Supporting Information. Designed Synthesis of TS-1 Crystals with Controllable. b-oriented Length

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1 Supporting Informtion Designed Synthesis of TS-1 rystls with ontrollble b-oriented Length Zhicho Shn, b Hong Wng, c Xingju Meng,*, Siyu Liu, b Ling Wng, b hunyu Wng, b Fei Li, b Jmes P. Lewis, c nd Feng-Shou Xio*, Deprtment of hemistry, Zhejing University, Hngzhou , hin, b Stte Key Lbortory of Inorgnic Synthesis nd Preprtive hemistry, Jilin University, hngchun , hin, c Deprtment of Mechnicl nd Aerospce Engineering, West Virgini University, Morgntown, West Virgini E-mil: fsxio@mil.jlu.edu.cn Synthesis of Mterils. All regents were used without ny further purifiction. Tetr-n-butyl titnte (TBOT), tetrethyl orthosilicte (TEOS) nd isopropyl lcohol (IPA) were obtined from Shnghi hemicl Regent ompny (hin).

2 Tetrpropylmmonium hydroxide (TPAOH, c %) ws supplied by hngling tlyst ompny (hin). Ure nd xylene were supplied by Beijing hemicl Regent ompny (hin). F-4 ws obtined from Shnghi Sinyc orportion Limited (hin). yclohexnone oxime ws supplied by Alf Aesr Regent ompny. Sheet-like TS-1 crystls (TS-1-S) were hydrothermlly synthesized from strting titnosilicte gels with molr rtios of SiO 2 /0.02 TBOT/0.3 TPAOH/40 H 2 O/0.33 IPA/ ure. Typiclly, (1) g of TBOT ws dissolved in g of IPA, followed by ddition of ml of TPAOH (12.6 % wt.), 6 ml of wter, nd 5 ml of TEOS; (2 ) After stirring t room temperture for overnight, 0.5 g of ure ws introduced into the gel; (3) After stirring for 4-5 h, the gel ws trnsferred into n utoclve to crystllize t 180 for 24 h; (4) After filtrting t room temperture, drying t bout 80, clcining t 550 for 4 h, sheet-like TS-1 crystls (TS-1-S1) were obtined. hin-like TS-1 crystls (TS-1-) were hydrothermlly synthesized from strting titnosilicte gels with molr rtios of SiO 2 /0.02 TBOT/0.3 TPAOH/40 H 2 O/0.33 IPA/ flurocrbon surfctnt (F-4). For comprison, norml TS-1 crystls were synthesized from strting titnosilicte gel with molr rtio of SiO 2 /0.02 TBOT/0.3 TPAOH/40 H 2 O/0.33 IPA.

3 hrcteriztion. Scnning electron microscopy (SEM) experiments were performed on JEOL electron microscopes (FE-JSM 6700, Jpn). Trnsmission electron microscopy (TEM) experiments were performed on JEM 3010 electron microscope (JEOL, Jpn) with n ccelertion voltge of 300 kv. X-ry diffrction (XRD) dt were collected on Rigku D/MAX 2550 diffrctometer with u KF rdition. UV-visible spectr were collected on PERKIN ELMER Lmbd 20. The 13 nd 19 F NMR spectr were recorded on Bruker Avnce 500 spectrometer. Beckmnn rerrngements. tlytic Beckmnn rerrngements were crried out in fixed-bed flow rector. 0.2 g of ctlyst ws fixed with qurtz wool in stinless steel rector. The rector ws plced inside temperture-controllble verticl furnce. After flowing N 2 t 350 for 2 h, 10 wt% of cyclohexnone oxime in toluene ws fed into the rector fter vporiztion by pump with rte of 2.0 ml/h. The rection products were collected in n ice-wter trp nd nlyzed using n Agilent 6890N G. Adsorption experiments of xylene isomers. Before the test, 0.2 g of the smple ws evcuted t 180 for 2 h to remove the dsorbte. Adsorptive cpcity of xylenes ws mesured by the difference in smple weight before nd fter the exposure to xylene vpor. DFT clcultion method. In this work, we used computtionl pckge

4 clled FIREBALL, which is bsed on density functionl theory (DFT-LDA for this work) with nonlocl pseudopotentil scheme. The core of this method is self-consistent version of the Hrris-Foulkes functionl with confined tomic-like orbitls used s bsis set for the determintion of the occupied eigenvlues nd eigenvectors of the one electron Hmiltonin. We recommend reder to Ref. [S1] for detiled description of the method. Previous work on different systems demonstrted tht FIREBALL pckge is cpble to predict energetic structurl properties of vriety of nnoscle systems. In this work, we chose miniml bsis set for Si (r c = 4.9, 5.3) nd O (r c = 3.3, 3.8); the r c vlues in prentheses re the cutoff of the wvefunctions (in tomic units, B ) for s nd p, respectively. The three MFI slbs re cut directly from the pure MFI (Si:O) zeolite crystl structure. As shown in Figure S1, the three orienttions re bsed upon the originl unit cell structure. In order to compre the totl energy of three slbs tht we cut from the MFI bulk structure, we keep the sme mount of toms in ech slb fixed s 288 toms. In Tble S1, both the grnd energy nd cohesive energy (per toms) re shown. The result demonstrtes tht the slb cut from the (010) direction shows the lowest energy, which indictes the higher stbility in the direction growing during the entire zeolite synthesis procedure. Bsed on our computtionl result, we propose tht MFI (010) surfce is the more fvorble orienttion. Supporting References:

