. State Key Laboratory of Pulp and Paper Engineering, School of Chemistry & Chemical Engineering, Guangdong Provincial Key Lab of Green Chemical Product Technology, South China University of Technology, Guangzhou 510640, China . Guangzhou Academy of Special Equipment Inspection & Testing, Guangzhou 510000, China . Quzhou Membrane Material Innovation Institute, Quzhou 324000, China
Metal-organic frameworks have a wide range of applications in the field of membrane separation, but the inherent flexible structure and the difficulty for scale-up hinder their further applications. Herein, the relatively rigid zeolitic imidazolate framework-8 particles prepared under an electric field (E-ZIF-8) were used as the fillers in polysulfone (PSF) to form series of mixed matrix membranes. It was found that the introduction of E-ZIF-8 improves both the C3H6 permeability and C3H6/C3H8 selectivity of the membranes. Compared with the bare PSF membrane, the C3H6/C3H8 selectivity of the 30 wt % E-ZIF-8@PSF membrane increased by ~230%, while the C3H6 permeability was enhanced by ~830%. In addition, time and pressure dependence analysis demonstrated that such E-ZIF-8@PSF membranes also exhibited good long-term stability and pressure resistance, offering significant industrialization advantages.
Fig.1 Diagram of a home-made Wicke-Kallenbach permeation cell for gas separation.
Fig.2 SEM images of the E-ZIF-8 crystals prepared with different Zn2+/2-methylimidazole ratios of (a) 1:1, (b) 1:2 and (c) 1:4.
Fig.3 XRD refinement results of the E-ZIF-8 synthesized by different Zn2+/2-methylimidazole ratios of (a) 1:1, (b) 1:2 and (c) 1:4 (Rwp: weighted profile R factor; Rexp: excepted profile R factor; GOF: goodness of fit); (d) ZIF-8_I 3m, ZIF-8_Cm, and ZIF-8_R3m proportion of E-ZIF-8-1:1, E-ZIF-8-1:2 and E-ZIF-8-1:4 particles.
Fig.4 The SEM images of (a, b) the top view surface and (c, d) the cross-sectional view of the MMMs prepared using the E-ZIF-8 particles with a relatively big size of 100 nm as the fillers.
Fig.5 SEM images of (a, b) the top view surface and (c, d) the cross-sectional view of the MMMs prepared using the E-ZIF-8 with a relatively big size of 5 μm.
Fig.6 (a) TGA results of the E-ZIF-8 particles, bare PSF membrane and E-ZIF-8@PSF MMMs. The inset shows DCS of the bare PSF membrane and E-ZIF-8@PSF MMMs. (b) XRD patterns of the E-ZIF-8 particles, E-ZIF-8@PSF MMMs and bare PSF membrane, (c, d) FTIR results of the E-ZIF-8@PSF MMMs and bare PSF membrane.
Fig.7 The SEM images of (a, c, d, e, f) the top view surface of the bare PSF membrane and the E-ZIF-8@PSF MMMs with various loadings and (b) the cross-sectional view of the bare PSF membrane.
Fig.8 Single gas permeation through the (a) 30 wt % E-ZIF-8@PSF MMMs and the bare PSF membrane. The gas selectivity for H2 over other gases and C3H6/C3H8 selectivity of (b) the 30 wt % E-ZIF-8@PSF MMMs and (c) bare PSF membrane.
Fig.9 (a) C3H6/C3H8 mixed-gas permeation results through the E-ZIF-8@PSF MMMs with different loadings and the bare PSF membrane. Feed pressure-dependent gas permeability and selectivity of (b) the bare PSF membrane and (c) the 30 wt % E-ZIF-8@PSF MMMs at 298 K for mixed C3H6/C3H8 separation.
Fig.10 (a) Long-term stability of the 9 wt % E-ZIF-8/PSF MMMs at 298?K and 100 kPa applied in C3H6/C3H8 separation, (b) comparison of the perm-selectivity of our E-ZIF-8@PSF MMMs with other polymer membranes and MMMs in the literatures for C3H6/C3H8 separation.
Membrane
C3H6 permeability /Barrer
C3H6/C3H8 selectivity
Ref.
Polymeric membranes
Matrimid
0.1
10
[10]
6FDA/BPDA-DAM
12
14
PPO
6
3.5
[44]
EC
52
3.25
[45]
CA
15.2
2.6
6FDA-6FPDA
0.89
16
[46]
PI-β-CD
81
13.9
[47]
PDMS
6600
1.1
[48]
MMMs
ZIF-8/6FDA-DAM
56.2
31
[49]
X-PI(370)/ZIF-8
2.3
43
[50]
ZIF-8@Ag3pz3/PIM-1
3708
9.5
[51]
DpyNhBt COF-Cu/6FDA-DAM
44.7
28.1
[52]
ZIF-67@Ag4tz4/6FDA-TMPDA
99
39
[53]
SBS/Cu@MIL-101(Cr)
80
5.2
[54]
EC/C60
60
4.9
[55]
PSF-S25
0.15
3.58
[56]
CC3/6FDA-DAM
390
12.1
[57]
QD-FCTF-1/PIM-1
1100
9.5
[58]
30 wt % ZIF-8@PSF
0.75a)
14.7a)
[16]
This work
PSF
0.53
1.62
－
9 wt % E-ZIF-8@PSF
1.00
5.25
－
18 wt % E-ZIF-8@PSF
1.37
9.09
－
30 wt % E-ZIF-8@PSF
1.75
15.03
－
30 wt % E-ZIF-8@PSF
4.2a)
50a)
－
Tab.1 Detailed data comparison of the separation performance of the E-ZIF-8@PSF MMMs and many other membranes, including other polymeric membranes and MMMs in the literatures for C3H6/C3H8 separation as shown in Fig.10(b)
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