Preparation and Gas Separation Properties of Metal-organic Frameworks/Polyimide Mixed Matrix Membranes†

doi:10.7503/cjcu20140076

Abstract

Abstract:

Three metal-organic frameworks(MOFs) with different structure, particle size and gas adsorption properties were synthesized: micron-scale Cu₃(BTC)₂, sub-micron ZIF-8 and S-Cu₃(BTC)₂. Nitrogen adsorption-desorption isotherms of MOFs showed that ZIF-8 and Cu₃(BTC)₂ possessed quite large BET surfaces(1653 and 1439 m²/g), and BET surface of S-Cu₃(BTC)₂ was 171.4 m²/g. MOFs were directly introduced into polyimide to fabricate mixed matrix membranes(MMMs). It was proved by XRD and FTIR-ATR characterizations that MOFs had no structural or chemical degradation in MMMs. Gas permeation test result indicated that gas separation properties of MMMs were enhanced as MOFs were added. Comparing with pure polyimide membrane, the adding of ZIF-8 or Cu₃(BTC)₂ brought gas permeability increase about 3 times, gas permeability of MMMs with S-Cu₃(BTC)₂ increased 175%. Meanwhile gas selectivies for O₂/N₂ and CO₂/CH₄ decreased slightly.

Key words: Metal-organic framework, Polyimide, Mixed matrix membrane, Gas separation

CLC Number:

O631

TrendMD:

DUAN Cuijia, CAO Yiming, JIE Xingming, WANG Lina, YUAN Quan. Preparation and Gas Separation Properties of Metal-organic Frameworks/Polyimide Mixed Matrix Membranes^†[J]. Chem. J. Chinese Universities, 2014, 35(7): 1584.

Figures/Tables 9

Scheme 1 Chemical structure of ODPA-TMPDA

Fig.1 Nitrogen adsorption-desorption isotherms of S-Cu3(BTC)2(a), Cu3(BTC)2(b) and ZIF-8(c)

Table 1 Structure properties of Cu3(BTC)2, S-Cu3(BTC)2 and ZIF-8

MOFs	BET surface/(m²·g^-1)	Pore volume/(cm³·g^-1)	Particle size/μm
Cu₃(BTC)₂	1439	0.642	2—9
S-Cu₃(BTC)₂	171.4	0.154	0.1—1.0
ZIF-8	1653	0.592	0.3—1.0

Fig.2 TGA curves of S-Cu3(BTC)2(a), Cu3(BTC)2(b), ODPA-TMPDA(c) and ZIF-8(d)

Fig.3 XRD patterns(A) and FTIR-ATR spectra(B) of ODPA-TMPDA membrane, MOFs and MOFs/ODPA-TMPDA mixed matrix membranes a. ODPA-TMPDA membrane; b. Cu3(BTC)2; c. Cu3(BTC)2/ODPA-TMPDA MMM; d. S-Cu3(BTC)2;

Fig.4 Cross-section SEM images of MOFs/ODPA-TMPDA mixed matrix membranes at low(A—C) and high(D—F) magnification (A),(D) Cu3(BTC)2/ODPA-TMPDA MMM; (B),(E) S-Cu3(BTC)2/ODPA-TMPDA MMM; (C),(F) ZIF-8/ODPA-TMPDA MMM.

Fig.5 Gas permeability of ODPA-TMPDA membrane and MOFs/ODPA-TMPDA mixed matrix membranes

Table 2 Gas separation properties of membranes in this work and model predictions

Membrane	P/Barrer				Selectivity
Membrane	O₂	N₂	CH₄	CO₂	O₂/N₂	CO₂/CH₄
ODPA-TMPDA	8.93	1.74	1.63	47.76	5.13	29.30
Cu₃(BTC)₂/ODPA-TMPDA	35.47	7.07	7.00	180.80	5.02	26.64
S-Cu₃(BTC)₂/ODPA-TMPDA	25.00	5.27	4.94	131.70	4.93	26.30
ZIF-8/ODPA-TMPDA	38.79	8.90	7.71	189.80	4.81	23.53
Maxwell model	20.41	3.98	3.73	109.20	5.13	29.30
Bruggeman model	26.03	5.07	4.75	139.20	5.13	29.30

Table 3 Gas diffusivity and solubility of ODPA-TMPDA membrane and MOFs/ODPA-TMPDA mixed matrix membranes

Membrane	10⁸ Diffusivity/(cm²·s^-1)				Solubility/(cm³·g^-1)
Membrane	O₂	N₂	CH₄	CO₂	O₂	N₂	CH₄	CO₂
ODPA-TMPDA	5.10	1.24	0.276	1.78	0.0176	0.0141	0.0591	0.269
Cu₃(BTC)₂/ODPA-TMPDA	10.00	2.39	0.643	4.88	0.0359	0.0298	0.1080	0.371
S-Cu₃(BTC)₂/ODPA-TMPDA	9.72	2.48	0.582	4.28	0.0267	0.0229	0.0839	0.310
ZIF-8/ODPA-TMPDA	17.10	3.99	1.150	7.42	0.0227	0.0203	0.0669	0.256

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