Fabrication of COF-MOF Composite Membranes and Their Highly ...
[Supporting Information]
Fabrication of COF-MOF Composite Membranes and Their Highly Selective Separation of H2/CO2 Jingru Fu,a Saikat Das,a Guolong Xing,a Teng Ben,a* Valentin Valtcheva,band Shilun Qiua [*]aDepartment of Chemistry, Jilin University, Changchun, China. Fax: (+86)431-85168298 E-mail: [email protected] b
Normandie Univ, ENSICAEN, UNICAEN, CNRS, Laboratoire Catalyse et
Spectrochimie, 14000 Caen, France
S1
Table of Contents
1. Instruments
S3
2. Materials
S7
3. Chemical reactions involved (Schemes S1, S2 and S3)
S8
4. Fourier transform infrared spectroscopy (FTIR)
S10
5. X-ray diffraction (XRD)
S13
6. Thermogravimetric analysis (TGA)
S15
7. Low pressure N2 sorption measurements
S16
8. Low pressure H2, CO2 and CH4 sorption measurements
S19
9. Gas separation measurements
S22
10. In-situ energy-dispersive X-ray spectroscopy (EDS) results
S29
S2
1. Instruments
1-1. Fourier transform infrared spectroscopy (FTIR) The FTIR spectra (KBr) were obtained using a SHIMADZU IRAffinity-1 Fourier transform infrared spectrophotometer. 1-2. X-ray diffraction (PXRD) The XRD measurements were carried out using SHIMADZU XRD-6000 X-ray diffractometer with Cu-Kα radiation, 40 kV, 30 mA and scanning rate of 0.3o min-1 (2θ). 1-3. Thermogravimetric analysis (TGA) The samples (COF-300 powder, Zn2(bdc)2(dabco) powder and ZIF-8 powder) were put in an alumina pan followed by thermogravimetric analysis (TGA) with SHIMADZU DTG-60 thermal analyzer at a heating rate of 10oC min-1 to 900oC in a dried air atmosphere. The air flow rate was 30 mL min-1. 1-4.Scanning electron microscopy (SEM) and elemental mapping analysis Scanning electron microscopy (SEM) and elemental mapping analysis were carried out with JEOS JSM 6700 scanning electron microscope. 1-5. Low pressure N2 sorption measurements The low pressure N2 sorption measurements were carried out with Micro Meritics Tristar II 3020 surface area and pore size analyzer. Firstly, the solvents (CH3OH, DMF etc.) in the pore were cleared followed by activation of the samples in dynamic vacuum at a certain S3
temperature overnight. After this, the samples were degassed at a certain temperature for 12 h. A sample (80 mg) and a nitrogen (99.999% purity) gas source were employed in the nitrogen sorption measurements at 77 K. 1-6. Low pressure H2, CO2 and CH4 sorption measurements Firstly, samples (COF-300 powder, Zn2(bdc)2(dabco) powder and ZIF-8 powder) of known weight (80 mg) were placed in the sample tubes (weighed beforehand) that were then sealed to avoid the samples from coming in contact with air and moisture. After this, the samples were heated in the sample tubes in vacuum (at a pressure of 100 mtorr or less) and were then kept at a certain temperature and pressure less than 50 mtorr for a minimum of 10 h. The lowpressure H2, CH4, and CO2 sorption measurements were carried out with Micromeritics Tristar II 3020 surface area and pore size analyzer. Post evacuation, the weight of the tubes holding the degassed samples was measured in pursuance of getting to know the mass of the evacuated samples. Ultra-high-purity grade H2,CO2 (99.999 % purity), and CH4 (99.99 % purity) gases were employed for the sorption measurements. The free space was measured with He (99.999 % purity). The H2 isotherms at 77 K were measured in a liquid nitrogen bath and H2isotherms at 87 K in a liquid argon bath. The CO2 isotherms at 273 K were measured in an ice-water bath and CO2 isotherms at 298 K in water bath. The CH4 isotherms at 273 K were measured in an ice-water bath and CH4 isotherms at 298 K in water bath.
S4
1-7. Gas separation measurements In regard to the single gas measurements, He was used as the sweep gas and H2, CO2 and CH4 were used as the feed gases. The flow rate of sweep gas was 150 mL min-1 and that of the feed gases were 50 mL min-1. The pressure at both sides of the membrane was maintained at 1 bar and the measurements were taken at room temperature. Concerning the mixed gas measurements, the feed flow rate for each gas in the 1:1 binary mixture was 50 mL min-1. The flow rate of the sweep gas (He) was 150 mL min-1. The pressure at both sides of the membrane was maintained at 1 bar and the measurements were taken at room temperature.
