color and concentration
of MOꢀ, AOꢀ, DY, SDꢀI and SDꢀII solutions keep almost constant
with the time shifting, while the changes are clearꢀcut for MB+, CV+,
BR+ and RB+ solutions (Figs.
4 and S17–23). The above
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phenomenon demonstrates that LIFMꢀWZꢀ3 only selectively adsorb dyes remain unchanged. It can thus be inferred that dye adsorption
cationic dyes.
can happen in facile via ionꢀexchange process between the
dimethylamine cations in the 1D channels of LIFMꢀWZꢀ3 and the
cations of MB+ in aqueous solution, while exchange with neutral and
negatively charged dyes are not allowed.
Fig. 4 Temporal evolution of UVꢀVis absorption spectra of 20 ml aqueous
solution containing a) RB+, b) MB+, c) CV+ and d) BR+ (10 mg lꢀ1 for each
kind of dye) by LIFMꢀWZꢀ3 (10 mg) adsorption. The photoꢀgraphs show the
colors of solution before and after 160 or 960 min of organic dye absorption.
Fig. 6 Temporal evolution of UVꢀVis absorption spectra of 40 ml aqueous
solution containing a) CV+/MB+, b) BR+/MB+, and c) RB+/MB+ (10 mg lꢀ1
for each kind of dye) by LIFMꢀWZꢀ3 (10 mg) adsorption. The photoꢀgraphs
show the colors of solution before and after 80 min of organic dyes
absorption. The removal efficiency of LIFMꢀWZꢀ3 with time for binary dye
mixtures, d) MB+/CV+, e) MB+/BR+, and f) MB+/RB+ (Removal efficiency =
(c0ꢀct) / c0 × 100%, c0 represents the original concentration and ct represents
the instantaneous concentration of t moment).
We also studied the discriminative adsorption and separation of
cationic dyes with variant sizes by LIFMꢀWZꢀ3. The four cationic
dyes MB+, CV+, BR+ and RB+ possessing the same kind of positive
charge but different molecular sizes were mixed into binary
solutions with the same concentration and volume ratio. As shown in
Table S3, the molecular sizes for the dyes are in order of MB+ < CV+
< BR+ < RB+ as calculated by software of material studio. Then
samples of LIFMꢀWZꢀ3 were immersed in aqueous solutions of
CV+/MB+, BR+/MB+ and RB+/MB+. Obviously, the homologous
colors of the mixed CV+/MB+, BR+/MB+ and RB+/MB+ aqueous
solution changed from blue to purple, from purple to pink and from
blue to pink, respectively (Figs. 6aꢀc). In UVꢀVis spectra, the
absorption peak intensity at 654 nm assigned for MB+ is dropped
more abruptly and almost faded away after 80 min. While the
absorption peaks of CV+, BR+ and RB+ are decreased sluggishly,
suggesting that the adsorption of these larger molecules are
suppressed upon the coꢀexistence of MB+, manifesting size and
steric effects. Meanwhile, we can also notice that the outer contour
of MB+ is more suitable for the spindleꢀlike channels of LIFMꢀWZꢀ3
and can easily get access into the channels by ion exchange process.
This size and shape effect can be more evidenced by the selective
Fig. 5 Temporal evolution of UVꢀVis absorption spectra of 40 ml aqueous
solution containing a) AOꢀ/MB+, b) MOꢀ/MB+, c) SDꢀI/MB+ and d) DY/MB+
(10 mg l−1 for each kind of dye) by LIFMꢀWZꢀ3 (10 mg) adsorption. The
photoꢀgraphs show the colors of solution before and after 160 or 960 min of
organic dyes absorption.
In order to further verify this conclusion, crystalline LIFMꢀWZꢀ3
samples were immersed into the aqueous solutions containing mixed
dyes of DY/MB+, SDꢀI/MB+, SDꢀII/MB+, MOꢀ/MB+ and AOꢀ/MB+,
respectively (Figs. 5 and S22). It can be observed that LIFMꢀWZꢀ3
only adsorb cationic dyes from the mixed solution, and therefore, the
solution colors change from green to yellow for AOꢀ/MB+, MOꢀ
/MB+ and SDꢀII/MB+, from jade to shallow green for SDꢀI/MB+, and
from green to shallow green for DY/MB+. The intensity changes of
relative adsorption peaks are more obvious, in which those related
with MB+ are drastically dropped, while the peaks related with other
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solution of organic dyes of MB+, CV+, RB+, respectively. The
temporal UVꢀVis spectra evolution relating to the decrease of MB+,
CV+ or RB+ was monitored to determine the uptake capacity of
LIFMꢀWZꢀ3 (Figs. S27ꢀ29). And the dye adsorption amount was
calculated using the equation qe=V(c0ꢀce)/M, where qe (mg/g) is the
equilibrium removal capacity; c0 (ppm) and ce (ppm) represent the
initial and equilibrium concentrations of ST solution, respectively; V
(L) is the volume of adsorbate solution; M (g) is the mass of
adsorbents. As a result, the maximum uptake capacities of LIFMꢀ
WZꢀ3 is determined to be 983 mg g−1 for MB+, 713.5 mg g−1 for
CV+, and 141.5 mg gꢀ1 for RB+, respectively (Table S4). The MB+
and CV+ uptake capacities rank the toppest compared with those
reported adsorbents including MOFs, graphene, activated carbon,
SiO2 complex, zeroꢀvalent iron, etc (Table 1), as far as we know.
removal efficiency curves for the binary dye mixtures (Figs. 6dꢀf).
