Supporting Information Mesoporous graphitic carbon nanodisks fabricated via catalytic carbonization of coordination polymers

Transcription

1 Supporting Informtion Mesoporous grphiti ron nnodisks frited vi tlyti roniztion of oordintion polymers Pnpn Su, Ling Jing, Jio Zho, Jingwng Yn, Cn Li nd Qihu Yng Stte Key Lortory of Ctlysis, Dlin Institute of Chemil Physis, Chinese Ademy of Sienes, 457 Zhongshn Rod, Dlin (Chin). Grdute Shool of the Chinese Ademy of Sienes, Beijing 139 (Chin). Lortory of Superpitors, Dlin Institute of Chemil Physis, Chinese Ademy of Sienes, 457 Zhongshn Rod, Dlin (Chin). To whom orrespondene should e ddressed. Emil Address: yngqh@dip..n; nli@dip..n. Tel: ; Fx Numer: URL:

2 Experimentl Setion Preprtion of the iron-sed CP nnodisks CP-FeSO 4 : 5 ml FeSO 4 7H 2 O (.5 mmol) queous solution ws dded to the queous solution of 1,4,5,8-nphthlenetetrroxyli dinhydride (NTCDA) (.25 mmol) dissolved in 25 ml NOH solution (.2 M). After stirring t room temperture for 3 min, the resulting mixture ws trnsformed into Teflon-lined stinless steel seled vessel nd heted t 6 C for 24 h. Susequently, the preipitte ws isolted y entrifugtion nd wshed thoroughly with deionized wter. The preprtion of CP-FeCl 2 ws in similr method to CP-FeSO 4 with the exeption tht FeCl 2 ws used s iron slt preursor. Croniztion of the iron-sed CP nnodisks The iron-sed CP nnodisks were lined t 2 o C for 2 h nd then the lintion temperture ws rised to 9 o C or 7 o C nd kept t this temperture for 4 h under N 2 tmosphere. The heting rte during the lintions step ws 5 o C/min. The ronized produts were denoted s Fe-C-Sx nd Fe-C-Clx respetively using CP-FeSO 4 nd CP-FeCl 2 s preursors, where x refers to the lintion temperture. Preprtion of mesoporous ron mterils.2 g Fe-C-Sx or Fe-C-Clx ws dispersed in 5 ml HCl (2 M) solution nd stirred t room temperture for 5 h. And then the ron mteril ws isolted y entrifugtion nd wshed thoroughly with deionized wter. Susequently it ws dried t 1 o C for 24 h. The otined ron mterils were leled s C-Sx nd C-Clx respetively using CP-FeSO 4 nd CP-FeCl 2 s preursors, where x refers to the lintion

3 temperture. Chrteriztion The FT-IR spetr were reorded using KBr diss on Niolet Impt 41 spetrophotometer in the rnge 4-4 m -1. The snning eletron mirosopy (SEM) ws undertken on JEOL JSM-636 snning eletron mirosope operting t n elertion voltge of 2 kv. The trnsmission eletron mirosopy (TEM) ws performed using n FEI Teni G 2 Spirit t n elertion voltge of 12 kv. The smples were pled onto n ultrthin ron film supported on opper grid. The powder X-ry diffrtion dt were olleted on Rigku D/Mx25PC diffrtometer with Cu Kα rdition (λ= Å) over the 2θ rnge of 5 o -7 o with sn speed of 5 o /min t room temperture. The thermogrvimetri nlysis (TGA) ws performed under N 2 tmosphere with heting rte of 5 o C/min y using NETZSCH STA-449F3 thermogrvimetri nlyzer. High resolution trnsmission eletron mirosopy (HRTEM) nd STEM imges were reorded on FEI Teni F3 mirosope with point resolution of.2 nm operted t 3 kv. The nitrogen sorption experiments were performed t 77 K on Miromeritis ASAP 22 system. Prior to the mesurement, the smples were degssed t 12 C for 6 h. Visile Rmn spetr were reorded t room temperture on Join Yvon LRAM HR 8 instrument with 532 nm exittion lser t power of round 1 mw. Eletrohemil mesurements Cyli voltmmetry experiments were rried out in three-eletrode system with n eletrohemil worksttion (CHI 7D, CH Instruments, In.). 6 M KOH queous

4 solution ws used s eletrolyte, mesoporous ron mterils s the working eletrode, pltinum wire s the ounter eletrode nd Ag/AgCl eletrode s the referene eletrode. The working eletrodes were prepred y mixing the ron mterils with etylene lk (1 w.t.%) nd polytetrfluoroethylene (PTFE, 5 w.t.%) nd then pressing the plstiine like mixtures onto nikel fom tht served s urrent olletor. Intensity (.u.) Wvenumer (m -1 ) Fig. S1 The FT-IR spetr of () orgni lignd, 1,4,5,8-nphthlenetetrroxyli dinhydride (NTCDA), () CP-FeSO 4 nd () CP-FeCl 2. Intensity (.u.) Thet (degree) Fig. S2 The XRD ptterns of () CP-FeSO 4 nd () CP-FeCl 2.