α H 2 /CO2
y H 2 /y CO2 x H 2 /x CO2
pH2
(S1)
pCO2
where H 2 / CO2 is the separation factor of mixture H2/CO2, x is the molar fraction in the retentate , y is the mole fraction in the permeate, p is the permeance. The permeance measurements were carried out in the 7890A Gas chromatograph. The permeance values ( p ) were converted to corresponding permeability values ( P ) using the formula: P
3.347 10
16
p t mol m /( m 2 s Pa )
(S2)
where p is the permeance (in mol·m-2·s-1·Pa-1), P is the permeability and t is the thickness (in m ) of the membrane. 1 Barrer = 3.347 × 10-16 mol·m-1·s-1·Pa-1.
S5
Figure S1. Schematic illustration of gas separation set-up. (Legends used: MFC: Mass flow controller; GC: Gas chromatograph).
1-8.
Transmission
electron
microscopy
(TEM)
and
energy-dispersive
X-ray
spectroscopy (EDS) The TEM and EDS measurements were accomplished with JEOL JEM-2100F transmission electron microscope operated at an accelerating voltage of 200 kV.
S6
2.Materials
Terephthalaldehyde was purchased from Tokyo Chemical industry Co. Ltd.; Isopentyl nitrite (90%), Hypophoaphoeous acid (50%), Aniline (99.0%), Raney-Nickel (50 µm), Triphenylmethanol (99%), Triethylenediamine (98%), Sodium formate (99.5%) and ZnCl2 (98%) were purchased from Aladdin; Polyaniline (PANI) (Mw = 1.5 x 104), H2BDC (98%), Zn(NO3)2·6H2O (98%) and 2-methylimidazole (99%) were purchased from Aldrich; DMF (99.5%), CH3OH (99.5%), 1,4-Dioxane (99.5%), CH3COOH (99.5%), N2H4·H2O (80%), THF (99.5%), HCl (35%), H2SO4 (98%) and C2H5OH (99.7%) were purchased from West Long Chemical industry. Nitric acid fuming was purchased from Gang Zhou Chemistry industry. All the glass instruments were purchased from Synthware Glass. SiO2 disks were purchased from Wanxianghuabo. Emery paper (500 mesh and 1200 mesh) was purchased from Shanghai New Five Kyrgyzstant Abrasives Co. Ltd. Teflon reactors were purchased from Jinan Henghua Sci.
S7
3. Chemical Reactions involved Scheme S1. Chemical reactions involved during fabrication of COF membrane
CHO
H N
CH N OH
CHO + n
n
CHO
NH2
H2N CHO
NH2
H2 N
NH2
NH2
+
N CH
CH N OH n
NH2
CH N OH n
S8
Scheme
S2.
Chemical
reactions
involved
during fabrication
of
[COF-300]-
[Zn2(bdc)2(dabco)] composite membrane
COOH O
R1 NH2
O O H N R1 H
HO COOH
Zn2+ + R2 NH2
2+
R2 NH2 Zn
3+
N COOH 2 R2 NH2 Zn
H2 N R2 N Zn O H2 R2 N Zn O N
N
2+ +
+
2 N
COOH
O
+
H+
OH
N
Scheme S3. Chemical reactions involved during fabrication of [COF-300]-[ZIF-8] composite membrane
HN
N
2+ Zn2+ + R NH2
R NH2 Zn
HN
S9
H N Zn N R H
2+
4. Fourier transform infrared spectroscopy (FTIR)
Figure S2. FTIR spectra (from 2000 cm-1 to 500 cm-1) of terephthaldehyde (red), PANI (blue), and the product obtained from PANI and terephthaldehyde mixture in anhydrous dioxane and 3M aqueous acetic acid water mixture solvent in teflon reactor at 100 oC for 3 days (black). C=N stretching: 1640 cm-1.
S10
Figure S3. FTIR spectra ( from 800 cm-1 to 400 cm-1) of COF-300 powder (green) and the product obtained with 15 mg COF-300, 272 mg ZnCl2 and 20 mL CH3OH in the teflon reactor at 120 oC for 4 hours (red). Zn-N stretching: 421 cm-1.
