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, ChineseAcademy of Sciences, Ningbo,Zhejiang 315201, China.

*Corresponding author: E-mail: ;

1. Breakthrough curve measurement. Breakthrough curveexperiments 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.

FigureS2 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 S3Weight loss curves of the pure PEI andMIL-101(Cr) before and after loading PEI.

Figure S4N2 adsorption-desorption isotherms for PEI-MIL-101-160 at 77.3 K. The symbols: filled, adsorption; blank, desorption.

Figure S5The CO2 adsorption isotherms of theMIL-101(Cr) before and after loading PEI at 50 oC. 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 S6Adsorption of CO2 on dry and humid PEI-MIL-101-100.

FigureS7CO2 adsorption kinetics of PEI-MIL-101-100.

FigureS8CO2 adsorption kinetics of PEI-MIL-101-50.

FigureS9CO2 adsorption kinetics of PEI-MIL-101-75.

Figure S10CO2 adsorption kinetics of PEI-MIL-101-125.

Figure S11The CO2 adsorption isotherms of theMIL-101(Cr) before and after loading PEI at 25 oC. Lines are the fitted isotherms.

FigureS12The CO2 adsorption isotherms of theMIL-101(Cr) before and after loading PEI at 50oC. Lines are the fitted isotherms.

FigureS13 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 S3Element analysis of PEI, MIL-101(Cr) and PEI-MIL-101-100.

C (wt%) / H (wt%) / N (wt%)
PEI / 49.27 / 13.05 / 32.84
ActivatedMIL-101(Cr) / 33.60 / 4.70 / 0.24
ActivatedPEI-MIL-101-100 / 44.07 / 8.68 / 16.58

The calculatedPEI content in PEI-MIL-101-100 is 101%, which is consistent with the designed value 100%.

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[2] K. Sumida, D. L. Rogow, J. A. Mason, T. M. McDonald, E. D. Bloch, Z. R. Herm, T. H. Bae and J. R. Long, Chem Rev, 2012, 112, 724-781