Supporting Information for

Effective Adsorption Separation of n-Hexane/2-

Methylpentane in Facilely Synthesized Zeolitic Imidazolate
Frameworks ZIF-8 and ZIF-69

Le Chen, Sheng Yuan, Jun-Feng Qian, Wei Fan, Ming-Yang He, Qun Chen*, and Zhi-Hui
Zhang*

Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology, Changzhou

University, Changzhou 213164, People’s Republic of China

* Corresponding author. Fax: 86-519-86330251. Tel: 86-519-86330251.

E-mail: zhangzhjpu@cczu.edu.cn (Z.-H. Zhang) and chenqunjpu@gmail.com (Q.C.)

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Batch adsorption modeling

Freundlich equation, Langmuir equation and Langmuir-Freundlich equation were used to

correlate experimental equilibrium isotherms data for pure components. The equations are as
follows:
Freundlich equation qe = K f C 1/e n (1)

qm K L C e
Langmuir equation qe = (2)
1 + K LCe

qm K h C1/e n
Langmuir-Freundlich equation qe = (3)
1 + K hC 1/e n

Where qe is the equilibrium adsorption capacity, qm is the monolayer maximum adsorption

capacity, Ce is the equilibrium concentration of n-paraffin solution (wt %), Kf and n in equation

(1) are Freundlich constants, the Freundlich equation represents adsorption in an inhomogeneous

sites surface. KL in equation (2) is Langmuir constant. The Langmuir equation perfectly

represents adsorption in a homogeneous sites surface where a sorbate molecule occupies one

active site when it has no interactions with other adsorbed molecules. Kh and n in equation (1)

are Langmuir-Freundlich constants. The Langmuir-Freundlich equation is perfect to represent

adsorption in an inhomogeneous sites surface where a sorbate molecule occupies one active site.

A nonlinear lest-squares regression program based on Gauss-Newton method was used to fit Eqs.

(1) and (2) to experimental equilibrium isotherms data. This program gave the parameters of

each equation and the agreement between experimental and calculated adsorption isotherms in

terms of R2. The fitting calculated constants for the three isotherms equations along with R2

values were presented in Table S2 and Table S3.

Table S2 illustrates that Langmuir-Freundlich model correlates experimental adsorption data

of n-hexane with higher R2 values (above 0.98) for all three adsorbents. For 2-methylpentane

adsorbed on ZIF-8 and ZIF-69, the fitting results are also very suitable with Langmuir-

S2
Freundlich model (see Table S3). While all three adsorption models fail in the prediction of

experimental adsorption data of 2-methylpentane in 5A zeolite with low R2 values due to its few

adsorption capacity.

S3
 100 ZIF-8
ZIF-69

80

Weight /%
60

40

20

0 200 400 600 800

Temperature /°C
Figure S1 TGA curve of ZIF-8 and ZIF-69 samples.

a b
Intensity
Intensity

Adsorbed ZIF-69
Adsorbed ZIF-8

Fresh ZIF-8 Fresh ZIF-69

10 20 30 40 10 20 30 40
2-Theta 2-Theta
Figure S2 XRD patterns of ZIF-8 (a) and ZIF-69 (b) samples before and after adsorption.

Figure S3 SEM images of ZIF-8 (a) and ZIF-69 (b) samples after adsorption.

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 Table S1. The pore structure parameters

sample BET Total pore Total pore volume Average

surface volume of micropores pore size
area (m2/g) (cm3/g) (cm3/g) /nm
ZIF-8 1285.2 0.564 0.436 1.832
ZIF-69 845.1 0.470 0.311 1.754
5A 515.4 0.282 0.210 1.614

Table S2. Isotherms model parameters of adsorption of n-hexane (nHEX) on three

adsorbents.

Freundlich equation Langmuir equation Langmuir-Freundlich equation

Adsorbent
Kf n R2 KL qm R2 Kh qm n R2
ZIF-8 0.0968 1.548 0.962 0.0224 0.147 0.980 0.0537 0.591 0.547 0.994

ZIF-69 0.0129 1.205 0.944 0.0335 0.568 0.956 0.0131 0.392 0.411 0.987

5A 0.0097 2.026 0.927 0.1600 0.0299 0.957 0.0798 0.167 0.494 0.980

Table S3. Isotherms model parameters of adsorption of 2-methylpentane (2MP) on

adsorbents ZIF-8 and ZIF-69.

Freundlich equation Langmuir equation Langmuir-Freundlich equation

Adsorbent
Kf n R2 KL qm R2 Kh qm n R2
ZIF-8 0.0418 3.125 0.917 0.3588 0.114 0.951 0.0967 0.0914 0.349 0.979
ZIF-69 0.0429 2.887 0.952 0.3112 0.129 0.981 0.1693 0.1054 0.508 0.996

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