5 S1. Lewis, J.P., et l., Further developments in the locl-orbitl density-functionl-theory tight-binding method, Physicl Review B, 2001, 64,

6 Tble S1. The DFT clculted energy of three MFI slbs in (001), (010) nd (101) orienttions. Ech slb hs 288 toms, nd the energy unit is clculted in ev Grnd Energy (per tom) Averge Energy (per tom)

7 Figure S1. The three principl MFI frmeworks in (001), (010) nd (101) orienttions.

8 Figure S2. (A) TEM imge of TS-1-2. (B) nd () re the enlrgements for selected res of () nd (b) in (A). These imges confirm tht there re strong interctions between crystls.

9 Intensity (.u.) A Thet/degree Absorbnce (.u.) B Wvelength (nm) Figure S3. (A) XRD pttern nd (B) UV-visible spectrum of TS-1-S1 synthesized t 180 from the strting gel with molr rtio of ure/sio 2 t These results indicte tht TS-1-S1 with pure 4-coordintive Ti sites hs good crystllinity.

10 A Intensity (.u.) Thet/ degree Absorbnce (.u.) B Wvelength (nm) Figure S4. (A) XRD pttern nd (B) UV-visible spectrum of TS-1-2 synthesized t 180 from the strting gel with molr rtio of F-4/SiO 2 t These results indicte tht TS-1-2 with pure 4-coordintive Ti sites hs good crystllinity.

11 Figure S5. SEM imges of TS-1-S1 crystllized t 180 for (A) 2.0, (B) 2.5, () 3.0, (D) 3.5, (E) 4.0, (F) 6.0, (G) 12.0, nd (H) 24.0 h, respectively. These results suggest tht the sheet-like crystls re minly formed in the period of 3-4 h.

12 Figure S6. SEM imges of TS-1-2 synthesized t 180 for (A) 2.0, (B) 2.2, () 2.3, (D) 3.0, (E) 6.0, (F) 12.0, (G) 18.0, nd (H) 24.0 h, respectively. These results indicte tht chin-like crystls re minly formed in the period of h.

13 Figure S7. High-resolution TEM imge of nnoprticles ( nm) for the synthesis of TS-1-2 product crystllized for 2.2 h t 180. This imge demonstrtes tht the nnoprticles for the synthesis of TS-1-2 product crystllized for 2.2 h t 180 hve become TS-1 zeolitic structure.

14 Figure S8. SEM imges of TS-1-S synthesized t 180 for 24 h in the strting gels with molr rtios of ure with SiO 2 t (A) 0.074, (B) 0.147, () 0.221, nd (D) 0.368, respectively. These results show tht the length of TS-1 crystls long b-orienttion could be djusted by chnging molr rtios of ure with silic.

15 Figure S9. SEM imges of TS-1- synthesized t 180 for 24 h in the strting gels with molr rtios of F-4 with silic t (A) 0.024, (B) 0.048, () 0.072, nd (D) 0.084, respectively. These results show tht the length of TS-1 crystls long b-orienttion could be djusted by chnging molr rtios of F-4 with silic.

16 O H 2 N NH 2 A B D Figure S NMR spectr of ure treted t 180 for (A) 0, (B) 3.0, () 4.0, nd (D) 5.0 h, respectively. These results suggest tht prtil molecules of ure still exist during the crystlliztion time of 3-5 h.

17 F 3 F 2 b c F F 2 O b F 2 O 2 c F O H N H 2 H 2 H 2 H 3 N I F 3 F 3 2 H 5 2 b c c b A B c b c b D Figure S F NMR spectr of F-4 treted t 180 for (A) 2.0, (B) 3.0, () 4.0, nd (D) 6.0 h, respectively. These results suggest tht prtil molecules of F-4 still exist during the crystlliztion time of 2-4 h.

18 Figure S12. SEM imge of sheet-like crystls of S-I synthesized t 180 from the gel with molr rtio of ure with silic t This imge shows tht the smple hs good crystllinity nd the crystlline morphology is sheet-like.

19 TEOS + TBOT + TPAOH + dditive ure F-4 Suppressed Growth of (010) Surfce ontinuous Stcking long (010) Orienttion Scheme S1. Proposed mechnism on the formtion of TS-1-S crystls or TS-1- crystls in the presence of ure or F-4. After preferentil dsorption of ure on (010) surfce, the crystl growth long (010) orienttion could be suppressed, giving TS-1-S crystls. On the contrry, F-4 surfctnts could be dsorbed on the two nerby TS-1 crystls. As result, F-4 is served s linker for the two nerby TS-1 crystls. After continuous linking TS-1 crystls, TS-1- crystls re formed finlly.