S11
Figure S4. FTIR spectra (from 4000 cm-1 to 400 cm-1) of PANI (black) and the product obtained by the mixture of PANI and ZnCl2 and CH3OH in the teflon reactor at 120 oC for 4 hours (red).
Figure S5. FTIR spectra (from 800 cm-1 to 400 cm-1 ) of PANI (black) and the product obtained by the mixture of PANI and ZnCl2 and CH3OH in the teflon ractor at 120 oC for 4 hours (red).
S12
5. X-ray diffraction (XRD)
Figure S6. XRD pattern of degassed COF-300 powder.
S13
Figure S7. XRD patterns of: (a) COF-300 powder, (b) COF-300 membrane, (c) Zn2(bdc)2(dabco) powder, (d) Zn2(bdc)2(dabco) membrane, (e) [COF-300]-[Zn2(bdc)2(dabco)] composite membrane, (f) ZIF-8 powder, (g) ZIF-8 membrane, (h) [COF-300]-[ZIF-8] composite membrane and (i) SiO2 support.
S14
6. Thermogravimetric analysis (TGA)
Figure S8. TGA plot of degassed COF-300 powder (a), Zn2(bdc)2(dabco) powder (b), and ZIF-8 powder (c) in dry air at a rate of 10oC min-1.
S15
7. Low pressure N2 sorption measurements
Figure S9. N2 sorption isotherms of degassed COF-300 powder (solid symbols: adsorption; open symbols: desorption). The inset illustrates the pore size distribution for COF-300 derived from N2 adsorption calculated by Density Functional Theory (DFT) method. The surface area is 2286.6 m2 g-1 and the pore size 2.00 nm.
S16
Figure S10. N2 sorption isotherms of degassed Zn2(bdc)2(dabco) powder (solid symbols: adsorption; open symbols: desorption). The inset illustrates the pore size distribution for Zn2(bdc)2(dabco) derived from N2 adsorption calculated by Density Functional Theory (DFT) method. The surface area is 1274.3 m2 g-1 and the pore size is 0.85 nm.
S17
Figure S11. N2 sorption isotherms of degassed ZIF-8 powder (solid symbols: adsorption; open symbols: desorption). The inset illustrates the pore size distribution for ZIF-8 derived from N2 adsorption calculated by Density Functional Theory (DFT) method. The surface area is 1869.5 m2 g-1 and the pore size is 1.18 nm.
S18
8. Low pressure H2, CO2 and CH4 sorption measurements 8-1. Low pressure gas sorption measurements of degassed COF-300 powder
Figure S12. (A,C,E) H2, CO2 and CH4 sorption isotherms (solid symbols: adsorption, open symbols: desorption) and (B,D,F) isoteric enthalpy Qst of H2, CO2 and CH4 adsorption respectively for degassed COF-300 powder.
S19
8-2. Low pressure gas sorption measurements of degassed Zn2(bdc)2(dabco) powder
Figure S13. (A,C,E) H2, CO2 and CH4 sorption isotherms (solid symbols: adsorption, open symbols: desorption) and (B,D,F) isoteric enthalpy Qst of H2, CO2 and CH4 adsorption respectively for degassed Zn2(bdc)2(dabco) powder.
S20
8-3. Low pressure gas sorption measurements of degassed ZIF-8 powder
Figure S14. (A,C,E) H2, CO2 and CH4 sorption isotherms (solid symbols: adsorption, open symbols: desorption) and (B,D,F) isoteric enthalpy Qst of H2, CO2 and CH4 adsorption respectively for degassed ZIF-8 powder. S21
9. Gas separation measurements Table S1. H2/CO2 separation performance for the COF-300 membrane at room temperature and 1 bar with 1:1 binary mixture of H2 and CO2.
Figure S15. Gas permeability and H2/CO2 selectivity of COF-300 membrane as function of the operating time at room temperature and 1 bar with 1:1 binary mixture of H2 and CO2. S22
Table S2. H2/CO2 separation performance for the Zn2(bdc)2(dabco) membrane at room temperature and 1 bar with 1:1 binary mixture of H2 and CO2.
Figure S16. Gas permeability and H2/CO2 selectivity of Zn2(bdc)2(dabco) membrane as function of the operating time at room temperature and 1 bar with 1:1 binary mixture of H2 and CO2. S23
Table S3. H2/CO2 separation performance for the ZIF-8 membrane at room temperature and 1 bar with 1:1 binary mixture of H2 and CO2.
