Supporting Information

Enhanced stability of MFI zeolite membranes for

separation of ethanol/water by eliminating surface

Si-OH groups

Zhengqi Wu‡, Chun Zhang‡, Li Peng, Xuerui Wang, Qingqing Kong, and Xuehong Gu*

College of Chemical Engineering, State Key Laboratory of Materials-Oriented Chemical

Engineering, Synergetic Innovation Center for Advanced Materials, Nanjing Tech University,

Nanjing 210009, P. R. China

E-mail: xhgu@njtech.edu.cn

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Table of Contents

Experimental Procedures 3

Table S1 The pervaporation performance of MFI zeolite membranes before dopamine modification 6

Figure S1 EDX result of dopamine modified MFI zeolite membrane 7

Figure S2 The 12h pervaporation performance of the MFI zeolite membranes with different dopamine

modification time 8

Figure S3 Pervaporation performance of MFI zeolite membrane before and after calcination 9

Figure S4 Permeation flux of MFI zeolite membrane in pure water at 60 °C 10

Figure S5 Permeation flux of MFI zeolite membrane in anhydrous ethanol at 60 °C 11

Figure S6 TG profiles of MFI zeolite particles in N2 stream before and after treatment with ethanol 12

Figure S7 29Si MAS NMR spectra of MFI zeolite particles before and after treatment with ethanol 13

Figure S8 XRD patterns of MFI zeolite particles before and after dopamine modification 14

Figure S9 Pervaporation performance of MFI zeolite membranes before and after TEOS modification 15

References 15

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Experimental Procedures

Materials: YSZ hollow fibers (1.78 mm O.D., 0.8 mm I.D.) were fabricated in our laboratory

by wet-spinning method. Hydroxypropyl cellulose (HPC, 99 %, Sigma-Aldrich),

tetraethoxysilane (TEOS, 98 wt%, Sinopharm Chemical Reagent Co., Ltd., China),

Tetrapropylammonium hydroxide (TPAOH, 1M, Sigma-Aldrich), Dopamine hyrochloride (98%,

Aladdin), and Tris(hydroxymethyl)aminomethane (Tris–HCl, 99.9%, Aladdin).

Preparation of MFI zeolite (silicalite-1) seeds: Details of the seed synthetic procedure have

been reported in our previous paper.1 The size of the MFI zeolite seed crystals is ca. 130 nm.

Seeding: Seeding suspension was prepared by dispersing 1 g silicalite-1 particles into 100 mL

of aqueous solution containing 0.1 wt % HPC. The suspension was stirred for 4 h before used for

dip-coating. The contacting time of the dip-coating process was 5 s. The seeded supports were

dried in an oven at 60 °C overnight and then calcined at 450 °C for 6 h.

Preparation of MFI zeolite membranes: The seeded supports were immersed in a synthesis

solution loaded with an autoclave vertically for hydrothermal crystallization. The synthesis

solution was prepared by mixing TEOS, TPAOH and deionized water at 40 °C with stirring for 6

h. The compositions of synthesis solution had a molar composition of SiO2: TPAOH: H2O=1:

0.17: 176. Hydrothermal synthesis was carried out at 180 °C for 10 hours. Detailed synthesis

method could be found in our previous publication.2

Dopamine modification: Dopamine (2 mg·mL-1) was dissolved in 10 mM Tris–HCl (pH=8.5)

in a graduated cylinder. MFI zeolite membranes with both ends sealed by Teflon tape were

allowed to contact with the dopamine solution (50 mL). The solution was stirred for 24 h at

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ambient temperature, leading to a polydopamine layer being deposited on the MFI zeolite

membrane surface. Then the membranes were rinsed and dried in oven.

TEOS modification: TEOS and D.I. water were respectively introduced into both sides of a

zeolite membrane. TEOS flowed over the membrane side and D.I. water flowed over the

substrate side. The membranes were continuously under modification at room temperature for 3

h. After drying at 120 °C for 12 h, the TEOS modified membranes were calcinated at 450 °C for

4 h.

