Supporting Information. Microwindows on the Shell

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1 Supporting Information Organic-inorganic Hybrid Hollow Nanospheres with Microwindows on the Shell Jian Liu,, Qihua Yang,*, Lei Zhang, Hengquan Yang, Jinsuo Gao,, and Can Li*, State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian , China, and Graduate School of the Chinese Academy of Sciences, Beijing , China RECEIVED DATE (to be automatically inserted after your manuscript is accepted if required according to the journal that you are submitting your paper to) * To whom correspondence should be addressed. yangqh@dicp.ac.cn; canli@dicp.ac.cn. Tel: ; Fax: URL: Dalian Institute of Chemical Physics, Chinese Academy of Sciences Graduate School of the Chinese Academy of Sciences S1

2 Contents 1. Table S1. Physicochemical properties of organic-inorganic hybrid materials (Et40) before and after adsorption with probe molecules. 2. Figure S1. Structures of ibuprofen, BINOL, and Co(Salen) molecules and their dynamic molecular sizes. 3. Figure S2. TEM image of the organic-inorganic hybrid hollow nanosphere (Et40) measured using the powder sample without dispersion in ethanol. 4. Figure S3. FT-IR spectra of the organic-inorganic hybrid hollow nanosphere (Et40): (a), before extraction of surfactant; (b) before after extraction of surfactant. 5. Figure S4. (a), 13 C CP-MAS-NMR and (b), 29 Si MAS-NMR spectra of the organic-inorganic hybrid hollow nanosphere (Et40). 6. Figure S5. TG and DTG profiles of the organic-inorganic hybrid hollow nanosphere (Et40): (a), before extraction of surfactant (red line); (b) after extraction of surfactant. 7. Figure S6. Hyperpolarized 129 Xe NMR spectra at variable temperatures of the organic-inorganic hybrid hollow nanosphere (Et40); and discussion of 129 Xe NMR spectra. 8. Figure S7. High resolution transmission electron microscopy (HRTEM) of the organic-inorganic hybrid hollow nanosphere (Et40). 9. Figure S8. XRD patterns of organic-inorganic hybrid materials synthesized with buffer solution at different concentrations. 10. Figure S9. Size distributions (DLS method) of Pluronic F127 micelles at different buffer solution concentrations: (a), 0 mm; (b), 40 mm; (c), 400 mm. 11. Figure S10. TEM images of the organic-inorganic hybrid hollow nanospheres synthesized at different hydrothermal temperature of (a), without hydrothermal treatment; (b), 80 C; (c), 100 C; (d), 120 C. 12. Figure S11. SEM and TEM images of the organic-inorganic hybrid hollow nanosphere synthesized with different molar ratio of BTME/F127 in the range of 63:1 to 220:1 (a), 63:1; (b), 95:1; (c), 157:1; (d), 220:1. S2

3 Table S1. Physicochemical properties of organic-inorganic hybrid materials (Et40) before and after adsorption with probe molecules. sample BET surface area BJH pore diameter pore volume micropore volume a (m 2 g -1 ) (nm) (cm 3 g -1 ) (cm 3 g -1 ) Et Co(Salen)/Et40 b BINOL/Et40 b Ibuprofen/Et40 b a Calculated by the HK method. b Organic-inorganic hybrid hollow nanospheres (Et40) loaded with the probe molecules. S3

4 Figure S1. Structures of ibuprofen, BINOL, and Co(Salen) molecules and their dynamic molecular sizes. S4

5 Figure S2. TEM image of the organic-inorganic hybrid hollow nanosphere (Et40) measured using the powder sample without dispersion in ethanol. S5

6 Intensity (a.u.) (a) (b) Intensity (a.u.) Et40-as Et40-ext Wavenumber (cm -1 ) Wavenumber (cm -1 ) Figure S3. FT-IR spectra of the organic-inorganic hybrid hollow nanosphere (Et40): (a), before extraction of the surfactant; (b) after extraction of the surfactant. S6

7 a b T T Chemical Shifts (ppm) Chemical Shift (ppm) Figure S4. (a), 13 C CP-MAS-NMR and (b), 29 Si MAS-NMR spectra of the organic-inorganic hybrid hollow nanosphere (Et40). S7

8 Weight Loss ( wt% ) (a) (b) (b) (a) DTG/ugC Temperature preature ( ) ( C) Figure S5. TG and DTG profiles of the organic-inorganic hybrid hollow nanosphere (Et40): (a), before extraction of the surfactant (red line); (b) after extraction of the surfactant. S8

9 138 K 143 K 153 K 163 K 173 K 193 K 213 K 233 K 253 K 273 K 293 K (ppm) 0 Figure S6. Hyperpolarized 129 Xe NMR spectra at variable temperatures of the organic-inorganic hybrid hollow nanosphere (Et40). Discussion of 129 Xe NMR spectra: At 293 K, the resonance band at 100 ppm are attributed to mesopores of the inner void of the hollow nanospheres. With the temperature decreasing from 273 to 138 K, the chemical shifts of xenon shift to low field for Et40 because of the strong interaction of xenon-xenon. The N 2 sorption isotherm clearly shows the existence of microporosity in Et40. The fact that the microporosity of Et40 can not be observed in hyperpolarized 129 Xe NMR spectrum is probably due to the fast exchange of xenon in the void space, suggesting that the micropore in the shell of the hybrid hollow nanospheres is well connected to the hollow interior. S9

10 Figure S7. High resolution transmission electron microscopy (HRTEM) of the organic-inorganic hybrid hollow nanosphere (Et40). S10

11 d=11.6 nm d=8.6 nm Intensity (a.u.) Intensity (a.u.) Et0 Et Theta/degree Theta/degree d=11.0 nm d=12.6 nm d=13.2 nm Intensity (a.u.) Intensity (a.u.) Intensity (a.u.) Et100 Et200 Et Theta/degree Theta/degree Theta/degree Figure S8. XRD patterns of the organic-inorganic hybrid materials synthesized with buffer solution of different concentrations. S11

12 a 3.0 nm b 18.9 nm c 75.4 nm Weight % Weight % Weight % 1503 nm Size (nm) Size (nm) Size (nm) Figure S9. Size distributions (DLS method) of Pluronic F127 micelles at different buffer solution concentrations: (a), 0 mm; (b), 40 mm; (c), 400 mm. S12

13 Figure S10. TEM images of the organic-inorganic hybrid hollow nanospheres synthesized at different hydrothermal temperature of (a), without hydrothermal treatment; (b), 80 C; (c), 100 C; (d), 120 C. S13

14 Figure S11. SEM and TEM images of the organic-inorganic hybrid hollow nanosphere synthesized with different molar ratio of BTME/F127 in the range of 63:1 to 220:1 (a), 63:1; (b), 95:1; (c), 157:1; (d), 220:1. S14