Supporting Information. Rapid synthesis of metal-organic frameworks MIL-101(Cr) without the addition of solvent and hydrofluoric acid

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1 Supporting Information Rapid synthesis of metal-organic frameworks MIL-11(Cr) without the addition of solvent and hydrofluoric acid Kunyue Leng a, Yinyong Sun a *, Xiaolin Li a, Shun Sun a, Wei Xu b a School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin, 151, China. Fax: , yysun@hit.edu.cn b State Key Lab of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun, 1312, China 1

2 Materials 1,4-benzene dicarboxylate (BDC) was purchased by Aldrich. Other reagents were purchased from Sinopharm Chemical Reagent Co. and used without further purification. Characterization Powder X-ray diffraction (XRD) patterns were recorded on a Rigaku D/Max-255 diffractometer equipped with a SolX detector Cu Kα radiation with wavelength of λ = Å. Nitrogen sorption isotherms were obtained at 77 K on a Beishide 3H-2PS1 Gas Sorption and Porosimetry system. Samples were normally prepared for measurement after degassing at 423 K under vacuum until a final pressure of Torr was reached. SEM images were recorded on SUPRA 55 operated with an acceleration voltage of 2 kv. Cr content was determined by inductively coupled plasma emission spectrometry (ICP) on a PerkinElmer Optima 53DV atomic emission spectrometer. FT-IR spectra were recorded on a NicoLET is1 spectrometer. Elemental analysis was performed on Vario EL III from Elementar. Thermogravimetric analysis was carried out on TGA Q5 from TA company. The 1 H NMR spectroscopy was recorded on a 5 MHz Bruker DMX5. Synthesis of MIL-11(Cr)-X-Y: Cr(NO 3 ) 3 9H 2 O and BDC were mixed and ground at room temperature about 3 min. Then, the mixture were transfered into autoclave and heated at 22 o C. After crystallization, the obtained solids were cooled to room temperaturewashed twice with hot EtOH at 6 o C for 6 h. Finally, the obtained green powders were dried at 12 o C for 12 h. Based on the difference in the molar ratio of Cr/BDC and crystallization time, the sample was named as MIL-11(Cr)-X-Y. X and Y represented Cr/BDC and crystallization time, respectively. The detailed information about the synthesis of MIL-11(Cr)-X-Y were listed in Table S1. Synthesis of MIL-11(Cr)-HF: MIL-11(Cr)-HF was synthesized according to the procedure reported by the literature 1. Synthesis of MIL-11(Cr)-solvent: MIL-11(Cr)-solvent was synthesized according to the procedure reported by the literature 2. Oxidation of cyclohexene All reactions were performed in a 1 ml round-bottom flask equipped with a condenser and a magnetic stirrer bar. Catalyst (2 mg) was added to a solution of alkene (2 mmol) in CH 3 CN (12 ml). After the above solution was maintained at 5 o C for 15 min, H 2 O 2 (3%, 1 ml, 1 mmol) was added to the mixture. After a reaction time of 5 h, the products were analyzed by gas chromatography on an Agilent 789A GC with FID detector using a 3 m packed HP5 column. The products were also identified by GC-MS (5975C-789A, Agilent). 2

3 Table S1. N 2 adsorption data of the MIL-11(Cr) materials prepared under various conditions. BET surface Pore Cr/BDC Crystallization Samples area volume (mol) time (h) (m 2 /g) (cm 3 /g) MIL-11(Cr) : MIL-11(Cr) : MIL-11(Cr) : MIL-11(Cr) : MIL-11(Cr) : MIL-11(Cr) : MIL-11(Cr) : MIL-11(Cr) : MIL-11(Cr) : MIL-11(Cr) : MIL-11(Cr) : MIL-11(Cr) : MIL-11(Cr) : MIL-11(Cr) : MIL-11(Cr) :

4 Transmittance Wavenumber (cm -1 ) MIL-11(Cr)-HF MIL-11(Cr)-solvent MIL-11(Cr) Fig. S1. FT-IR spectra of various samples 3 COOH NO 2 COOH Chemical shift (ppm) Fig. S2. 1 H-NMR spectrum of the linker in MIL-11(Cr) The H resonance signal of the benzene rings in un-nitrified terephthalic acid is marked with a star. 3,4 * 4

5 1.7:1 Intensity (a.u.) 1.5:1 1.3:1 1:1.7: Theta (degree) Fig. S3. XRD patterns of MIL-11(Cr) synthesized at different Cr/BDC ratios. 3 BET surface area (cm 2 /g) :1 1:1 1.3:1 1.5:1 1.7:1 2:1 Cr/BDC (molar ratio) Fig. S4. BET surface area of MIL-11(Cr) synthesized at different Cr/BDC ratios. 5

6 MIL-11(Cr) Intensity (a.u.) MIL-11(Cr) MIL-11(Cr) MIL-11(Cr) MIL-11(Cr) MIL-11(Cr) MIL-11(Cr) MIL-11(Cr) Theta (degree) ` Fig. S5. XRD patterns of MIL-11(Cr) synthesized with Cr/BDC of 1.5:1 in different crystallization time BET surface area (cm 2 /g) h 2 h 3 h 4 h 5 h 1 h 15 h 2 h 3 h 4 h Crystallization time Fig. S6. BET surface area of various MIL-11(Cr) synthesized with Cr/BDC of 1.5:1 in different crystallization time. 6

7 References 1. Férey, G.; Mellot-Draznieks, C., Serre, C.; Millange, F.; Dutour, J.; Surblé, S.; Margiolaki, I. Science, 25, 39, Bromberg, Lev; Diao,Y.; Wu, H.; Speakman, S A.; Hatton, T. A. Chem. Mater. 212, 24, Bernt, S.; Guillerm, V.; Serreb, C.; Stock, N. Chem. Commun., 211, 47, Lammert, M.; Bernt, S.; Vermoortele, F.; De Vos, D. E.; Stock, N. Inorg. Chem. 213, 52,