Supporting Information

Metal-Organic Framework ZIF-8 Nanocrystals Coated Capillary for Molecular

Sieving of Branched Alkanes from Linear Alkanes along with High-Resolution

Chromatographic Separation of Linear Alkanes

Na Chang, Zhi-Yuan Gu, Xiu-Ping Yan*

Research Center for Analytical Sciences, College of Chemistry, Nankai University, Tianjin 300071, China

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1. Synthesis, Activation and Characterization of ZIF-8 Nanocrystals

ZIF-8 nanocrystal was synthesized at room temperature according to Cravillon et al.S1 Typically, a solution of

Zn(NO3)2·6H2O (293.3 mg, 0.987 mmol) in 20mL of methanol was rapidly poured into a solution of

2-methylimidazole (648.9 mg, 7.904 mmol) in 20mL of methanol under stirring with a magnetic bar. The mixture

slowly turned turbid and after 1 h the nanocrystals were obtained. The nanocrystals were separated from the milky

dispersion by centrifugation at 10000 rpm for 10 min, and then washed with fresh methanol. The procedure was

repeated 3 times to eliminate the unreacted 2-methylimidazole from ZIF-8. The nanocrystals were dried at 100 ℃ in

air. XRD, TGA, SEM, TEM and N2 adsorption were employed to characterize the prepared ZIF-8 nanocrystals.

The XRD patterns were recorded with a D/max-2500 diffractometer (Rigaku, Japan) using CuKa radiation

(λ=1.5418 Å). The XRD pattern of synthesized ZIF-8 was in accordance with the simulated one (Figure S2). The TGA

experiments were performed on a PTC-10A thermal gravimetric analyzer (Rigaku, Japan) form room temperature to

800 ℃ at a ramp rate of 10 ℃ min-1. TGA curve (Figure S3) shows the frameworks of ZIF-8 began to decompose at

350 ℃. BET surface area was measured on a TriStar 3000 sorptometer (Micromeritics, Norcross, GA) using nitrogen

adsorption at 77 K in the range 0.02≤P/P0≤0.20, respectively. The determined BET surface area of ZIF-8 was 1641 m2

g-1. The SEM images (Figure S4) were recorded on a Shimadzu SS-550 scanning electron microscope at 15.0 kV. The

TEM image (Figure S5) was recorded on a JEOL 100CX II microscope (Akishima, Japan) operating at a 100 kV

accelerating voltage.

2. Synthesis, Activation and Characterization of ZIF-7 Nanocrystals

ZIF-7 nanocrystal was synthesized at room temperature according to Li et al.S2 A typical synthesis procedure

was as follows: a solution of Zn(NO3)2·6H2O (302 mg) in 50 mL of DMF was rapidly poured into a solution of

benzimidazole (769 mg) in 50 mL of DMF under stirring with a magnetic bar. After the reaction mixture had been

kept at room temperature for 48 h, the product was separated by centrifugation at 10000 rpm for 10 min, and then

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washed with fresh methanol. The procedure was repeated 3 times to eliminate the unreacted benzimidazole from

ZIF-7. The nanocrystals were dried at 100 ℃ in air. XRD, TGA, SEM and TEM were employed to characterize the

prepared ZIF-7 nanocrystals.

The XRD pattern of synthesized ZIF-7 was in accordance with the simulated one (Figure S11). TGA (Figure

S12) shows the ZIF-7 was stable up to 450 ℃, followed by decomposition of the frameworks. SEM images and TEM

image of ZIF-7 were shown in Figure S13 and Figure S14.

3. Capillary Pretreatment S3

Fused silica capillary (20-m long × 0.25-mm i.d., Yongnian Optic Fiber Plant, Hebei, China) was treated

according to the following recipe before dynamic coating: the capillary was washed with 1 M NaOH for 2 h, ultrapure

water for 30 min, 0.1 M HCl for 2 h, and ultrapure water until the outflow reached pH 7.0. The capillary was dried

with nitrogen purge at 150 ℃ over night.

