Copyright WILEY-VCH Verlag GmbH & Co. KGaA, 69469 Weinheim, Germany, 2012. Supporting Information for Adv. Mater., DOI: 10.1002/adma.201202447 Hypercrosslinked Aromatic Heterocyclic Microporous Polymers: A New Class of Highly Selective CO 2 Capturing Materials Yali Luo, Buyi Li, Wei Wang, Kangbing Wu, and Bien Tan*
Supporting Informaion Submitted to Hypercrosslinked Aromatic Heterocyclic Microporous Polymers: A New Class of Highly Selective CO 2 Capturing Materials By Yali Luo, Buyi Li, Wei Wang, Kangbing Wu and Bien Tan* Both Yali Luo and Buyi Li contributed equally to this work [*] Prof. B. Tan, Prof. K. Wu, Dr. Y. Luo, Dr. B. Li Hubei Key Laboratory of Material Chemistry and Service Failure Key Laboratory for Large-Format Battery Materials and System, Ministry of Education School of Chemistry and Chemical Engineering Huazhong University of Science and Technology Wuhan 430074 (P.R. China) E-mail: bien.tan@mail.hust.edu.cn. Prof. W. Wang State Key Laboratory of Applied Organic Chemistry College of Chemistry and Chemical Engineering Lanzhou University Lanzhou 730000 (P.R. China) 1
Materials. Thiophene (Th), pyrrole (Py) and formaldehyde dimethyl acetal (FDA) were purchased from Aladdin Reagent Limited Company (Shanghai, China). Pyrrole was distilled under reduced pressure and stored in a refrigerator prior to use. Furan (Fu), anhydrous iron (III) chloride (FeCl 3 ), methanol and 1, 2-dichloroethane (DCE) were purchased from National Medicines Corporation Ltd. of China. All chemicals and reagents were used without further purification unless otherwise stated. Synthesis of monolith (thiophene-based). Mixture of thiophene (1.68 g, 0.02 mol), FDA (3.04 g, 0.04 mol) and 1 ml DCE was put into a 10 ml centrifuge tube made from polyterafluoroethylene. FeCl 3 (3.25 g, 0.02 mol) was added to the centrifuge tube slowly and shake it rapidly. Five minute later, this heterogeneous mixture was then consolidated by centrifugation (11000 rpm, 10 min), followed by heating (24 h, 80 C). The resulting monolith was removed from the centrifuge tube, washed with methanol in a Soxhlet for 72 h and finally dried under reduced pressure at 60 C for 24 h. The monolith (thiophene-based) photograph was shown in Figure S1. Characterization. Fourier-transformed infrared (FTIR) spectra were collected on KBr disks in transmission mode using a Bruker Vertex 70 FTIR spectrometer. 13 C cross polarization magic angle spinning nuclear magnetic resonance ( 13 C CP/MAS NMR) spectra were recorded on a WB 400 MHz Bruker Avance II spectrometer with the contact time of 2 ms (ramp 100) and pulse delay of 3 s. Elemental analysis (EA) was determined using a Vario Micro cube Elemental Analyzer (Elementar, Germany). Thermogravimetric analysis (TGA) was performed using a Perkin-Elmer Pyrisl TGA. The samples were heated at the rate of 10 C/min under a nitrogen atmosphere up to 900 C. Field emission scanning electron microscope (FE-SEM) micrographs were obtained using a Sirion 200 microscope (FEI Corp., NL) with an accelerating voltage of 10 kv. The samples were mounted on aluminum studs using adhesive graphite tape and sputter coated with platinum before analysis. Transmission electron microscopy (TEM) images were taken on a Tecnai G20 microscope (FEI Corp. USA) 2
operated at an accelerating voltage of 200 kv. Surface areas and pore size distributions were measured by nitrogen adsorption and desorption at 77 K using a Micromeritics ASAP 2020 volumetric adsorption analyzer. The surface areas were calculated by the Brunauer-Emmett- Teller (BET) method in the relative pressure (P/P o ) range from 0.05 to 0.20, whereas the total pore volumes were calculated at a relative pressure of P/P o = 0.995. The pore size distributions were derived from the adsorption branches of the isotherms using the nonlocal density functional theory (NLDFT). Prior to analysis the samples were degassed at 110 C for 8 h under vacuum (10-5 bar) to remove residual moisture and other trapped gases. The H 2 gas sorption isotherm was monitored at 77.3 K and CO 2 gas isotherm was measured at 273 K. Electrochemical measurements were performed on a CHI 660D electrochemical workstation (Chenhua Instrument, Shanghai, China) with a conventional three-electrode system. The working electrode was a Fu-1/GCE or a bare GCE, the reference electrode was a saturated calomel electrode (SCE), and the counter electrode was a platinum wire. 3
