Supporting Information

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1 Supporting Informtion Wiley-VCH Weinheim, Germny Single-Crystl-like Titni Mesocges** Zhenfeng Bin, Jin Zhu, Jing Wen, Fenglei Co, Yuning Huo, Xufng Qin, Yong Co, Meiqing Shen,* Hexing Li,* nd Yunfeng Lu* nie_ _sm_miscellneous_informtion.pdf

2 Experimentl 1. Mterils Chrcteriztion The smples were chrcterized using X-ry diffrction (D/MAX-2000 with CuKα rdition), scnning electron microscopy (HITACHI S4800) nd trnsmission electronic microgrph (JEOL JEM-2100, operted t 200 KV) nd nitrogen sorption (Quntchrome NOVA 4000e). The Brunuer-Emmett-Teller (BET) method ws utilized to clculte the specific surfce re; pore volume nd pore dimeter distriution ws derived from the dsorption isotherms y the Brrett-Joyner-Hlend (BJH) model. ζ potentils of the polycrystlline TiO 2 prticles (0.05 g/l in tert-utyl lcohol) were mesured fter dding ech cid (ph mintined t 1.0) using Mlvern Zetsizer Nno ZS. 2. Photoctlytic Activity Test The oxidtion rections were crried out in self-designed 150 ml rector contining 0.10 g of TiO 2, 10 ml of deionized H 2 O nd ml of toluene or cinnmyl lcohol. Six 6-W lmps (wvelengths 310 nm) were used s the UV light source. Before we mesured the photoctlytic properties, ll the smples including P-25 were wshed with 0.2 M NOH nd distilled wter for severl times. Energy dispersive X-ry spectroscopy (EDX, JEM-2100) nlysis (Tle S2) reveled tht no significnt S species were detected, indicting tht the sulfte ws removed. After rection t 20 C for 2 h, the products were extrcted with diethyl ether nd nlyzed using gs chromtogrph (Shimdzu, GC-17A); lnk experiments showed no mesurle oxidtive products; the rections were repeted three times with vrition of ± 3%. Tle S1. Surfce re (S BET ), pore dimeter (D p ), nd pore volume (V p ) of vrious TiO 2 Smple S BET (m 2 /g) D p (nm) V p (cm 3 /g) P Polycrystlline TiO TiO 2 single crystls with disordered pores TiO 2 single crystls with 2D ordered pores TiO 2 single crystls with 3D ordered pores Tle S2. Structurl prmeters of mesoporous single crystls synthesized t different solvents Solution S BET (m 2 /g) Vp (cm 3 /g) Dp (nm) Crystllite Size (nm) Tert-utyl lcohol Isopropnol Benzyl lcohol Tle S3. Atom rtios of Ti, S nd O in single-crystlline TiO 2 smples fter wshing single-crystlline TiO 2 smples Atom rtio (%) Ti O S Disordered Ordered 2D Ordered 3D

3 c Intensity (.u.) Figure S1 () TEM microgrph nd () SAED recorded from the side of crystl nd (c) schemtic depicting the crystllogrphic configurtion nd plcement of the plnes with prticle morphology Figure S2 Low-ngle XRD pttern of the TiO2 single crystls with disordered mesoporous chnnels

4 101 ntse Intensity (.u.) c d Figure S3 Wide-ngle XRD ptterns of () polycrystlline TiO 2, () single-crystlline TiO 2 with disordered pores, (c) single-crystlline TiO 2 with 2D ordered pores (P6mm), nd (d) single-crystlline TiO 2 with 3D ordered pores (I3d) (100) (211) Intensity (.u.) (110) (200) SBA-15 Intensity (.u.) X 5 KIT-6 X 3 meso-tio 2 (420) (332) meso-tio Figure S4 Low-ngle XRD ptterns of () SBA scffold with 2D ordered mesoporous structure (P6mm) nd the replicted mesoporous TiO 2 single crystl, nd () KIT-6 scffold with 3D ordered mesoporous chnnels (I3d) nd the replicted single crystls.

