Electronic Supporting Information

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1 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 Zittau, Germany *Corresponding author: charl.faul@bristol.ac.uk Figure S1 Appearances of melamine, PTCDA, PI-1, and PI-2. 1

2 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

3 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

4 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 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

5 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

6 Figure S12 CO2 adsorption/desorption isotherms of PI-1 type networks synthesized with varied melamine concentrations at 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

7 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

8 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

9 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

10 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 / / / / / / / / 3.29 / 3.12 / 3.01 / 2.35 PTCDA / 9.18 / 7.06 / 5.09 / 4.62 / 4.35 / 3.57 / 3.40 / 3.22 / 3.18 / 3.06 PI / / 7.40 / 4.87 / 4.45 / 4.10 / 3.60 / 3.44 / 3.22 / 3.06 PI / 8.88 / 7.48 / 3.59 / 3.42 / 3.22 PI-1-C / 3.53 / 2.06 PI-2-C / 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 PI-1-C PI PI-2-C 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 PI-1-C PI PI-2-C

11 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 PI-1/CO 2 /303K PI-1-C/N 2 /303K PI-1-C/CO 2 /303K PI-opt-C/N 2 /303K PI-opt-C/CO 2 /303K (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) PI (n.d.) 1 PI (n.d.) 1 11

12 PI (n.d.) 1 PMDA (~ 1000) 2 BAPF PI 5 n.d. (n.d.) 3 - PTPA (75) 4 MPI (102) 5 - MPI (71) 5 - MPI (41) 5 12

13 CMP (15.1) 6 COF (n.d.) 7 COF (n.d.) 7 COF (n.d.) 7 COF (n.d.)

14 COF (n.d.) PAF (n.d.) 8 CMP (n.d.) 9 (OH) 2 Tet (n.d.) 10 A (9-20) 11 G (9-20) 11 BF (43) 12 VR-5-P Carbon molecular sieves (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, M. M. Unterlass, F. Emmerling, M. Antonietti and J. Weber. Chem. Commun., 2014, 50, 14

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