The separation performance: The separation performance of MFI zeolite membrane was

tested by pervaporation separation of 5 wt% ethanol solution at 60 °C. One end of membrane

was sealed with silica rubber, while the other end was connected to vacuum line. The inner of

hollow-fiber membrane was evacuated to maintain a pressure below 200 Pa throughout the

operation. The permeate stream was collected by two liquid nitrogen traps in parallel for

sampling without interruption of the operation. The compositions of the feed and permeate were

analyzed by a gas chromatography (GC-2014, Shimadzu) equipped with a thermal conductivity

detector (TCD) and a packed column of Paropark Q. The permeation flux (J, kg·m-2·h-1) and

separation factor (α) for ethanol over water are defined as in Equations (1) and (2), respectively:

w
J = (1)
A ⋅ ∆t

ye / yw
α = (2)
xe / xw

In the equations, w is total mass (kg) permeated over a time period of ∆t (h); A is the effective

membrane area (m2); ye, yw are the weight fractions of ethanol and water in the permeate and xe,

xw are the weight fractions of ethanol and water in the feed.

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 Characterization: The crystal phases of samples were determined by X-ray diffraction (XRD,

MiniFlex 600, Rigaku) with a Cu−Kα radiation source in the 2 theta range of 5−50°. The textures

of MFI zeolite membranes were observed by scanning electron microscopy (SEM, S4800,

Hitachi). The elemental distribution of zeolite membrane was determined by an electron probe

microanalyzer (EMAX x-act, Horiba). The compositional properties of the obtained MFI zeolite

powders were examined by Thermogravimetric analyzer (TG, STA 209F1, Netzsch), Fourier-

transform infrared spectroscopy (FT-IR, Nicolet 8700, Nicolet), and Solid state nuclear magnetic

resonance instrument (29Si MAS NMR, Advance 400, Bruker). The surface hydrophilicity of

hollow fiber MFI zeolite membranes was determined by contact angle measurement (CA,

DropMeter A-100p, MAIST) using a sessile drop method with a 0.2 µL droplet of deionized

water.

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Table/Figure

Table S1 The pervaporation performance of MFI zeolite membranes before dopamine

modification. (Feed condition: 5 wt% ethanol/water mixture, 60 °C)

Pervaporation performance

Flux (kg·m-2·h-1) Separation factor

M1 4.7 44

M2 4.7 38

M3 4.5 40

M4 4.8 41

M5 4.9 43

M6 4.7 40

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Figure S1 EDX spectrum of dopamine modified MFI zeolite membrane

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Figure S2. The 12h pervaporation performance of the MFI zeolite membranes with different

dopamine modification time (0 h: M1, 6 h: M2, 12 h: M3, 18 h: M4, 24 h: M5, 36 h: M6) (Feed

condition: 5 wt% ethanol/water mixture at 60 °C).

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Figure S3. Pervaporation performance of MFI zeolite membrane before and after calcination.

(Feed condition: 5 wt% ethanol/water mixture, 60 °C)

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Figure S4. Permeation flux of MFI zeolite membrane in pure water at 60 °C.

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Figure S5. Permeation flux of MFI zeolite membrane in anhydrous ethanol at 60 °C.

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Figure S6. TG profiles of MFI zeolite particles in N2 stream before and after treatment with

ethanol.

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 29
Figure S7. Si MAS NMR spectra of MFI zeolite particles before (a) and after (b) treatment

with ethanol

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Figure S8. XRD patterns of MFI zeolite particles before (a) and after (b) dopamine modification

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Figure S9. Pervaporation performance of MFI zeolite membranes before and after TEOS

modification

References

(1) Gu X. H.; Dong J. H.; Nenoff T. M.; Ozokwelu D. E. Separation of p-xylene from

multicomponent vapor mixtures using tubular MFI zeolite mmbranes. J. Membr. Sci., 2006, 280,

624-633.

(2) Shu X. J.; Wang X. R.; Kong Q. Q.; Gu X. H.; Xu N. P. High-Flux MFI Zeolite Membrane

Supported on YSZ Hollow Fiber for Separation of Ethanol/Water. Ind. Eng. Chem. Res., 2012,

51, 12073-12080.

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