Supporting Information

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1 Supporting Information Conjugated Miroporous Polyarazole Networks as Preursors for Nitrogen Enrihed Miroporous Carons for CO 2 Storage and Eletrohemial Capaitors Haige Wang #,1 Zhonghua Cheng #,1 Yaozu Liao, *,1,2,3 Jiahuan Li, 1 Jens Weer, 4 Arne Thomas, *,2 Charl F. J. Faul *,3 [*] Prof. Dr. Yaozu Liao, Haige Wang, Zhonghua Cheng, Jiahuan Li 1 State Key Laoratory for Modifiation of Chemial Fiers and Polymer Materials & College of Materials Siene and Engineering, Donghua University, Shanghai 16, P. R. China yzliao@dhu.edu.n Prof. Dr. Arne Thomas, Prof. Dr. Yaozu Liao 2 Department of Chemistry & Funtional Materials, Tehnishe Universität Berlin, Hardenergstrasse, 1623 Berlin, Germany arne.thomas@tu-erlin.de Prof. Dr. Charl F. J. Faul, Prof. Dr. Yaozu Liao 3 Shool of Chemistry, University of Bristol, Bristol, England BS8 1TS, UK harl.faul@ristol.a.uk Prof. Dr. Jens Weer 4 Department of Chemistry, Hohshule Zittau/Görlitz (University of Applied Siene), Theodor-Körner-Allee 16, D-2763 Zittau, Germany [#] Haige Wang and Zhonghua Cheng ontriute equally to this work. 1

2 Tale of Content 1. Experimental Setion 1.1. Chemials and materials 1.2. Syntheses of polyarazole networks 1.3. Syntheses of polyarazole-derived arons 2. Charaterization and Measurements 2.1. Struture and morphology haraterization 2.2. Gas adsorption/desorption measurements 2.3. Eletrohemial apaity haraterization 3. Supplementary Figures and Tales Figure S1 FT-IR spetra of arazole-sustituted monomers and their polyarazole networks. Figure S2 13 C CP/MAS NMR spetra of polyarazole networks. Figure S3 XRD patterns of (a) polyarazole networks and () their derived arons. Figure S4 Pore size distriutions of polyarazole networks and their derived arons. Figure S5 CO 2 adsorption isotherms of polyarazole networks at (a) 273 and () 293 K. The dashed lines indiate the CO 2 adsorption at.15 ar. Figure S6 TGA sans of arazole monomers and polyarazole networks. Figure S7 CO 2 adsorption of polyarazole-derived arons at (a) 273 and () 293 K with low pressure (p/p =.25-.2). Figure S8 Isosteri heat of CO 2 adsorption of polyarazole networks and their derived arons ased on fitting adsorption isotherms at 273 and 293 K. Figure S9 CV urves of (a) -C and () -C otained at different san rates, GCD urves of (a) -C and () -C otained at different urrent densities. Tale S1 Porosity and CO 2 uptake apaity omparisons of our polyarazole networks and struturally losed polymers. Tale S2 N1s ore-level XPS results of and -C. 4. Referenes 2

3 1. Experimental Setion 1.1. Chemials and materials 4,6-tri(9H-arazol-9-yl)-1,3,5-triazine (TCT, >98%), 4,4',4''-tri-9-arazolyl triphenylamine (TCA, >98%), and 4,4'-is(9H-arazol-9-yl)iphenyl (BCP, >98%) were purhased from Tokyo Chemial Industry Ltd. Anhydrous ferri hloride (FeCl 3, >98%), nitromethane (CH 3 NO 2, >96%), hloroform (CHCl 3, 99%) and other hemials were ought from Sigma Aldrih Company Syntheses of polyarazole networks The syntheses of polyarazole networks were adopted y modified previous reported methods. 1-3 Typially, A 25 ml of round flask was harged with the arazole-sustituted monomer TCT, TCA, or BCP (1 mmol, 1 equiv.) and 5 ml of CHCl 3. An oxidant anhydrous FeCl 3 (3 equiv. per arazole unit) was previously dissolved in ml of CH 3 NO 2 and then added into the flash harged with monomer solution affording a homogenous reation. The preipitation was immediately oserved. The mixture was vigorously stirred overnight, thin-layer hromatography (TLC) analysis indiated omplete onsumption of the arazole-sustituted monomer. The preipitate was filtered and washed with 35% HCl (1 1 ml), soxhleted y methanol (24 h) and CHCl 3 (24 h), and then dried 72 h in a vauum oven to yield orresponding, or networks in quantitative yield as yellow, rown or light-yellow solids, respetively. Anal. Cald. (%) for : C (82.9), H (3.18), N (14.73); Anal. Found (%) for : C (8.23), H (4.21), N (14.19). Anal. Cald. (%) for : C (88.26), H (4.12), N (7.62); Anal. Found (%) for : C (86.67), H (4.), N (7.72). Anal. Cald. (%) for : C (89.98), H (4.19), N (5.83); Anal. Found (%) for : C (87.18), H (4.39), N (5.78). 3