Figure S17. Gas permeability and H2/CO2 selectivity of ZIF-8 membrane as function of the operating time at room temperature and 1 bar with 1:1 binary mixture of H2 and CO2.
S24
Table S4. H2/CO2 separation performance for the [COF-300]-[Zn2(bdc)2(dabco)] composite membrane at room temperature and 1 bar with 1:1 binary mixture of H2 and CO2.
Figure S18. Gas permeability and H2/CO2 selectivity of [COF-300]-[Zn2(bdc)2(dabco)] composite membrane as function of the operating time at room temperature and 1 bar with 1:1 binary mixture of H2 and CO2.
S25
Table S5. H2/CO2 separation performance for the [COF-300]-[ZIF-8] composite membrane at room temperature and 1 bar with 1:1 binary mixture of H2 and CO2.
Figure S19. Gas permeability and H2/CO2 selectivity of [COF-300]-[ZIF-8] composite membrane as function of the operating time at room temperature and 1 bar with 1:1 binary mixture of H2 and CO2.
S26
Table S6. Single and mixed gas permeability and separation factors for the [COF-300][Zn2(bdc)2(dabco)] composite membrane prepared on porous SiO2 disk at room temperature and 1 bar (in mixed gases permeation, equimolar mixtures have been used).
Permeability is calculated as the membrane permeability multiplied by the membrane thickness. 1 Barrer = 3.347 × 10-16 mol·m-1·s-1·Pa-1. ISF: Ideal separation factor, SF: Separation factor
S27
Table S7. Single and mixed gas permeability and separation factors for the [COF-300]-[ZIF8] composite membrane prepared on porous SiO2 disk at room temperature and 1bar (in mixed gases permeation, equimolar mixtures have been used).
Permeability is calculated as the membrane permeability multiplied by the membrane thickness. 1 Barrer = 3.347 × 10-16 mol·m-1·s-1·Pa-1. ISF: Ideal separation factor, SF: Separation factor
S28
10. In-situ energy-dispersive X-ray spectroscopy (EDS) results
Figure S20. EDS spectrum of [COF-300]-[Zn2(bdc)2(dabco)] composite membrane.
S29
Fabrication of COF-MOF Composite Membranes and Their Highly Selective Separation of H2/CO2 Jingru Fu,a Saikat Das,a Guolong Xing,a Teng Ben,a* Valentin Valtcheva,band Shilun Qiua [*]aDepartment of Chemistry, Jilin University, Changchun, China. Fax: (+86)431-85168298 E-mail: [email protected] b
Normandie Univ, ENSICAEN, UNICAEN, CNRS, Laboratoire Catalyse et
Spectrochimie, 14000 Caen, France
S1
Table of Contents
1. Instruments
S3
2. Materials
S7
3. Chemical reactions involved (Schemes S1, S2 and S3)
S8
4. Fourier transform infrared spectroscopy (FTIR)
S10
5. X-ray diffraction (XRD)
S13
6. Thermogravimetric analysis (TGA)
S15
7. Low pressure N2 sorption measurements
S16
8. Low pressure H2, CO2 and CH4 sorption measurements
S19
9. Gas separation measurements
S22
10. In-situ energy-dispersive X-ray spectroscopy (EDS) results
S29
S2
1. Instruments
1-1. Fourier transform infrared spectroscopy (FTIR) The FTIR spectra (KBr) were obtained using a SHIMADZU IRAffinity-1 Fourier transform infrared spectrophotometer. 1-2. X-ray diffraction (PXRD) The XRD measurements were carried out using SHIMADZU XRD-6000 X-ray diffractometer with Cu-Kα radiation, 40 kV, 30 mA and scanning rate of 0.3o min-1 (2θ). 1-3. Thermogravimetric analysis (TGA) The samples (COF-300 powder, Zn2(bdc)2(dabco) powder and ZIF-8 powder) were put in an alumina pan followed by thermogravimetric analysis (TGA) with SHIMADZU DTG-60 thermal analyzer at a heating rate of 10oC min-1 to 900oC in a dried air atmosphere. The air flow rate was 30 mL min-1. 1-4.Scanning electron microscopy (SEM) and elemental mapping analysis Scanning electron microscopy (SEM) and elemental mapping analysis were carried out with JEOS JSM 6700 scanning electron microscope. 1-5. Low pressure N2 sorption measurements The low pressure N2 sorption measurements were carried out with Micro Meritics Tristar II 3020 surface area and pore size analyzer. Firstly, the solvents (CH3OH, DMF etc.) in the pore were cleared followed by activation of the samples in dynamic vacuum at a certain S3
