Electronic Supporting Information Fluorescent Microporous Polyimides based on Perylene and Triazine for Highly CO 2 -Selective Carbon Materials Yaozu Liao, a Jens Weber b and Charl F.J. Faul a* a School of Chemistry, University of Bristol, Bristol, England BS8 1TS, UK. b Department of Chemistry, Hochschule Zittau/Görlitz (University of Applied Science), Theodor-Körner-Allee 16, D-02763 Zittau, Germany *Corresponding author: charl.faul@bristol.ac.uk Figure S1 Appearances of melamine, PTCDA, PI-1, and PI-2. 1
Figure S2 TEM images of PI-1 and PI-2 at (left) low and (right) high magnifications. Figure S3 TGA thermograms of PI-1 and PI-2. Figure S4 FT-IR spectra of PI-1 and PI-1-C. 2
Figure S5 High resolution TEM image (top) and SAED pattern (bottom) of PI-1-C. Figure S6 EDX spectrum of PI-1-C. The observed tiny sulfur and zinc residues are probably owing to some water-insoluble by-products such as ZnS, which might be derived from the decomposition of DMSO and Zn(OAc) 2 at high temperature for long time (200 o C and 4 days). Figure S7 Solid-state 13 C CP/MAS NMR spectrum of PI-1 (asterisks mark spinning side bands). 3
C KLL Zn 2s C 1s N KLL Zn 2p1/2 Zn 2p O KLL Cps /a.u. Zn LMM O 1s N 1s PI-2 PI-2-C S 2s S 2p3/2 PI-1 PI-1-C 1200 1000 800 600 400 200 0 Binding energy /ev Figure S8 XPS survey spectra of PIs and derived carbons. Figure S9 UV-Vis/NIR spectra of PI-1, PI-2, and PTCDA as THF dispersions (0.5 g L -1 ). 4
Figure S10 Emission fluorescence spectra of PI-1 as THF dispersion (0.5 g L -1 ) and upon adding aqueous metal ions at a 1 mmol L -1 concentration excited at 507 nm. Figure S11 Nitrogen adsorption/desorption isotherms of PIs and derived carbons (77.4 K). 5
Figure S12 CO2 adsorption/desorption isotherms of PI-1 type networks synthesized with varied melamine concentrations at 273.15 K. Figure S13 PSD of PI-1 type networks synthesized with varied melamine concentrations (determined using analysis of the adsorption branch by commercialized GCMC methods; please note that the isotherm of PI-1 synthesized at cmelamine = 30 g L-1 was not analyzed due to the exceptionally larger hysteresis). 6
Figure S14 Plot of CO 2 uptake measured at 273 K and 1 bar versus apparent BET surface area, as calculated from N 2 sorption at 77 K, for a range of PIs (blue shaded area) and POPs (red shaded area) previously reported. See ESI, Table S3 for a key to the symbols used here. Figure S15 CO 2 and N 2 experimental adsorption/desorption isotherms (single gas) of PI-1 at 303 K (symbol+line) together with predicted adsorption isotherms (line only) from a 0.15/0.85 v/v gas mixture of CO 2 and N 2 at 303 K (based on IAST methodology); plotted on a log scale to highlight the prediction of N 2 uptake. 7
Figure S16 Langmuir fit (dual- or single site) of the CO2 desorption and N2 adsorption/desorption on PI-1 at 303 K, respective fit parameters were used for calculation of the IAST data (all fit parameters are summarized in Table S4). Figure S17 CO2 adsorption/desorption isotherms of PI-1-C and PI-opt-C carbon materials at 303 K and 1 bar. 8
Figure S18 Langmuir fit (dual- or single site) of the CO2 / N2 adsorption on PI-1-C, respective fit parameters were used for calculation of the IAST data. Figure S19 Langmuir fit (dual- or single site) of the CO2 / N2 adsorption on PI-opt-C, respective fit parameters were used for calculation of the IAST data. 9