4 1.3. Syntheses of polyarazole-derived arons The, and networks were heated to 1 o C in N 2 with a heating rate of 3 o C/min and aronized at 1 o C for 3 min, yielding aron materials -C, -C and -C, respetively. Char yield for : 82.3%; Anal. Found. for -C: C, 85.88%; N, 6.7%. Char yield for : 8.2%; Anal. Found. for -C: C, 89.21%; N, 3.6%. Char yield for : 78.6%; Anal. Found. for -C: C, 9.66%; N, 2.99%. 2. Charaterization and Measurements 2.1. Struture and morphology haraterization Elemental analyses were arried out using a Euro Vetor EuroEA3 Elemental Analyzer. Solid-state ultra-violet (UV-vis) spetra were reorded on a Shimadzu UV-26 Spetrometer. Fourier transform infrared (FT-IR) spetra were taken on a Perkin Elmer Spetrum 1 spetrometer. Fluoresent spetra were otained on a JASCO FP-65 spetrofluorometer. Powder X-ray diffration (XRD) patterns were otained on a Bruker D8 Advane diffratometer ( kv, 3 Ma) using Cu Kα radiation (2θ = 2 75 o ). Solid-state 13 C rosspolarization magi angle spinning nulear magneti resonane (CP/MAS NMR) spetra were taken at Solid state NMR Servie, Durham University on a Varian VNMRS-6 spetrometer using a spin-rate of 68 Hz. Thermal gravimetri analysis (TGA) was arried out on a TGA Q5 apparatus in nitrogen atmosphere (flow rate 3 ml min -1 ) in the temperature range 3 1 o C (heating rate 1 o C/min). Sanning eletron mirosope (SEM) images were otained on a JEO 56LV and High-resolution transmission eletron mirosope (TEM) images were otained on JEOL 1 TEM mirosope. X-ray photoeletron spetra (XPS) were otained on a PHI5 1 Versaproe-II multifuntional 2 sanning and imaging photoeletron spetrometer (Japan) equipped with an Al Kα X-ray soure. 4

5 2.2. Gas adsorption/desorption measurements Nitrogen adsorption/desorption measurements at 77.4 K, CO 2 adsorption/desorption measurements at 273 and 293 K were performed after degassing the samples under high vauum at 15 C for 15 hours using a Quantahrome Quadrasor iq2-mp mahine. The speifi surfae areas were alulated y applying the Brunauer-Emmett-Teller (BET) model to adsorption or desorption ranhes of the isotherms (N 2 at 77.4 K) using the ASiQwin software pakage. Analyses of the isotherms y ommerialized nonloal density funtional theory (NLDFT) methodologies were also done using the ASiQwin software pakage Eletrohemial apaity haraterization The yli voltammetry (CV) sans was onduted in a onventional three-eletrode ell onfiguration, employing platinum as the ounter eletrode, a saturated alomel eletrode (Hg/HgO) as the referene eletrode. The working eletrode was prepared y mixing polyarazole-derived aron materials with aron lak and poly-tetrafluoroethylene (PTFE) linder at a mass ratio of 8:1:1. The potential range for CV sans was kept etween -1 to V (SCE vs. Hg/HgO) at different san rates. The galvanostati harge/disharge (GCD) and eletrohemial impedane spetrosopy (EIS) were arried out in a two-eletrode ell onfiguration with two same prepared eletrodes undled together. 4 All the experiments were arried out in 6. M KOH solution at amient temperature. The speifi apaitane (C) from GCD measurements was alulated y the equation: 5,6 C = 2I t/(m V) where C (F g -1 ), I (A), t (s), m (g) and V (V) represent the speifi apaitane, the disharge urrent, the disharge time, the mass of the ative materials in one eletrode, and the potential window, respetively. 5

6 3. Supplementary Figures and Tales BCP Transmittane /a.u. TCA TCT Wavenumer /m-1 Figure S1 FT-IR spetra of arazole monomers and their polyarazole networks. a N N e a N N e Intensity /a.u. a a d d d N a d a a N d d a a N Chemial shift /ppm Figure S2 13 C CP/MAS NMR spetra of polyarazole networks. 6