4. Capillary Coating

ZIF-8 and ZIF-7 were coated onto the pre-treated capillary column by a dynamic coating method as follows:S4

1-mL methanol suspension of ZIF-8 (or ZIF-7) was first filled into the capillary column under gas pressure, and then

pushed through the column at a velocity of 40 cm min-1 to leave a wet coating layer on the inner wall of the capillary

column. To avoid acceleration of the solution plug near the end of the column, a 1 m-long buffer tube was attached to

the capillary column end as a restrictor. After coating, the capillary column settled for 2 h for conditioning under

nitrogen. Further conditioning of the capillary column was carried out using a temperature program: 30 °C for 10 min,

ramp from 30 °C to 300 °C at a rate of 3 °C min-1, and 300 °C for 30 min. The temperature program was repeated for

3 times.

5. Instrumentation

Gas chromatographic measurements were performed on an Agilent 7890 GC system with flame ionization detector

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(FID). Nitrogen (99.999%) was used as the carrier gas. Measurements for gas chromatography-mass spectrometry

(GC-MS) were performed on an Agilent 7890 GC-Agilent 5975c inert MSD with triple axis detector. Helium

(99.999%) was used as the carrier gas for the GC-MS system.

6. Selectivity of Linear Alkanes vs Branched Alkanes on the ZIF-8 Capillary Column

Table S1. Selectivity of linear alkanes vs branched alkanes on the ZIF-8 capillary column at a N2 flow rate of 1 mL

min-1 under 170 °C

2-methyl-mono-branched 2,2-dimethyl-branched
n C-6 1.3 1.3
n C-7 1.6 1.8
n C-8 1.9 2.7

7. Selectivity of Linear Alkanes on the ZIF-8 and ZIF-7 Capillary Columns

Table S2. Selectivity of linear alkanes on the ZIF-8 and ZIF-7 coated capillary columns at a N2 flow rate of 1 mL

min-1 under 170 °C

ZIF-8 ZIF-7
n C-6 n C-7 n C-8 n C-6 n C-7 n C-8
n C-7 1.41 - - 0.85 - -
n C-8 2.34 1.66 - 0.85 0.61 -
n C-9 4.35 3.09 1.86 0.85 0.61 1.00

8. Precision for Separation of Linear Alkanes on the ZIF-8 Coated Capillary Columns

Table S3. Precision for separation of linear alkanes on the ZIF-8 coated capillary column at a N2 flow rate of 1 mL
min-1 under 170 °C.
Analyte RSD (%) (n=5)
Retention Time Half peak width Peak height Peak area
Hexane 0.19 1.5 3.5 4.5
Heptane 0.13 1.2 4.2 5.0
Octane 0.08 0.9 4.9 5.4
Nonane 0.04 0.6 4.3 4.4

References
(S1) J. Cravillon, S. Münzer, S. J. Lohmeier, A. Feldhoff, K. Huber, M. Wiebcke, Chem. Mater. 2009, 21, 1410.
(S2) Y. S. Li, F. Y. Liang, H. Bux, A. Feldhoff, W. S. Yang, J. Caro, Angew. Chem. Int. Ed. 2010, 49, 548.
(S3) Z.Y. Gu, X.P. Yan, Angew. Chem. Int. Ed. 2010, 49, 1477.

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(S4) Ji, Z. H.; Majors, R. E.; Guthrie, E. J. J. Chromatogr. A 1999, 842, 115.

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Figure S1. (left) Sodalite topology and (right) narrow six-membered-ring opening through which molecules have to
pass.5a

Figure S2. XRD pattern of simulated ZIF-8 and synthesized ZIF-8 (after treatment 373K for 4 h).

Figure S3. TGA curves of synthesized ZIF-8.

Figure S4. Typical SEM images of (a) as-synthesized ZIF-8 and (b) the ZIF-8 deposited on the inner wall of the
capillary column.

