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aromatic BTC ligands in ionic liquid microemulsions at room Material characterization
temperature and two different Zn-MOF crystal structures have
Powder X-ray diffraction data from the studied samples were
also been afforded. The inuence of different parameters such
as the pH value, the ratio of reactants and the reaction time on
the morphology and size of the Zn-MOFs was demonstrated.
Although, to some extent, the low surface area of the Zn-MOFs
synthesized in these ionic liquid microemulsions may restrict
their application range, the synthesis of metal–organic frame-
works in ionic liquid microemulsions at room temperature is
simple and ts the green chemistry idea, and we believe that
this method can also be widely applied in synthesizing new
materials with various sizes and morphologies.
˚
collected on a D8 ADVANCE with Cu Ka radiation (l ¼ 1.5418 A).
FT-IR spectra were obtained on a Bruker VERTEX70 FT-IR
spectrometer using KBr pellets prepared with sample
powders, and measured in the wavenumber range 4000–
ꢂ1
4
00 cm . Morphology analyses for Zn-MOFs were carried out
on a NTC JSM-6390LV. Thermogravimetric (TG) analyses was
performed in an air atmosphere with a heating rate of
ꢁ
ꢂ1
ꢁ
1
0 C min from 25 to 600 C, using a NETZSCH TG209C
instrument. The single crystal data were collected using
a Bruker SMART X-ray diffractometer, equipped with an APEX-
CCD area detector.
Experimental
Materials
Conflicts of interest
1,3,5-Benzenetricarboxylic acid (BTC) with a purity of >97% was
There are no conicts to declare.
purchased from Accela ChemBio Co., Ltd. Nonionic surfactant
Triton X-100 (TX-100, polyoxyethylene (10) isooctylphenyl
ether, M.W. ¼ 646, Sinopharm Chemical Reagent Co., Ltd.,)
was used without further purication. Zn(NO ) $6H O and
Acknowledgements
3
2
2
This research was nancially supported by the Natural Science
Foundation of Hubei Province of China (2018CFB166) and the
Fundamental Research Funds for the Central Universities
NaOH were purchased from Sinopharm Chemical Reagent Co.,
ꢂ1
Ltd. Water was puried with a Milli-Q 18.3 MU cm water
system. All solvents and reagents for the syntheses were used
as received from commercial sources without further
purication.
(2662017QD029, 2662018JC009).
Notes and references
Synthesis of the ionic liquid [Bmim]PF
6
1
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Synthesis of the ionic liquid was performed in a 250 mL round
bottom ask using a procedure similar to that previously
2
3
1–34
described.
chloride (30.14 g, 0.172 mol) was added to react with 20%
theoretical) excess of KPF (37.98 g, 0.206 mol) in water (150
The ionic liquid 1-butyl-3-methylimidazolinium
3
4
5
(
6
mL) under continuous stirring at room temperature for 12 h.
The organic layer in the reaction mixture was washed with
water (3 ꢃ 30 mL) aer 12 hours and the product was dried
6
7
under vacuum for 8 hours, the pure ionic liquid ([Bmim]PF )
6
1
was obtained and the yield was 32.45 g (0.114 mol, 66.35%). H
NMR characterization is presented in Fig. S4 in the ESI.† H
NMR (600 MHz, d, ppm, DMSO): 2.442 (s), 9.048 (s, H), 7.711–
1
8
9
Z. Q. Li, A. Wang, C. Y. Guo, W. N. Hu and Y. F. Tai, Chem. J.
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7
2
.714 (d, H), 7.645–7.647 (d, H), 3.801 (s, 3H), 4.102–4.126 (t,
H), 1.696–1.745 (m, 2H), 1.186–1.223 (q, 2H), 0.848–0.872
1
1
0 P. Horcajada, R. Gref, T. Baati, P. K. Allan, G. Maurin,
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and G. Ouyang, Anal. Chim. Acta, 2015, 853, 303.
(
t, 3H).
Preparation of the Zn-MOFs
For the experiments, the ionic liquid microemulsions with
desired compositions containing water, [Bmim]PF
X-100 were prepared using a previously reported method.
Zn(NO $6H O (1.0 mmol), NaOH (1.0 mmol) and BTC (1.0 13 Y. Fu, G. Li, F. Liao, M. Xiong and J. Lin, J. Mol. Struct., 2011,
mmol) were added into the ionic liquid microemulsions (20 g). 1004, 252.
The mixed solution was stirred for 24 hours at room tempera- 14 I. A. Ibarra, P. A. Bayliss, E. Perez, S. Yang, A. J. Blake,
6
, and Triton 12 L. E. Kreno, K. Leong, O. K. Farha, M. Allendorf, R. P. Van
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Duyne and J. T. Hupp, Chem. Rev., 2012, 112, 1105.
3
)
2
2
ture. Then, the product was collected by centrifugation at
H. Nowell, D. R. Allan, M. Poliakoff and M. Schroder,
Green Chem., 2012, 14, 117.
4
500 rpm and washed with ethanol three times (3 ꢃ 20 mL) to
remove the surfactant and [Bmim]PF
6
. Then, the white products 15 F. Alosfur, M. Jumali, S. Radiman, N. Ridha, M. Yarmo and
ꢁ
were dried in a vacuum oven at 60 C for 24 hours.
A. Umar, Nanoscale Res. Lett., 2013, 8, 1.
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