Table S1 XRD peaks and d-spacing of the melamine, PTCDA, PI-1, PI-2, PI-1-C and PI-2-C Chemicals Peaks ( o ) / d-spacing (Å) Melamine 12.84 14.64 / 17.40 21.37 / 21.81 / 25.82 / 26.82 / 27.09 28.56 29.66 38.21 / 6.89 6.05 / 5.09 4.15 4.07 3.45 3.32 / 3.29 / 3.12 / 3.01 / 2.35 PTCDA 9.62 12.52 17.39 19.18 20.42 24.91 26.17 27.67 28.05 29.15 / 9.18 / 7.06 / 5.09 / 4.62 / 4.35 / 3.57 / 3.40 / 3.22 / 3.18 / 3.06 PI-1 8.47 11.94 18.22 19.94 21.66 24.73 25.84 27.68 29.17 / 10.43 / 7.40 / 4.87 / 4.45 / 4.10 / 3.60 / 3.44 / 3.22 / 3.06 PI-2 9.95 11.82 24.75 26.07 27.68 / 8.88 / 7.48 / 3.59 / 3.42 / 3.22 PI-1-C 25.24 43.78 / 3.53 / 2.06 PI-2-C 25.28 44.12 / 3.53 / 2.05 Table S2 Relative composition contents of C1s, N1s and O1s of PIs and derived carbons (only the C, N and O atoms were counted) Samples C1s /At% N1s /At% O1s /At% PI-1 69.81 24.47 5.71 PI-1-C 80.16 15.33 4.51 PI-2 74.59 17.22 8.19 PI-2-C 79.48 15.61 4.91 Table S3 Relative area ratios of C1s, N1s and O1s peaks of PIs and derived carbons Samples R I/III (C1s) R II/III (C1s) R II/I (N1s) R II/I (O1s) PI-1 0.56 1.32 0.82 1.28 PI-1-C 0.46 2.07 1.07 0.64 PI-2 0.75 0.94 0.76 1.42 PI-2-C 0.56 1.26 0.82 1.07 10
Table S4 Fit parameters of dual site Langmuir or simple Langmuir fits used for IAST calculations Material/Gas/T K 1 Q 1 K 2 Q 2 PI-1/N 2 /303K 0.001180 0.793940 - - PI-1/CO 2 /303K 0.021470 3.399010 0.001350 13.345170 PI-1-C/N 2 /303K 0.000800 10.976500 - - PI-1-C/CO 2 /303K 0.002853 38.848120 0.097160 12.916540 PI-opt-C/N 2 /303K 0.000545 16.966335 - - PI-opt-C/CO 2 /303K 0.002640 59.696694 0.065837 14.439506 (note: those parameters apply to the use of pressures measured in mmhg and uptake measured in cm³/g STP) According formulas for simple Langmuir and dual-site Langmuir models are the following: Table S5 Surface area and CO 2 uptake comparison of PIs and POPs Polyimi Chemical structure Surface area a CO 2 uptake c /wt% Refs. Symbs des /m 2 g -1 (selectivity d ). PI-1 PI-opt 19 a / 148 b - 3 (~ 1000) 5.9 (n.d.) This study PI-1-C 13 a / 483 b 10.3 (~ 80) PI-opt-C 181 a 15 (240) PI1 660 7.3 (n.d.) 1 PI2 265 2.7 (n.d.) 1 11
PI3 366 6.0 (n.d.) 1 PMDA- 0 5.0 (~ 1000) 2 BAPF PI 5 n.d. (n.d.) 3 - PTPA-3 530 6.5 (75) 4 MPI-1 1454 16.8 (102) 5 - MPI-2 814 13.8 (71) 5 - MPI-3 586 9.9 (41) 5 12
CMP-0 1018 8.5 (15.1) 6 COF-5 1670 5.6 (n.d.) 7 COF-8 1350 5.9 (n.d.) 7 COF-10 1760 5.1 (n.d.) 7 COF- 3620 6.4 (n.d.) 7 102 13
COF- 3530 7.0 (n.d.) 7 103 PAF-1 5640 8.3 (n.d.) 8 CMP-1-1043 7.3 (n.d.) 9 (OH) 2 Tet2 1102 7.9 (n.d.) 10 A 4077 10.4 (9-20) 11 G 1056 8.6 (9-20) 11 BF 1022 10.2 (43) 12 VR-5-P Carbon molecular sieves 3100 19.1 (2) 13 - a Surface area calculated from nitrogen adsorption isotherms using the BET equation if no specific points are indicated; b from GCMC analysis of the CO 2 adsorption data at 273 K; c CO 2 uptake at 273 K and 1 bar; d best CO 2 selectivity over N 2 reported in literatures. References 1. Y. L. Luo, B. Y. Li, L. Y. Liang and B. E. Tan, Chem. Commun., 2011, 47, 7704-7706. 2. M. M. Unterlass, F. Emmerling, M. Antonietti and J. Weber. Chem. Commun., 2014, 50, 14
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