5 Tle S1 The textul prmeters of Fe-sed CPs nd the ron nnodisks nd pitne of the ron nnodisks. Smple S BET (m 2 /g) V p (m 3 /g) D meso (nm) D d miro (nm) e I D /I G C f g (F/g) C g s (F/m 2 ) CP-FeSO CP-FeCl C-S , C-S , C-Cl C-Cl the Brunuer-Emmett-Teller (BET) speifi surfe res lulted from dsorption dt in the reltive pressure rnge of P/P =.5~.25. the totl pore volume determined from the mounts dsored t the reltive pressure of.99. the mesopore size distriution lulted from the N 2 dsorption rnh using the Brrett-Joyner-Hlend (BJH) method. d the miropore size distriution lulted using the Horvth-Kwzoe (HK) method. e the degree of grphitiztion lulted from the rtio of the D nd Q pek intensity. f the speifi pitne lulted t -.5V with sn rte of 2 mv/s. g the speifi pitne lulted t -.5V using Cg nd S BET. Volume Adsored (/g STP) Reltive pressure (P/P ) Fig. S3 The nitrogen dsorption-desorption isotherm for () CP-FeSO 4 nd () CP-FeCl 2 prtiles. d Fig. S4 The EDX results of different ron mterils: () C-S9, () C-S7, () C-Cl9 nd (d) C-Cl7.

6 () (d) () 5 nm (d) () 5 nm 5 nm (f) (e).34 nm 5 nm 5 nm Fig. S5 The SEM imges of the roniztion produts () Fe-C-S7, () C-S7, (d) Fe-C-Cl7, (e) C-Cl7 nd HRTEM imges of () C-S7 nd (f) C-Cl7. Fig. S6 The SEM imges of () Fe-C-S9, () Fe-C-Cl9, () Fe-C-S9-NCl; nd TEM imges of (d) Fe-C-S9, (e) Fe-C-Cl9 nd (f) Fe-C-S9-NCl (the lrge spheres in the imge re the iron speies prtiles).

7 Volume Adsored (/g STP) A d dv /dlog(d) [/nm/g STP] B d Reltive Pressure (P/P ) Pore Dimeter (nm) Fig. S7 (A) The nitrogen dsorption-desorption isotherms nd (B) pore size distriution urves of () C-S7, () C-S9, () C-Cl7 nd (d) C-Cl9. A B Intensity (.u.) d Intensity(.u.) d Thet (degree) Rmn Shift (m -1 ) Fig. S8 (A) The XRD ptterns nd (B) Rmn spetr of ron nnodisks () C-Cl9, () C-Cl7, () C-S9 nd (d) C-S Weight Loss (%) CP-FeCl 2 4 CP-FeSO Temperture ( o C) Fig. S9 The TGA urves of CP-FeSO 4 nd CP-FeCl 2 nnodisks in N 2 tmosphere.

8 . Fe Fe 3 O 4 Fe 3 C Intensity (.u.) Fe-C-S9 Fe-C-S Thet (degree) Fig. S1 The XRD ptterns of the roniztion produts: Fe-C-S9 nd Fe-C-S7.. Fe 3 O 4 Fe Intensity (.u.) Fe-C-Cl7 Fe-C-Cl Thet (degree) Fig. S11 The XRD ptterns of the roniztion produt: Fe-C-Cl9 nd Fe-C-Cl7.

9 Current Density (A/g) A 2mv/s 5 mv/s 1 mv/s 2 mv/s 5 mv/s 1 mv/s Current Density (A/g) B 2 mv/s 5 mv/s 1 mv/s 2 mv/s 5 mv/s 1 mv/s Potentil (V vs. Ag/AgCl) Potentil (V vs. Ag/AgCl) Fig. S12 Cyli voltmmogrms of (A) C-S9 nd (B) C-Cl9 eletrodes t different sn rtes in 6 M KOH eletrolyte. speifi pitne /(F/g) () 2 mv/s 1 mv/s 2 mv/s 5 mv/s 1 mv/s Poventil (V vs. Ag/AgCl) speifi pitne /(F/g) () 2 mv/s 1 mv/s 2 mv/s 5 mv/s 1 mv/s Poventil (V vs. Ag/AgCl) 2 () 2 (d) speifi pitne /(F/g) mv/s 1 mv/s 2 mv/s 5 mv/s 1 mv/s Poventil (V vs. Ag/AgCl) speifi pitne /(F/g) mv/s 1 mv/s 2 mv/s 5 mv/s 1 mv/s Poventil (V vs. Ag/AgCl) Fig. S13 Cyli voltmmogrms of () C-S7, () C-S9, () C-Cl7 nd (d) C-Cl9 eletrodes t different sn rtes in 6 M KOH eletrolyte.

10 1 nm 1 nm 1 nm Fig. S14 HRSEM imges of () C-S7 nd () C-S9..34 nm Fig. S15 HRTEM imges of () Fe-C-S9 nd () Fe-C-Cl9 (the iron speies were irled y red lines.).