temperature overnight. After this, the samples were degassed at a certain temperature for 12 h. A sample (80 mg) and a nitrogen (99.999% purity) gas source were employed in the nitrogen sorption measurements at 77 K. 1-6. Low pressure H2, CO2 and CH4 sorption measurements Firstly, samples (COF-300 powder, Zn2(bdc)2(dabco) powder and ZIF-8 powder) of known weight (80 mg) were placed in the sample tubes (weighed beforehand) that were then sealed to avoid the samples from coming in contact with air and moisture. After this, the samples were heated in the sample tubes in vacuum (at a pressure of 100 mtorr or less) and were then kept at a certain temperature and pressure less than 50 mtorr for a minimum of 10 h. The lowpressure H2, CH4, and CO2 sorption measurements were carried out with Micromeritics Tristar II 3020 surface area and pore size analyzer. Post evacuation, the weight of the tubes holding the degassed samples was measured in pursuance of getting to know the mass of the evacuated samples. Ultra-high-purity grade H2,CO2 (99.999 % purity), and CH4 (99.99 % purity) gases were employed for the sorption measurements. The free space was measured with He (99.999 % purity). The H2 isotherms at 77 K were measured in a liquid nitrogen bath and H2isotherms at 87 K in a liquid argon bath. The CO2 isotherms at 273 K were measured in an ice-water bath and CO2 isotherms at 298 K in water bath. The CH4 isotherms at 273 K were measured in an ice-water bath and CH4 isotherms at 298 K in water bath.
S4
1-7. Gas separation measurements In regard to the single gas measurements, He was used as the sweep gas and H2, CO2 and CH4 were used as the feed gases. The flow rate of sweep gas was 150 mL min-1 and that of the feed gases were 50 mL min-1. The pressure at both sides of the membrane was maintained at 1 bar and the measurements were taken at room temperature. Concerning the mixed gas measurements, the feed flow rate for each gas in the 1:1 binary mixture was 50 mL min-1. The flow rate of the sweep gas (He) was 150 mL min-1. The pressure at both sides of the membrane was maintained at 1 bar and the measurements were taken at room temperature.
α H 2 /CO2
y H 2 /y CO2 x H 2 /x CO2
pH2
(S1)
pCO2
where H 2 / CO2 is the separation factor of mixture H2/CO2, x is the molar fraction in the retentate , y is the mole fraction in the permeate, p is the permeance. The permeance measurements were carried out in the 7890A Gas chromatograph. The permeance values ( p ) were converted to corresponding permeability values ( P ) using the formula: P
3.347 10
16
p t mol m /( m 2 s Pa )
(S2)
where p is the permeance (in mol·m-2·s-1·Pa-1), P is the permeability and t is the thickness (in m ) of the membrane. 1 Barrer = 3.347 × 10-16 mol·m-1·s-1·Pa-1.
S5
Figure S1. Schematic illustration of gas separation set-up. (Legends used: MFC: Mass flow controller; GC: Gas chromatograph).
1-8.
Transmission
electron
microscopy
(TEM)
and
energy-dispersive
X-ray
spectroscopy (EDS) The TEM and EDS measurements were accomplished with JEOL JEM-2100F transmission electron microscope operated at an accelerating voltage of 200 kV.
S6
2.Materials
Terephthalaldehyde was purchased from Tokyo Chemical industry Co. Ltd.; Isopentyl nitrite (90%), Hypophoaphoeous acid (50%), Aniline (99.0%), Raney-Nickel (50 µm), Triphenylmethanol (99%), Triethylenediamine (98%), Sodium formate (99.5%) and ZnCl2 (98%) were purchased from Aladdin; Polyaniline (PANI) (Mw = 1.5 x 104), H2BDC (98%), Zn(NO3)2·6H2O (98%) and 2-methylimidazole (99%) were purchased from Aldrich; DMF (99.5%), CH3OH (99.5%), 1,4-Dioxane (99.5%), CH3COOH (99.5%), N2H4·H2O (80%), THF (99.5%), HCl (35%), H2SO4 (98%) and C2H5OH (99.7%) were purchased from West Long Chemical industry. Nitric acid fuming was purchased from Gang Zhou Chemistry industry. All the glass instruments were purchased from Synthware Glass. SiO2 disks were purchased from Wanxianghuabo. Emery paper (500 mesh and 1200 mesh) was purchased from Shanghai New Five Kyrgyzstant Abrasives Co. Ltd. Teflon reactors were purchased from Jinan Henghua Sci.
