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1 Supporting Informtion Control Synthesis of Tuulr Hyperrosslinke Polymers for Highly Porous Cron Nnotues Xioyn Wng, Pn Mu, Chong Zhng, Yu Chen, Jinghui Zeng, Feng Wng n Ji-Xing Jing *, Shnxi Key Lortory for Avne Energy Devies, Key Lortory for Mromoleulr Siene of Shnxi Provine, Shool of Mterils Siene n Engineering, Shnxi Norml University, Xi n, Shnxi, , P. R. Chin. E-mil: jixing@snnu.eu.n. Key Lortory for Green Chemil Proess of Ministry of Eution, Wuhn Institute of Tehnology, Wuhn, , P. R. Chin. Synthesis of HCPT-B using solvotherml metho Benzene (1 mmol, 78 mg) ws ilute in 20 ml 1,2-ihloroethne, fter stirre for severl minutes, nhyrous FeCl 3 (3 mmol, 486 mg) n formlehye imethyl etl (3 mmol, 228 mg) were e in the mixture. The mixture ws hete t 50 o C n trnsferre into stinless steel utolve with Teflon-line hmer, whih ws hete to 80 o C n mintine for 24 h. The resulting mixture ws oole own to room temperture n wshe y methnol, istille wter, ihloromethne n etone suessively. Further purifition of the polymer ws rrie out y Soxhlet extrtion from methnol for 48 h. The prout ws rie in vuum for 24 h t 70 o C to give rown power (yiel: 99%). Synthesis of HCPT-B using ultrsoni metho Benzene (1 mmol, 78 mg) ws ilute in 20 ml 1,2-ihloroethne, fter stirre for severl minutes, nhyrous FeCl 3 (3 mmol, 486 mg) n formlehye imethyl etl (3 mmol, 228 mg) were e in the mixture. The mixture ws stirre uniform S-1

2 n resulting yellow solution ultrsonite t room temperture in th sonitor for 2 h. The resulting mixture ws wshe y methnol, istille wter, ihloromethne n etone suessively. Further purifition of the polymer ws rrie out y Soxhlet extrtion from methnol for 48 h. The prout ws rie in vuum for 24 h t 70 o C to give mroon power (yiel: 70%). S-2

3 Tle S1. Effet of monomer onentrtion on morphology of the hyperrosslinke porous polymer preursors Con. Polymer HCPT-B tue/prtile tue/prtile tue tue prtile prtile prtile HCPT-An tue tue tue ulk HCPT-Ph tue/prtile tue prtile ulk HCPT-Py sphere tue/prtile tue ulk monomer onentrtion (mol/l) Preursor Tle S2. Summry of surfe re for HCPTs n PCNTs S BET [m 2 g -1 ] Yiel % (HCPTs) Porous ron nnotue Yiel % (PCNTs) S BET [m 2 g -1 ] HCPT-B PCNT-B HCPT-B PCNT-B HCPT-B PCNT-B HCPB-B HCPT-An e PCNT-An HCPT-Ph f PCNT-Ph HCPT-Py g PCNT-Py otine from solution synthesis metho with 0.05 M enzene, otine from solvotherml metho with 0.05 M enzene, otine from ultrsoni metho with 0.05 M enzene, otine from solution synthesis metho with 1.0 M enzene. e otine from solution synthesis metho with 0.05 M nthrene, f otine from solution synthesis metho with 0.02 M phennthrene, g otine from solution synthesis metho with 0.05 M pyrene. S-3

4 10 µm Figure S1. SEM imge of PCNT-B from solvent metho HCPT-B. HCPT-B Intensive (.u.) PCNT-B Wvenumer(m -1 ) Figure S2. FT-IR spetr of HCPT-B, PCNT-B n. S-4

5 PCNT-B Intensity (.u.) Atomi rtion: O/C= 3.6% O/C= 1.7% Bining enery (ev) Figure S3. Survey XPS spetr of PCNT-B n. Intensity (.u.) PCNT-B I D /I G =0.91 I D /I G = Rmn shift (m -1 ) Figure S4. Rmn spetr of PCNT-B n. S-5

6 Intensive (.u.) PCNT-B HCPT-B Thet ( o ) Figure S5. Power XRD profiles for HCPT-B, PCNT-B n Weight (%) HCPT-B-Nitrogen PCNT-B-Nitrogen PCNT-B-Air Temperture ( o C) Figure S6. Thermogrvimetri nlysis urves of HCPT-B n PCNT-B. S-6

