Chemistry - A European Journal
10.1002/chem.201701884
FULL PAPER
To examine capture and separation of organic dyes with
different molecular sizes by PCN-124-stu based on visible color
of dyes and the colorless nature of the crystal, PCN-124-stu(Zn)
2
In order to evaluate the adsorption mechanism of CO , ENR,
NOR, and OFL molecules in adsorbent at molecular level, the
non-covalent interactions between adsorbates and Framework
are described using Dreiding force field, and the atomic charges
calculated by charge equilibration method were used to describe
electrostatic interaction by spherical Lennard-Jones (LJ) 12-6
potentials. In this work, Grand canonical Monte Carlo (GCMC)
(
5 mg) was soaked in EtOH solution containing dyes of large
molecules and test their PXRD respectively (Figure S16 and
S17 in the Supporting Information). For R-250 adsorption, an
aqueous stock solution of R-250 (C ) was prepared by dissolving
0
R-250 in water. The activated adsorbents (5 mg) were added
into vials filled with R-250 solutions (5 mL) of different
2
were performed to obtain the density distribution of CO within
PCN-124-stu at 1 bar and 273 K, and Configurational bias
Monte Carlo (CBMC) simulations were performed to FQs
molecules at 1 bar and 303 K. In Monte Carlo simulation, a total
of 4 107 steps were used; the first 50 % of these moves were
used for equilibration, and the remaining 107 steps were used
for calculating the ensemble averages. Above all, three
antibiotics’ optimal structures were simulated via B3LYP/6-
-4
-1
concentrations (5–200 × 10 mol∙L ), which were prepared by
successive dilution of the stock solution. After quiescence at
room temperature for 2 days, the solutions were separated from
the adsorbents, and monitored with a UV-vis spectrophotometer
-1
at 588 nm. The adsorbed amount Q
e
(mg∙g ) of R-250 was
calculated using the mass balance with eq. 1.
3
7
11+G* in Gaussian 09. Process detail is provided in the Section
of Supporting Information
Q
e
0
e
= (C -C )V/M
(1)
where C
0
e
and C are the initial and equilibrium concentrations of
-1
solutions on centration of R-250 (mg∙L ); V is the volume of
solution (L); and M is the mass of adsorbent (g). And the Acknowledgements
resulting adsorption isotherms are fitted by Langmuir mode.
We gratefully acknowledge financial support from the National
Basic Research Program of China (973 Program,
2013CB834803), NSFC (No. 21571122 , 21171113), and
C
e
/Q
e
=1/(K
L
∙Q
m
)+ C
e
/Q
m
(2)
-1
where C
and Q are the equilibrium and maximum monolayer adsorbed
amount (mg∙g ); K
e e
is the equilibrium concentration of R-250 (mg∙L ); Q
m
Department
of
Education
in
Guangdong
Province
-1
-1
L
(L∙g ) is the Langmuir constant related to the
(
2014KCXTDO12).
free energy of adsorption.
Keywords: amide functionalization • Metal-organic frameworks •
chemical stability• antibiotics removal • dyes adsorption
Adsorption of FQs.
At room temperature, activated PCN-124-stu(Cu) (5 mg) was
transtransferred to water solutions (10 mL) containing given
concentrations of ENR (enrofloxacin), NOR (norfloxacin) and
OFL (ofloxacin), respectively. After three days of soakage (for
adsorption balance), HPLC-FLD of the solutions were recorded
to characterize the adsorption performances of PCN-124-
stu(Cu) at specific condition (exciting wavelength: 280 nm,
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emission wavelength: 450 nm; injection volume: 2 L; flowing
[
phase: acetonitrile-0.067 moL∙L-
1
H
3
PO
solution in volume ratio
4
-
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samples were carried out with parallel experiments. For study of
solvent effect, PBS buffer solution (30 mL, pH = 7.4) was used
for ENR release (Figure S25 in the Supporting Information).
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2
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2
tested using PXRD and N adsorb test (Figure S27-28 in the
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[
Computational Methods.
1
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