S7
3. Chemical Reactions involved Scheme S1. Chemical reactions involved during fabrication of COF membrane
CHO
H N
CH N OH
CHO + n
n
CHO
NH2
H2N CHO
NH2
H2 N
NH2
NH2
+
N CH
CH N OH n
NH2
CH N OH n
S8
Scheme
S2.
Chemical
reactions
involved
during fabrication
of
[COF-300]-
[Zn2(bdc)2(dabco)] composite membrane
COOH O
R1 NH2
O O H N R1 H
HO COOH
Zn2+ + R2 NH2
2+
R2 NH2 Zn
3+
N COOH 2 R2 NH2 Zn
H2 N R2 N Zn O H2 R2 N Zn O N
N
2+ +
+
2 N
COOH
O
+
H+
OH
N
Scheme S3. Chemical reactions involved during fabrication of [COF-300]-[ZIF-8] composite membrane
HN
N
2+ Zn2+ + R NH2
R NH2 Zn
HN
S9
H N Zn N R H
2+
4. Fourier transform infrared spectroscopy (FTIR)
Figure S2. FTIR spectra (from 2000 cm-1 to 500 cm-1) of terephthaldehyde (red), PANI (blue), and the product obtained from PANI and terephthaldehyde mixture in anhydrous dioxane and 3M aqueous acetic acid water mixture solvent in teflon reactor at 100 oC for 3 days (black). C=N stretching: 1640 cm-1.
S10
Figure S3. FTIR spectra ( from 800 cm-1 to 400 cm-1) of COF-300 powder (green) and the product obtained with 15 mg COF-300, 272 mg ZnCl2 and 20 mL CH3OH in the teflon reactor at 120 oC for 4 hours (red). Zn-N stretching: 421 cm-1.
S11
Figure S4. FTIR spectra (from 4000 cm-1 to 400 cm-1) of PANI (black) and the product obtained by the mixture of PANI and ZnCl2 and CH3OH in the teflon reactor at 120 oC for 4 hours (red).
Figure S5. FTIR spectra (from 800 cm-1 to 400 cm-1 ) of PANI (black) and the product obtained by the mixture of PANI and ZnCl2 and CH3OH in the teflon ractor at 120 oC for 4 hours (red).
S12
5. X-ray diffraction (XRD)
Figure S6. XRD pattern of degassed COF-300 powder.
S13
Figure S7. XRD patterns of: (a) COF-300 powder, (b) COF-300 membrane, (c) Zn2(bdc)2(dabco) powder, (d) Zn2(bdc)2(dabco) membrane, (e) [COF-300]-[Zn2(bdc)2(dabco)] composite membrane, (f) ZIF-8 powder, (g) ZIF-8 membrane, (h) [COF-300]-[ZIF-8] composite membrane and (i) SiO2 support.
S14
6. Thermogravimetric analysis (TGA)
Figure S8. TGA plot of degassed COF-300 powder (a), Zn2(bdc)2(dabco) powder (b), and ZIF-8 powder (c) in dry air at a rate of 10oC min-1.
S15
7. Low pressure N2 sorption measurements
Figure S9. N2 sorption isotherms of degassed COF-300 powder (solid symbols: adsorption; open symbols: desorption). The inset illustrates the pore size distribution for COF-300 derived from N2 adsorption calculated by Density Functional Theory (DFT) method. The surface area is 2286.6 m2 g-1 and the pore size 2.00 nm.
S16
Figure S10. N2 sorption isotherms of degassed Zn2(bdc)2(dabco) powder (solid symbols: adsorption; open symbols: desorption). The inset illustrates the pore size distribution for Zn2(bdc)2(dabco) derived from N2 adsorption calculated by Density Functional Theory (DFT) method. The surface area is 1274.3 m2 g-1 and the pore size is 0.85 nm.