5 Figure S5 Representtive HRTEM imges of the edge of the spheroidl TiO2 crystl nd schemtic illustrting their stck into single-crystl-like TiO2. The truncted octhedron TiO2 uilding crystl orientted long the [001] nd [11 1 ] zone xis. Fig. S5 displyed squre shpe indictive of {001} fcet which clerly demonstrted tomic plnes of (200) or (020) crystl fces with the interfcil ngle of 90o nd the d-spcing round nm. The rhomus shpe in Fig. S5 ws oserved through [11 1 ] zone xis which displyed the (101) nd (011) fces with the interfcil ngle of 82.4o. The interfcil ngle is consistent with the theoreticl vlue. Bsed on the nlysis of HRTEM imge, the geometry of single crystlline ntse TiO2 is dechedron with the exposure of {001} fcets (see the model 3D view).

6 Intensity (.u.) Intensity (.u.) Volume (cm 3 STP/g) c dv/dd (cm 3 STP/(g.nm)) Pore Dimeter (nm) Reltive Pressure (P/P 0 ) Volume (cm 3 STP/g) dv/dd (cm 3 STP/(g.nm)) Pore Dimeter (nm) d Reltive Pressure (P/P 0 ) Figure S6 Wide ngle XRD ptterns nd nitrogen sorption isotherms nd pore size distriution of (, c) ZrO 2 nd (, d) CeO 2 mesoporous single crystls. N 2 dsorption-desorption isotherms nd pore size distriution of (c) ZrO 2 nd (d) CeO 2 mesoporous single crystls t 77 K. To synthesize the ZrO 2, zirconium(iv) sulfte oxide hydrte: H 2 O: sodium sulfte (N 2 SO 4 ) : mmonium fluoride (NH 4 F): queous mmoni (mole rtio = 1:3955:6:10:115) were dded into 50 ml utoclve nd llowed to lcoholyze t 100 C under solvotherml condition for 48 h. To synthesize CeO 2, cerium (IV) sulphte (Ce(SO 4 ) 2 ) : H 2 O : sodium sulfte (N 2 SO 4 ) : mmonium fluoride (NH 4 F) : queous mmoni (mole rtio = 1:1797:3:4:10) solution ws dded into 50 ml utoclve nd llowed to lcoholyze t 100 C under solvotherml condition for 48 h. The precipitted powders were filtered, wshed thoroughly with de-ionized wter, nd dried t 100 C. The surfce re nd verge pore dimeter of the ZrO 2 nd CeO 2 crystls re listed elow. S BET (m 2 /g) V P (cc/g) D P(v) (nm) ZrO CeO

7 c d e f Figure S7 SEM () nd TEM () imges nd SAED pttern (inset) of typicl polycrystlline TiO2 prticles synthesized in the sence of SO42-. The molr rtio of TiCl4 to tert-utyl lcohol ws kept t 1:165. The rection ws occurred t 110 oc for 48 hour. Addition of (c, d) H2SO4 or (e, f) HF to the ove precursor solution followed y similr rections led to the formtion of mesoporous TiO2 single crystls. The inserted SAED ptterns confirm the single crystlline structure.

8 c d Figure S8 Representtive TEM morphologies of mesoporous single-crystlline TiO2 clcined t elevted tempertures () 350, () 450, (c) 550, nd (d) 650 oc. Incresing the clcintion temperture resulted in grdul decrese of mesoporous structure. Nevertheless, mesoporous structure ws still oserved even fter eing clcined t 450 C. The retined surfce re ws determined s 105 m2/g, which is significntly higher thn polycrystlline TiO2 (62 m2/g) Further increse of the clcintion temperture to 650 C cused collpse of the mesoporous structure, corresponding to the surfce re decresed to 26 m2/g.