7 Figure S7. Energy-ispersive X-ry spetrosopy spetrum for PCNT-B. Quntity Asore (m 3 /g) Quntity Asore (m 3 /g) HCPT-B (Solvotherml) HCPT-B (Ultrsoni) HCPB-B Reltive Pressure (P/P 0 ) PCNT-B (Solvotherml) PCNT-B (Ultrsoni) Reltive Pressure (P/P 0 ) Differentil Pore Volume (m 3 /g) Differentil Pore Volume (m 3 /g) HCPT-B (Solvotherml) HCPT-B (Ultrsoni) HCPB-B 1 10 Pore Dimeter (nm) PCNT-B (Solvotherml) PCNT-B (Ultrsoni) 1 10 Pore Dimeter (nm) Figure S8. Nitrogen sorption/esorption isotherms (fille symols for sorption rnh n open symols for esorption rnh) of enzene se HCPTs-B n HCPB-B (); pore size istriutions for enzene se HCPTs-B n HCPB-B (). Nitrogen sorption/esorption isotherms (fille symols for sorption rnh n open symols for esorption rnh) for enzene se PCNTs-B n (); pore size istriutions for enzene se PCNTs-B n (). S-7

8 Quntity Asore (m 3 /g) Quntity Asore (m 3 /g) Reltive Pressure (P/P 0 ) HCPT-An HCPT-Ph HCPT-Py PCNT-An PCNT-Ph PCNT-Py Reltive Pressure (P/P 0 ) Differentil Pore Volume (m 3 /g) Differentil Pore Volume (m 3 /g) HCPT-An HCPT-Ph HCPT-Py 1 10 Pore Dimeter (nm) PCNT-An PCNT-Ph PCNT-Py 1 10 Pore Dimeter (nm) Figure S9. Nitrogen sorption/esorption isotherms of nthrene, phennthrene n pyrene se HCPTs () n the orresponing PCNTs () (fille symols for sorption rnh n open symols for esorption rnh); Pore size istriutions for the nthrene, phennthrene n pyrene se HCPTs () n PCNTs (). Figure S10. SEM imges of HCPT-B from solvotherml metho () n orresponing porous ron nnotuees of PCNT-B (); HCPT-B from ultrsoni metho () n orresponing porous ron nnotuees PCNT-B (). S-8

9 0.5 µm 0.5 µm 0.5 µm 0.5 µm Figure S11. TEM imges of HCPT-B from solvotherml metho () n orresponing porous ron nnotuees of PCNT-B (); HCPT-B from ultrsoni metho () n orresponing porous ron nnotuees PCNT-B (). e f g Figure S12. SEM imges of enzene se hyperrosslinke porous polymers with ifferent monomer onentrtions: () 0.01 M, () 0.02 M, () 0.05 M, () 0.1 M, (e) 0.2 M, (f) 0.4 M n (g) 1 M. S-9

10 Figure S13. SEM imges of nthrene se hyperrosslinke porous polymers with ifferent monomer onentrtions: () 0.01 M, () 0.02 M, () 0.05 M n () 0.1 M. Figure S14. SEM imges of phennthrene se hyperrosslinke porous polymers with ifferent monomer onentrtions: () 0.01 M, () 0.02 M, () 0.05 M n () 0.1 M. S-10

11 Figure S15. SEM imges of pyrene se hyperrosslinke porous polymers with ifferent monomer onentrtions: () 0.01 M, () 0.02 M, () 0.05 M n () 0.1 M. 50 nm 20 min 0.5 µm 40 min 0.5 µm 24 h e f 50 nm 20 min 0.5 µm 40 min 0.5 µm 24 h Figure S16. TEM imges of enzene se hyperrosslinke porous polymers with ifferent retion urtions: () 20 min with stirring, () 40 min with stirring, () 24 h with stirring, () 20 min without stirring (e) 40 min without stirring n (f) 24 h without stirring. S-11

12 200 nm 100 nm Figure S17. SEM imge () n TEM imge () of enzene se HCPB-B proue from the monomer onentrtion of 1.0 M. Current ensity (A g -1 ) PCNT-B Voltge (V) 50mv s -1 Voltge (V) PCNT-B 0.12V 20 A g Time (s) Figure S18. () CV urves of PCNT-B n se superpitors t sn rte of 50 mv s 1 in 6.0 M KOH eletrolyte; () IR rops of PCNT-B n se superpitors t urrent ensity of 20.0 A g V S-12