Figures and Tables Submitted to Table S1. CO 2 gas adsorption and H 2 gas adsorption of the samples. Polymer work FDA a) SABET S LANGMUIR CO 2 uptake (m 2 g -1 ) b) (m 2 g -1 ) c) wt% (mmol g -1 ) d) H 2 uptake wt% (mmol g- 1 ) e) Th-1 2 726 966 12.7 (2.88) 1.11 (5.57) Th-2 3 549 735 11.1 (2.51) 1.04 (5.20) Th-3 4 513 687 10.9 (2.47) 0.94 (4.71) Py-1 2 437 578 11.9 (2.71) 0.95 (4.76) Py-2 3 395 529 11.6 (2.64) 0.67 (3.33) Py-3 4 340 466 11.9 (2.71) 0.96 (4.82) Fu-1 2 514 685 9.70 (2.21) 0.84 (4.19) Fu-2 3 314 424 8.92 (2.03) 0.74 (3.72) Fu-3 4 194 302 7.51 (1.71) 0.66 (3.28) a) Molar ratio with respect to monomer; b) Surface area calculated from nitrogen adsorption isotherms at 77 K using BET equation; c) Surface area calculated from nitrogen adsorption isotherms at 77 K using Langmuir equation; d) CO 2 uptake determined volumetrically using a Micromeritics ASAP 2020 M analyzer at 1 bar and 273.15 K; e) H 2 uptake determined volumetrically using a Micromeritics ASAP 2020 M analyzer at 1.13 bar and 77 K. Figure S1. The monolith (thiophene-based) photograph. 4
Figure S2. FTIR spectra of the microporous aromatic heterocyclic polymers. Figure S3. 13 C CP-MAS NMR spectra of the microporous aromatic heterocyclic polymers recorded at a MAS rate of 10 khz. Asterisks denote spinning sidebands. 5
Submitted to Figure S4. SEM (left) and TEM (right) images of Th-1. Figure S5. SEM (left) and TEM (right) images of Py-1. Figure S6. SEM (left) and TEM (right) images of Fu-1. 6
Figure S7. TGA curves for Th-1, Py-1 and Fu-1 under N 2 flow. 7
Figure S8. Adsorption isotherms for CO 2 at 273 K and 298 K and for N 2 at 273 K. (a) Th-1, (b) Py-1, (c) Fu-1. 8
Calculation of CO 2 :N 2 selectivity Submitted to We calculated the initial slope of the gas uptake for both CO 2 and N 2. The ratio of the slopes was used to calculate the selectivity at 273 K. 9
Figure S9. Initial slope calculation for CO 2 and N 2 isotherms collected at 273 K. (a) Th-1 (CO 2 : blue squares; N 2 : red squares), (b) Py-1 (CO 2 : purple circles; N 2 : red circles), (c) Fu- 1(CO 2 : green triangles; N 2 : red triangles) Figure S10. Initial slope calculation for CO 2 and N 2 isotherms collected at 273 K for hypercrosslinked benzene. 10
Atomistic Simulation details Submitted to A series of model was constructed using Material Studio 4.3 to describe the structure of Th network, Py network and Fu network respectively. All models gave the best overall agreement with the characterizarion data for the physical samples. These three particular models were constructed from a combination of clusters containing 509 carbon atoms and 59 carbon atoms, respectively, in a 2:3 ratio. Each cluster was fully relaxed using the Discover module and the COMPASS force field previously, and the models were again fully relaxed the Discover module and the COMPASS force field to ensure the cell parameters and hence the density remained constant. A Connolly surface was created for model using Atom, Volumes and Surface tool in Materials Studio using a fine grid resolution (0.25 Å) and a Connolly radius set to 1.82 Å ( the kinetic radius of N 2 ). CO 2 and N 2 sorption isotherms were calculated at 298 K and 273 K for this model using the Sorption module within Materials Studio. The Universal forcefield was used at a medium-quality calculation level. (a) 11
(b) (c) (d) 12
