Framework Isomerism in Vanadium Metal. Organic Frameworks: MIL-88B(V) and MIL- 101(V)

Transcription

1 Supporting Information Framework Isomerism in Vanadium Metal Organic Frameworks: MIL-88B(V) and MIL- 101(V) Fabian Carson, a,b Jie Su, a,b Ana E. Platero Prats, a,b Wei Wan, a,b Yifeng Yun, a,b Louise Samain b and Xiaodong Zou a,b* a Berzelii Center EXSELENT on Porous Materials, Stockholm University, SE Stockholm, Sweden, b Department of Materials and Environmental Chemistry, Stockholm University, SE Stockholm, Sweden xiaodong.zou@mmk.su.se Page number Table of Contents S2 S2 S3 S3 S4 S6 Synthesis Conditions for MIL-88B and MIL-101 vanadium MOFs Figure S1. XRPD patterns of MIL-88B(V) and MIL-101(V) Figure S2. Scanning Electron Microscopy (SEM) images of MIL-88B(V), MIL- 101(V) and MIL-47 Figure S3. XRPD patterns of phase synthesized with H 2 O Figure S4. Pawley Refinement Profile Fittings of MIL-88B(V) Figure S5. In situ XRPD of MIL-88B(V) under vacuum S1

2 S6 Figures S6 and S7. Fourier-Transform Infrared Spectroscopy (FTIR) of MIL- 88B(V) and MIL-101(V) Synthesis of Vanadium MOFs: MIL-88B(V): BDC ( g, 1 mmol) and VCl 3 ( g, 1 mmol) were added to a Teflon liner. Absolute ethanol (5 ml) and 1M HCl (1 ml) were added and the mixture was stirred for 30 min, followed by sonication for 15 min. The autoclave heated at 120 C for 48 h. After cooling to room temperature, the precipitate was washed with ethanol and separated by centrifugation. MIL-101(V): BDC ( g, 1 mmol) and VCl 3 ( g, 1 mmol) were added to a Teflon-lined autoclave. Absolute ethanol (5 ml) was added and the mixture was stirred for 30 min, followed by sonication for 15 min. The autoclave was heated at 120 C for 48 h. After cooling to room temperature, the precipitate was washed with ethanol and separated by centrifugation. X-Ray Powder Diffraction (XRPD): Figure S1. Experimental XRPD patterns of MIL-88B(V) (purple) and MIL-101(V) (green) and simulated XRPD patterns of MIL-88B(Cr) (black) and MIL-101(Cr) (blue). Since MIL-88B is a flexible MOF, the pattern for MIL-88B(Cr) corresponds to the structure dried in water, whereas the pattern for MIL-88B(V) corresponds to the structure dried in ethanol (due to MIL-88B(V) being sensitive to water). λ = Å (Cu, K α1 ) S2

3 Scanning Electron Microscopy (SEM): Figure S2. SEM images of as-synthesized samples of MIL-88(B) (upper left), MIL-101(V) (upper right) and MIL-47 (lower middle). Upper right inset: a MIL-101(V) crystal. Figure S3. XRPD pattern of phase synthesized with ethanol (5 ml) and H 2 O (1 ml) instead of 1M HCl (1 ml). S3

4 Pawley Refinement Profile Fittings of MIL-88B(V) Profile Fittings: Full pattern decomposition was performed using Pawley refinement conducted in Topas Academic V4.1 using data in the range 2θ = The background was fitted with a 15 th order Chebyschev polynomial. The profile fitting results are shown in Figures S5, S6, S7 and S8. The refinement was conducted using a Pearson VII peak profile function, followed by refinement of unit cells and the zero-shift. (a) MIL-88B(V) in ethanol Rp 2.09 Rp 4.99 Rwp 2.88 Rwp 5.72 χ (b) MIL-88B(V) in methanol Rp 1.70 Rp 4.04 Rwp 2.61 Rwp 5.13 χ S4

5 (c) MIL-88B(V) in N,Ndimethylformamide Rp 0.98 Rp 4.67 Rwp 1.27 Rwp 4.85 χ d) MIL-88B(V) under vacuum Rp 5.22 Rp 1.03 Rwp 8.20 Rwp 2.32 χ Figure S4. Profile fittings of MIL-88B(V) in (a) ethanol, (b) methanol, (c) N,Ndimethylformamide and (d) under vacuum at room temperature. S5

6 In situ XRPD of MIL-88B(V) under vacuum: Figure S5. In situ XRPD patterns of MIL-88B(V) collected at temperatures increasing from 50 to 250 C under vacuum. Heating rate was 2 C/min and the furnace was held at the temperature for 10 min before collecting the diffraction pattern. λ = Å (Cu, K α ) Fourier-Transform Infrared Spectroscopy (FTIR): 100 Transmittance (%) Wavenumber (cm 1 ) Figure S6. Far-FTIR spectra of MIL-88B(V) (purple) and MIL-101(V) (green). S6

7 100 Transmittance (%) Wavenumber (cm 1 ) Figure S7. FTIR spectra of MIL-88B(V) (purple) and MIL-101(V) (green). 1) S. Surblé, C. Serre, C. Mellot-Draznieks, F. Millange, and G. Férey, Chem. Commun., 2006, ) C. Serre, C. Mellot-Draznieks, S. Surblé, N. Audebrand, Y. Filinchuk, and G. Férey, Science, 2007, 315, ) Y.-H. Shih, S.-H. Lo, N.-S. Yang, B. Singco, Y.-J. Cheng, C.-Y. Wu, I.-H. Chang, H.-Y. Huang, C.-H. Lin, ChemPlusChem, 2012, 77, ) G. Férey, C. Mellot-Draznieks, C. Serre, F. Millange, J. Dutour, S. Surblé, and I. Margiolaki, Science, 2005, 309, ) C. Serre, C. Mellot-Draznieks, S. Surblé, N. Audebrand, Y. Filinchuk, and G. Férey, Science, 2007, 315, ) K. M. L. Taylor-Pashow, J. D. Rocca, Z. Xie, S. Tran, and W. Lin, J. Am. Chem. Soc., 2009, 131, ) J. P. S. Mowat, S. R. Miller, A. M. Z. Slawin, V. R. Seymour, S. E. Ashbrook, and P. A. Wright, Microporous and Mesoporous Materials, 2011, 142, ) Y.-T. Li, K.-H. Cui, J. Li, J.-Q. Zhu, X. Wang, and Y.-Q. Tian, Chinese Journal of Inorganic Chemistry, S7