S17
Figure S11. N2 sorption isotherms of degassed ZIF-8 powder (solid symbols: adsorption; open symbols: desorption). The inset illustrates the pore size distribution for ZIF-8 derived from N2 adsorption calculated by Density Functional Theory (DFT) method. The surface area is 1869.5 m2 g-1 and the pore size is 1.18 nm.
S18
8. Low pressure H2, CO2 and CH4 sorption measurements 8-1. Low pressure gas sorption measurements of degassed COF-300 powder
Figure S12. (A,C,E) H2, CO2 and CH4 sorption isotherms (solid symbols: adsorption, open symbols: desorption) and (B,D,F) isoteric enthalpy Qst of H2, CO2 and CH4 adsorption respectively for degassed COF-300 powder.
S19
8-2. Low pressure gas sorption measurements of degassed Zn2(bdc)2(dabco) powder
Figure S13. (A,C,E) H2, CO2 and CH4 sorption isotherms (solid symbols: adsorption, open symbols: desorption) and (B,D,F) isoteric enthalpy Qst of H2, CO2 and CH4 adsorption respectively for degassed Zn2(bdc)2(dabco) powder.
S20
8-3. Low pressure gas sorption measurements of degassed ZIF-8 powder
Figure S14. (A,C,E) H2, CO2 and CH4 sorption isotherms (solid symbols: adsorption, open symbols: desorption) and (B,D,F) isoteric enthalpy Qst of H2, CO2 and CH4 adsorption respectively for degassed ZIF-8 powder. S21
9. Gas separation measurements Table S1. H2/CO2 separation performance for the COF-300 membrane at room temperature and 1 bar with 1:1 binary mixture of H2 and CO2.
Figure S15. Gas permeability and H2/CO2 selectivity of COF-300 membrane as function of the operating time at room temperature and 1 bar with 1:1 binary mixture of H2 and CO2. S22
Table S2. H2/CO2 separation performance for the Zn2(bdc)2(dabco) membrane at room temperature and 1 bar with 1:1 binary mixture of H2 and CO2.
Figure S16. Gas permeability and H2/CO2 selectivity of Zn2(bdc)2(dabco) membrane as function of the operating time at room temperature and 1 bar with 1:1 binary mixture of H2 and CO2. S23
Table S3. H2/CO2 separation performance for the ZIF-8 membrane at room temperature and 1 bar with 1:1 binary mixture of H2 and CO2.
Figure S17. Gas permeability and H2/CO2 selectivity of ZIF-8 membrane as function of the operating time at room temperature and 1 bar with 1:1 binary mixture of H2 and CO2.
S24
Table S4. H2/CO2 separation performance for the [COF-300]-[Zn2(bdc)2(dabco)] composite membrane at room temperature and 1 bar with 1:1 binary mixture of H2 and CO2.
Figure S18. Gas permeability and H2/CO2 selectivity of [COF-300]-[Zn2(bdc)2(dabco)] composite membrane as function of the operating time at room temperature and 1 bar with 1:1 binary mixture of H2 and CO2.
S25
Table S5. H2/CO2 separation performance for the [COF-300]-[ZIF-8] composite membrane at room temperature and 1 bar with 1:1 binary mixture of H2 and CO2.
Figure S19. Gas permeability and H2/CO2 selectivity of [COF-300]-[ZIF-8] composite membrane as function of the operating time at room temperature and 1 bar with 1:1 binary mixture of H2 and CO2.
S26
Table S6. Single and mixed gas permeability and separation factors for the [COF-300][Zn2(bdc)2(dabco)] composite membrane prepared on porous SiO2 disk at room temperature and 1 bar (in mixed gases permeation, equimolar mixtures have been used).
Permeability is calculated as the membrane permeability multiplied by the membrane thickness. 1 Barrer = 3.347 × 10-16 mol·m-1·s-1·Pa-1. ISF: Ideal separation factor, SF: Separation factor
S27
Table S7. Single and mixed gas permeability and separation factors for the [COF-300]-[ZIF8] composite membrane prepared on porous SiO2 disk at room temperature and 1bar (in mixed gases permeation, equimolar mixtures have been used).
Permeability is calculated as the membrane permeability multiplied by the membrane thickness. 1 Barrer = 3.347 × 10-16 mol·m-1·s-1·Pa-1. ISF: Ideal separation factor, SF: Separation factor
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10. In-situ energy-dispersive X-ray spectroscopy (EDS) results
Figure S20. EDS spectrum of [COF-300]-[Zn2(bdc)2(dabco)] composite membrane.
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