Supporting Information
Polyethyleneimine Incorporated Metal-Organic Frameworks
Adsorbent for Highly Selective CO2 Capture
Yichao Lin, Qiuju Yan, Chunlong Kong* & Liang Chen*
Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo, Zhejiang 315201, China.
*Corresponding author: E-mail: chenliang@nimte.ac.cn; kongchl@nimte.ac.cn
1. Breakthrough curve measurement. Breakthrough curve experiments were
carried out using a column with a length of 20 cm and an internal diameter of 0.8 cm.
The sample powder was packed in the middle part of the column. Here, the sample mass
we used is 0.15 g. Breakthrough allows in situ activation of the sample under Ar flow.
The experiment methodology is fully described in [1,2]. The CO2 and N2 flow is 20
Nml/min, the total CO2 and N2 mixture flow is 40 Nml/min. The flow rates of all the pure
gases were controlled by mass flow controllers. Before the measurement, the sample
was activated at 110 oC for 1 hours. The gas stream from the outlet of the column was
analyzed on-line with a mass spectrometer.
2. CO2 adsorption measurement of humid PEI-MIL-101 sample. The PEI-MIL-101
sample was first activated under 110 oC under vacuum condition for 12 hours, and then
the mass was immediately measured (m1). After that, the PEI-MIL-101 sample was
quickly transferred to a vacuum box, together with a cup of deionized water. The
vacuum box was then evacuated and heated at 80 oC. 6 hours later, the sample was
taken out of the vacuum box and the mass was measured (m2). The value of (m2- m1) is
the amount of adsorbed water. Finally, the sample was quickly transferred to an
apparatus sample holder for CO2 adsorption measurement without any pre-treatment.
In our experiments, m1 and m2 were 0.2939 and 0.3209 g, respectively. As shown in
Figure S6, the obtained humid PEI-MIL-101-100 with 9.2 wt% water exhibited even no
decreased CO2 adsorption capacity than that of dry PEI-MIL-101-100.
2. Figures
Figure S1 PXRD patterns of MIL-101(Cr) and PEI-MIL-101 with different PEI loadings.
Figure S2 IR spectra ofMIL-101(Cr) before and after loading PEI, and pure PEI. From
bottom to top: MIL-101(Cr), PEI-MIL-101-50, PEI-MIL-101-75, PEI-MIL-101-100,
PEI-MIL-101-125, PEI. he N-H bending vibration was observed at 1570 cm-1, which was
labeled with asterisk.
Figure S3 Weight loss curves of the pure PEI and MIL-101(Cr) before and after loading
PEI.
Figure S4 N2 adsorption-desorption isotherms for PEI-MIL-101-160 at 77.3 K. The
symbols: filled, adsorption; blank, desorption.
Figure S5 The CO2 adsorption isotherms of the MIL-101(Cr) before and after loading
PEI
at
50
C.
o
Symbol:
■MIL-101(Cr),
●
PEI-MIL-101-50,
★PEI-MIL-101-75,
◆PEI-MIL-101-100, ▲PEI-MIL-101-125. Lines are the fitted isotherms.
Figure S6 Adsorption of CO2 on dry and humid PEI-MIL-101-100.
Figure S7 CO2 adsorption kinetics of PEI-MIL-101-100.
Figure S8 CO2 adsorption kinetics of PEI-MIL-101-50.
Figure S9 CO2 adsorption kinetics of PEI-MIL-101-75.
Figure S10 CO2 adsorption kinetics of PEI-MIL-101-125.
Figure S11 The CO2 adsorption isotherms of the MIL-101(Cr) before and after loading
PEI at 25 oC. Lines are the fitted isotherms.
Figure S12 The CO2 adsorption isotherms of the MIL-101(Cr) before and after loading
PEI at 50 oC. Lines are the fitted isotherms.
Figure S13 Breakthrough curves of PEI-MIL-101-100 with an equimolar CO2/N2 mixture
at 25 oC.
Table S1 The mass of PEI-MIL-101 before adsorption and after desorption
measurements.
m1 (g)
m2 (g)
PEI-MIL-101-50
0.2245
0.2245
PEI-MIL-101-75
0.2398
0.2395
PEI-MIL-101-100
0.2941
0.2939
PEI-MIL-101-125
0.3134
0.3130
To confirm the complete desorption of CO2, we compared the mass of PEI-MIL-101
materials before adsorption and after desorption. First, we measured the mass of
activated sample before measurement and obtained a value of m1. Then, when the CO2
adsorption measurement was completed, we further activated the sample at 110 oC for
1 hour under vacuum condition. After that, we measured the sample mass again and
obtained a value of m2. If the values of m2 and m1 are equal, the CO2 desorption should
be complete.
Table S2 Gas selectivities at the tested temperatures.
Mass (CO2) at 0.15bar/Mass (N2) at 0.75bar
25 oC
50 oC
MIL-101
2.3
2.2
PEI-MIL-101-50
22
24
PEI-MIL-101-75
84
90
PEI-MIL-101-100
120
150
PEI-MIL-101-125
150
240
Table S3 Element analysis of PEI, MIL-101(Cr) and PEI-MIL-101-100.
C (wt%)
H (wt%)
N (wt%)
PEI
49.27
13.05
32.84
Activated MIL-101(Cr)
33.60
4.70
0.24
Activated PEI-MIL-101-100
44.07
8.68
16.58
The calculated PEI content in PEI-MIL-101-100 is 101%, which is consistent with the
designed value 100%.
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