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Figure S5. Typical TEM image of as-synthesized ZIF-8.

Figure S6. SEM images of the ZIF-8 coatings at different locations on the inner walls of the capillary (a-c), and the
cross sections of the ZIF-8 coating in different parts of the capillary (d-f), showing homogenous coverage and
thickness of the ZIF-8 coating. The inset of (d) shows the overall view of the cross section of the coated capillary.

Figure S7. Gas chromatograms of linear and branched alkanes (a) on the HP-5 ((5%-phenyl)-methylpolysiloxane)
capillary column (30-m long × 0.25-mm i.d.) for the separation of 1: heptane; 2: 2,2-dimethylpentane; 3:
2-methylhexane; 4: octane at a He flow rate of 1 mL min-1 using a temperature program: 50 °C for 1 min, then 3 °C
min-1 to 65 °C; (b) on the MOF-5 coated capillary column (25-m long × 0.25-mm i.d.) for the separation of 1: heptane;
2: 2,2,4-trimethylpentane; 3: 2,2-dimethylhexane; 4: 2-methylheptane; 5: octane at a N2 flow rate of 1 mL min-1 using
a temperature program: 60 °C for 1 min, then 10 °C min-1 to 120 °C.

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Figure S8. Chromatograms on the ZIF-8 coated capillary column (20-m long × 0.25-mm i.d.) for GC separation of
2-methyl-mono-branched alkanes and linear alkanes (1: 2-methylpentane; 2: 2-methylhexane; 3: 2-methylheptane; 4:
hexane; 5: heptane; 6: octane) at a N2 flow rate of 1 mL min-1 under 170 °C.

Figure S9. Gas chromatograms on the ZIF-8 coated capillary column (20-m long × 0.25-mm i.d.) for the separation

of linear alkanes under a N2 flow rate of 1 mL min-1 at 210 °C.

Figure S10. Comparison of peak width between 2,2-dimethyl-branched alkanes and 2-methylpentane under different
temperature conditions.

Figure S11. van’t Hoff plot (variation in capacity factor with temperature) for alkanes.

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Figure S12. XRD pattern of simulated ZIF-7 and synthesized ZIF-7 (after treatment at 373K for 4 h).

Figure S13. TGA curves of synthesized ZIF-7.

Figure S14. Typical SEM images of (a) as-synthesized ZIF-7 and (b) the ZIF-7 deposited on the inner wall of the
capillary column.

Figure S15. Typical TEM image of as-synthesized ZIF-7.

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Figure S16. Gas chromatograms of four linear alkanes on ZIF-7 coated capillary column (20-m long × 0.25-mm i.d.)
at a N2 flow rate of 1 mL min-1 under 140 °C.

Figure S17. Temperature effect on column efficiency for hexane (100 ng) at a N2 flow rate of 1 mL min-1.

Figure S18. Flow effect on column efficiency for hexane (100 ng) at a 140°C.

Figure S19. Effect of analyte mass on (a) the peak area response, and (b) capacity factor on the ZIF-8 capillary

column at a N2 flow rate of 1 mL min-1 under the temperature of 140 °C.

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Figure S20. Typical SEM images of ZIF-8 coated capillary column: (a) a newly coated ZIF-8 capillary column; (b)

the same ZIF-8 capillary column after using for separation of alkanes and petrol samples for several months.

Figure S21. Gas chromatograms of four linear alkanes on ZIF-8 coated capillary column (20-m long × 0.25-mm i.d.)

at a N2 flow rate of 1 mL min-1 under 170 °C (black chromatogram: chromatogram of linear alkanes on a newly coated

ZIF-8 capillary column; red chromatogram: the same linear alkanes on the same ZIF-8 capillary column which has

been used for separation of alkanes and petrol samples for several months).

Figure S22. van Deemter plot for hexane (250 ng) on ZIF-8 capillary column under 140 °C.

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Figure S23. van Deemter plot for hexane (250 ng) on HP-5 capillary column under 140 °C.

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