Department of Chemistry, Pohang University of Science and Technology, Pohang ,

Transcription

1 Highly stable CO 2 /N 2 and CO 2 /CH 4 selectivity in hypercrosslinked heterocyclic porous polymers Muhammad Saleh,, Han Myoung Lee, K. Christian Kemp and Kwang S. Kim*, Department of Chemistry, Pohang University of Science and Technology, Pohang , Korea. Department of Chemistry, Ulsan National Institute of Science and Technology (UNIST), Ulsan , Korea *kimks@unist.ac.kr

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3 Figure. S1 TEM (Left) and HRTEM (right) images of the polymers.

4 Intensity (a.u) CBZ DBT DBF BT BF IN Theta (2 degree) Figure. S2 XRD data for the polymers.

5 BT % Transmittance (a.u) Wavenumber (cm -1 ) DBT % Transmittance (a.u) Wavenumber (cm -1 )

6 IN % Transmittance (a.u) CBZ Wavenumber (cm -1 ) % Transmittance (a.u) Wavenumber (cm -1 )

7 BF % Transmittance (a.u) DBF Wavenumber (cm -1 ) % Transmittance (a.u) Figure. S3 FTIR spectra of the polymers. 119 Wavenumber (cm -1 )

8 Figure. S4 EDX spectra of the polymers (for clarity Si and Pt labeling have been eliminated.)

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11 Figure. S5 13 C CP-MAS NMR spectra of the polymers.

12 1 Weight loss (%) CBZ DBT DBF BT BF IN Temperature ( o C) Figure. S6 Thermogravimetric analysis for the polymers.

13 Heat of adsorption (kj mol -1 ) CBZ DBT DBF IN BT BF Volume of CH 4 adsorbed (cm 3 (STP) g -1 ) Figure. S7 Isosteric heat of adsorption of CH 4 for the polymers.

14 BF (a) CO 2 CH 4 N (b) CO 2 CH 4 N (c) CO 2 : y = 24.47x, R 2 =.982 CH 4 : y = 1.68x, R 2 =.995 N 2 : y =.555x, R 2 = (d) 2 CO 2 : y = 1.817x, R 2 =.996 CH 4 : y =.828x, R 2 =.999 N 2 : y =.264x, R 2 =

15 BT (a) CO 2 CH 4 N (b) CO 2 CH 4 N (c) CO 2 : y = x, R 2 =.978 CH 4 : y = 2.166x, R 2 =.993 N 2 : y =.534x, R 2 = (d) CO 2 : y = x, R 2 =.992 CH 4 : y = 1.45x, R 2 =.999 N 2 : y =.264x, R 2 =

16 DBF (a) CO 2 CH 4 N (b) CO 2 CH 4 N (c) 2. (d) CO 2 : y = x, R 2 =.985 CH 4 : y = 2.325x, R 2 =.997 N 2 : y =.339x, R 2 = CO 2 : y = x, R 2 =.994 CH 4 : y = 1.227x, R 2 =.999 N 2 : y =.198x, R 2 =

17 IN (a) (c) CO 2 CH 4 N 2 CO 2 : y = 22.14x, R 2 =.945 CH 4 : y = 1.467x, R 2 =.997 N 2 : y =.34x, R 2 = (b) CO 2 CH 4 N (d) CO 2 : y = 12.12x, R 2 =.993 CH 4 : y =.785x, R 2 =.995 N 2 : y =.182x, R 2 = Figure S8 Selective gas adsorption at (a) 273 K and (b) 298 K. Initial slope fitting for gases at (c) 273 K and (d) 298 K.

18 4 (a) 2. (b) CO 2 : y = x, R 2 =.985 CH 4 : y = 1.932x, R 2 =.997 N 2 : y =.255x, R 2 = CO 2 : y = x, R 2 =.996 CH 4 : y = 1.2x, R 2 =.999 N 2 : y =.172x, R 2 = Figure S9 Initial slope fitting for gases of CBZ at (a) 273 K and (b) 298 K (a) CO 2 : y = x, R 2 =.978 CH 4 : y = 2.328x, R 2 =.994 N 2 : y =.29, R 2 = (b) CO 2 : y = 12.4x, R 2 =.995 CH 4 : y = 1.138x, R 2 =.999 N 2 : y =.15x, R 2 = Figure S1 Initial slope fitting for gases of DBT at (a) 273 K and (b) 298 K.

19 Table S1 Comparison of different microporous materials with respect to their textural and adsorption properties. Material BET (m 2 g -1 ) CO 2 uptake (wt %) at 273 K CO 2 uptake (wt %) at 298 K Selectivity (CO 2 /N 2 ) at 273 K Selectivity (CO 2 /N 2 ) at 298 K References CBZ This work DBT This work DBF This work IN This work BT This work BF This work BILP PECONF PECONF PECONF MPI TBI BPOP CTF HCP-E HCP HCP BDM Benzene

20 Table S2 Gas adsorption capacity of the polymers. CO 2 CH 4 N 2 Polymer wt % (mmol g -1 ) wt % (mmol g -1 ) wt % 273K 298K 273K 298K 273K 298K CBZ 9.2 (2.1) 6.2 (1.37) 1.16 (.72).65 (.41) DBT 9.7 (2.2) 6.6 (1.38) 1.34 (.83).89 (.56) DBF 11.4 (2.6) 9.7 (2.2) 1.47 (.91).91 (.57) IN 7.5 (1.7) 4.85 (1.1).73 (.45).56 (.35) BT 1.6 (2.42) 6.14 (1.39) 1.43 (.89).77 (.48) BF 1.6 (2.42) 6.4 (1.37) 1.22 (.76).65 (.41) Theoretical calculations The interactions between six unit systems and a CO 2 molecule were estimated by using the density functional theory (DFT) M6-2X method, the spin-component-scaled Møller-Plesset second-order perturbation theory method with the resolution-of-identity approximation (RI-scs-MP2) 11,12 and the coupled cluster theory method with single, double and perturbative triple excitations with the resolutionof-identity approximation (RI-CCSD(T)) levels of theory. The M6-2X calculations were performed by using the Gaussian9 suite of programs 13 and the RI-scs-MP2 and RI-CCSD(T) calculations were carried out by using the Turbomole 6.4 program package. 14 The basis set used was the aug-cc-pvdz at the M6-2X method, the aug-cc-pvtz at the RI-scs-MP2 level and the aug-cc-pvdz at the RI-CCSD(T) level of theory. The geometries were fully optimized without any symmetry constraint at the M6-2X and RI-scs- MP2 levels of theory. At the RI-CCSD(T) level, the distance between the CO 2 and each unit system was optimized using the RI-scs-MP2 geometries. The RI-CCSD(T) geometries of these systems are shown in Figure. 6. The non-covalent interactions tend to be somewhat overestimated at the DFT and CCSD(T) levels 15 and slightly underestimated at the RI-scs-MP2 level of theory. Therefore, the binding energies (BEs) of the CO 2 molecule and six unit systems are corrected by the half basis set superposition error (BSSE) only at the M6-2X and RI-CCSD(T) levels of theory. References (1) Rabbani, M. G.; El-Kaderi, H. M. Synthesis and Characterization of Porous Benzimidazole- Linked Polymers and Their Performance in Small Gas Storage and Selective Uptake. Chem. Mater. 212, 24,

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