7 (a) () Intensity /a.u. PBCB Intensity /a.u. -C -C -C Theta /Degrees Theta /Degrees Figure S3 XRD patterns of (a) polyarazole networks and () their derived arons..75 nm Differential pore volume 1.8 nm 1.13 nm.71 nm.93 nm.94 nm -C -C -C Pore width /nm Figure S4 Pore size distriutions of polyarazole networks and their derived arons. 7

8 (a) V ads /m 3 g -1 STP PCBP CO K () V ads /m 3 g -1 STP PCBP CO K Pressure /ar Pressure /ar Figure S5 CO 2 adsorption isotherms of polyarazole networks at (a) 273 and () 293 K. The dashed lines indiate the CO 2 adsorption at.15 ar. Tale S1 Porosity and CO 2 uptake apaity omparisons of our polyarazole networks and struturally losed polymers. Polymer S BET Pore width V miro V total CO 2 uptake@ Referene a,, (m 2 /g) (nm) (m 3 /g) (m 3 /g) 1ar,273K (%) a This study PCBZ a This study CPOP N/A CPOP N/A Polymer a: = PCBZ; polymer : = CPOP-5; polymer : = CPOP-3. 8

9 1 Weight (wt%) 8 6 TCT TCA BCP Temperature ( o C) Figure S6 TGA sans of arazole monomers and polyarazole networks under nitrogen. (a) V ads /m 3 g -1 STP C -C PCBP-C CO K () V ads /m 3 g -1 STP 5 3 -C -C PCBP-C CO K Pressure /ar Pressure /ar Figure S7 CO 2 adsorption of polyarazole-derived arons at (a) 273 and () 293 K with low pressure (p/p =.25-.2). The dashed lines indiate the CO 2 adsorption at.15 ar. 9

10 Tale S2 N1s ore-level XPS results of and -C. Porous Nitrogen inding energy /ev materials C=N C-N C Q st /kj mol C -C -C Amount adsored / mmol g -1 Figure S8 Isosteri heat of CO 2 adsorption of polyarazole networks and their derived arons ased on fitting adsorption isotherms at 273 and 293 K. (a) mv s mv s -1 mv s -1 Current density /A g -1 5 mv s Potential (V) vs. Hg/HgO () 15 Current density /A g mv s -1 1 mv s -1 mv s -1 5 mv s Potential (V) vs. Hg/HgO 1

11 () 1. Voltage (V) C 1. A g A g A g -1 1 A g -1 (d) CVoltage /V 1. A g A g A g -1 1 A g Time /s Time /s Figure S9 CV urves of (a) -C and () -C otained at different san rates, GCD urves of () -C and (d) -C otained at different urrent densities. 4. Referenes (1) Chen, Q.; Luo, M.; Hammershøj, P.; Zhou, D.; Han, Y.; Laursen, B. W.; Yan, C.-G.; Han, B.-H. Miroporous Polyarazole with High Speifi Surfae Area for Gas Storage and Separation. J. Am. Chem. So. 12, 134, (2) Chen, Q.; Liu, D.-P.; Luo, M.; Feng, L.-J.; Zhao, Y.-C.; Han, B.-H. Nitrogen-Containing Miroporous Conjugated Polymers via Carazole-Based Oxidative Coupling Polymerization: Preparation, Porosity, and Gas Uptake. Small 14, 1, (3) Chen, Q.; Liu, D.-P.; Zhu, J.-H.; Han, B.-H. Mesoporous Conjugated Polyarazole with High Porosity via Struture Tuning. Maromoleules 14, 47, (4) Liu, M.; Qian, J.; Zhao, Y.; Zhu, D.; Gan, L.; Chen, L., Core-Shell Ultramiroporous@Miroporous Caron Nanospheres as Advaned Superapaitor Eletrodes. J. Mater. Chem. A 15, 3, (5) Li, L.; Zhong, Q.; Kim, N. D.; Ruan, G.; Yang, Y.; Gao, C.; Fei, H.; Li, Y.; Ji, Y.; Tour, J. M., Nitrogen-Doped Caronized Cotton for Highly Flexile Superapaitors. Caron 16, 15, (6) Saleh, M.; Baek, S. B. Lee, H. M.; Kim, K. S. Triazine-Based Miroporous Polymers for Seletive Adsorption of CO 2. J. Phys. Chem. C 15, 119,