For comparison, the ground MOF powders were further used for dye
adsorption and the removal efficiency is obvious increased than
large crystals. This is due to the fact that the smaller size in powder
samples leads to more surface contact with the dye molecules, and
results in more fast adsorption. As we can see in Fig. S24, the
adsorption rate for MB+ ion with MOF powders was several orders
of magnitude higher than that of MOF crystals. Similarly, the
adsorption rate for CV+, RB+ and BR+ are also increased by using
the MOF powders.
For practical application of both the adsorbents and aimed dyes
with recycle purpose in industry, release experiments were
performed in pure CH3CN and NaCl saturated solution of CH3CN,
for MB+/LIFMꢀWZꢀ3, CV+/LIFMꢀWZꢀ3, BR+/LIFMꢀWZꢀ3 and
RB+/LIFMꢀWZꢀ3 samples after loading dyes. As shown in Fig. 7,
MB+, CV+, BR+, and RB+ can be released into NaCl saturated
CH3CN solution from the loaded samples, and the release rate for
MB+ is more sharply than CV+ and RB+ in the same time of 12 h.
However, no dyes can be released from the loaded samples in pure
CH3CN solution. This confirms that the release of cationic dyes from
the loaded MOFs is also via ionꢀion exchange pathway in Na+
containing CH3CN solution, and further illustrates the MOF with an
anionic attribute. Furthermore, recycling adsorption experiments
were done after dyes release. As can be seen from Fig. S25, the
recovered MOF can be recycled and reused for further dyes
absorption experiment for more than 8 runs without losing the
uptake capacity. And PXRD tests also manifest the stability of the
framework after repeating cycles of dye adsorption and release (Fig.
S26).
Table 1 Comparison of MB+ and CV+ adsorption capacity in various
materials.
Adsorption capacity
(mg/g)
Materials
Ref
Fe3O4@Ag/SiO2
magnesium silicate
Graphene
128.5 (MB+)
602 (MB+)
29a
29b
397 (MB+)
30
Activated carbon
zeroꢀvalent iron
InꢀMOF
135 (MB+)
31
151.5 (MB+), 172.4 (CV+)
724 (MB+)
32
33
AminoꢀMILꢀ101(Al)
ErCuꢀPOM (Erꢀ3)
ZJUꢀ24ꢀ0.89
762 (MB+)
34
391.3 (MB+)
902 (MB+)
35
36
Ce(III)ꢀdoped UiOꢀ66
CdꢀMOF
145.3 (MB+)
221 (CV+)
37
38
BTTC
270 (MB+), 184 (CV+)
713.5 (CV+)
983 (MB+)
4
LIFMꢀWZꢀ3
This work
This work
LIFMꢀWZꢀ3
Conclusions
In summary, a unique tetrazolyl porphyrinꢀbased microporous
2D+3D→3D anionic MOF (LIFMꢀWZꢀ3) has been successfully
synthesized, showing good thermal and chemical stabilities. The
spindleꢀlike 1D pores and abundant nitrogen vacant sites in the
framework afford selective adsorption and separation abilities for
CO2/N2, CO2/CH4, and C3/C2 hydrocarbons over CH4 gases.
Meanwhile, LIFMꢀWZꢀ3 can selectively adsorb cationic dyes with
appropriate sizes and shapes in aqueous solutions through an ionꢀion
exchange process and manifests recordꢀhigh adsorption capacities
for MB+ and CV+, respectively. Furthermore, the adsorbed dyes can
be released again from the framework in saturated NaCl solution of
CH3CN, qualifying the recycle of both MOF adsorbents and aimed
Fig. 7 a) MB+, b) CV+ and c) RB+ release experiment from the corresponding
LIFMꢀWZꢀ3 adsorbed samples in NaCl saturated solution of CH3CN; d) the
dye release rate in CH3CN and NaCl saturated solution of CH3CN (black line
for MB+/LIFMꢀWZꢀ3 in CH3CN, green, blue and red line for MB+/LIFMꢀ
WZꢀ3, CV+/LIFMꢀWZꢀ3 and RB+/LIFMꢀWZꢀ3 in NaCl saturated solution of
CH3CN, respectively).
To further quantify the dye uptake capacities of LIFMꢀWZꢀ3,
amounts of adsorbents from 1 to 5 mg were added into five different
centrifuge plastic tubes containing 20 ml (20 mg lꢀ1) aqueous
6 | J. Name., 2017, 00, 1-3
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dyes. This work provides more direct evidence of MOFs in the
application of selective adsorption and separation of gases,
hydrocarbons and dyes, and paves the way for the design of MOFs
with specific functionalities in sustainable production and
environmental protection fields.
9
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STP Project of Guangzhou (201504010031), NSF of
Guangdong Province (S2013030013474), Local Innovative and
Research Teams Project of Guangdong Pearl River Talents
Program (2017BT01C161), and FRF for the Central
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Journal of Materials Chemistry A
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DOI: 10.1039/C8TA06249H
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