(e) Figure S11. (a) Simulated Th network, Dimension of simulation box (the amorphous cell ) = 3.658 nm. Carbon atom was gray, Hydrogen atom was white, sulfur atom was purple. (b) 3- Dimensional array of eight (2 2 2) amorphous cells with periodic boundary conditions. (Expansion of (a)) A Connolly surface was shown in blue/gray. Connolly surface area = 2200 m 2 /g, simulated micropore volume = 0.6155 cm 3 /g. (c) 2-Dimensional slices through the simulated pore structure. The occupied and unoccupied volume is shown in red and blue, respectively. (d) 1-Dimensional slices through the simulated pore structure. The occupied and unoccupied volume is shown in red and blue, respectively. (e) Snapshot of CO 2 (green) and N 2 (red) sorption in the simulated pore structure at 1.2 bar/273 K. (a) 13
(b) (c) (d) 14
(e) Figure S12. (a) Simulated Py network, Dimension of simulation box (the amorphous cell ) = 3.428 nm. Carbon atom was gray, Hydrogen atom was white, Nitrogen atom was light blue. (b) 3-Dimensional array of eight (2 2 2) amorphous cells with periodic boundary conditions. (Expansion of (a)) A Connolly surface was shown in blue/gray. Connolly surface area = 1864 m 2 /g, simulated micropore volume = 0.4756 cm 3 /g. (c) 2-Dimensional slices through the simulated pore structure. The occupied and unoccupied volume is shown in red and blue, respectively. (d) 1- Dimensional slices through the simulated pore structure. The occupied and unoccupied volume is shown in red and blue, respectively. (e) Snapshot of CO 2 (green) and N 2 (red) sorption in the simulated pore structure at 1.2 bar/273 K. (a) 15
(b) (c) (d) 16
(e) Figure S13. (a) Simulated Fu network, Dimension of simulation box (the amorphous cell ) = 3.4420 nm. Carbon atom was gray, Hydrogen atom was white, oxygen atom was yellow. (b) 3-Dimensional array of eight (2 2 2) amorphous cells with periodic boundary conditions. (Expansion of (a)) A Connolly surface was shown in blue/gray. Connolly surface area = 1980 m 2 /g, simulated micropore volume = 0.5857 cm 3 /g. (c) 2-Dimensional slices through the simulated pore structure. The occupied and unoccupied volume is shown in red and blue, respectively. (d) 1- Dimensional slices through the simulated pore structure. The occupied and unoccupied volume is shown in red and blue, respectively. (e) Snapshot of CO 2 (green) and N 2 (red) sorption in the simulated pore structure at 1.2 bar/273 K. 17
(a) (b) Figure S14. (a) Simulated CO 2 and N 2 sorption isotherms in the Th network. (b) Simulated distribution of CO 2 and N 2 sorption energies in the Th network. The y-axis represents a distribution function, PE, which is a measure of the probability of a sorbate molecule being at a given sorption energy. 18
(a) (b) Figure S15. (a) Simulated CO 2 and N 2 sorption isotherms in the Py network. (b) Simulated distribution of CO 2 and N 2 sorption energies in the Py network. The y-axis represents a distribution function, PE, which is a measure of the probability of a sorbate molecule being at a given sorption energy. 19
(a) (b) Figure S16. (a) Simulated CO 2 and N 2 sorption isotherms in the Fu network. (b) Simulated distribution of CO 2 and N 2 sorption energies in the Fu network. The y-axis represents a distribution function, PE, which is a measure of the probability of a sorbate molecule being at a given sorption energy. 20
Figure S17. DPV curves of 20 µg L -1 Pb 2+ at CPE and Fu-1/CPE after 2-min accumulation under -1 V. 21
Table S2. Summary of surface area, CO 2 uptake and selectivity (CO 2 /N 2 ) (at 273 K) in selected porous materials. Material BET (m 2 g -1 ) CO 2 uptake (wt%) Selectivity (CO 2/N 2) reference Th-1 726 12.7 39 this work Py-1 437 11.9 117 this work Fu-1 514 9.7 50 this work BILP-1 1172 18.8 70 [1] BILP-2 708 14.9 113 [1] BILP-3 1306 22.5 59 [1] BILP-4 1135 23.5 79 [1] BILP-5 599 12.8 95 [1] BILP-6 1261 21.1 63 [1] BILP-7 1122 19.3 62 [1] PECONF-1 499 8.2 109 [2] PECONF-2 637 12.5 74 [2] PECONF-3 851 15.4 77 [2] PECONF-4-0.6 83 [2] bio-mof-11 1040 26.4 81 [3] CAU-1 1268 31.7 101 [4] References [1] M. G. Rabbani, H. M. El-Kaderi, Chem. Mater. 2012, 24, 1511. [2] P. Mohanty, L. D. Kull, K. Landskron, Nat. Commun. 2011, 2, 401. [3] J. An, S. J. Geib, N. L. Rosi, J. Am. Chem. Soc. 2010, 132, 38. [4] X. Si, C. Jiao, F. Li, J. Zhang, S. Wang, S. Liu, Z. Li, L. Sun, F. Xu, Z. Gabelica, C. Schick, Energ. Environ. Sci. 2011, 4, 4522. 22