Supporting information for

Transcription

1 Supporting information for Combining Linker Design and Linker Exchange Strategies for the Synthesis of a Stable Large Pore Zr-Based Metal Organic Framework Hue T. T. Nguyen,, Thach N. Tu,*,, My V. Nguyen,, Tien H. N. Lo,,, Hiroyasu Furukawa, Ngoc N. Nguyen,,, My D. Nguyen, Center for Innovative Materials and Architectures (INOMAR) and University of Science, Vietnam National University-Ho Chi Minh (VNU-HCM), Ho Chi Minh City , Vietnam Nguyen Tat Thanh University, 300A Nguyen Tat Thanh Street, District 4, Ho Chi Minh City , Vietnam Department of Chemistry, University of California, Berkeley, California 94720, United States *To whom correspondence should be addressed: tnthach@inomar.edu.vn; tnthach@ntt.edu.vn S-1

2 Table of Contents Section S1 Materials and Analytical Techniques S-3 Section S2 Scanning Electron Microscope (SEM) Images of reo- MOF-1 and reo-mof-1a S-4 Section S3 Powder X-ray Diffraction Patterns at Different Mixedlinker Conditions S-6 Section S4 Structural Solution of reo-mof-1 S-9 Section S5 Fourier Transform Infrared (FT-IR) Analyses S-14 Section S6 Thermogravimetric Analyses (TGA) S-16 Section S7 PXRD Patterns of Linker-exchanged Samples S-17 Section S8 1 H-NMR Analysis of Digested Samples S-19 Section S9 77 K N2 Uptake Measurements S-21 Section S10 Catalytic Studies for the Synthesis of 2-phenylbenzoxazole S-23 Section S11 Stability of reo-mof-1a after Catalytic Recycles S-29 Section S12 Probing the Relationship between Catalytic Activity and the Amount of Acidic Functionalities S-31 References S-37 S-2

3 Section S1 Materials and Analytical Techniques Starting Materials and General Procedures. Napthalene-2,6-dicarboxylic acid (H2NDC, 95%), benzene-1,4-dicarboxylic acid (98%), benzene-1,3,5-tricarboxylic acid (95%), zirconium(iv) oxychloride octahydrate (ZrOCl2 8H2O, 98%), anhydrous N,N-dimethylformamide (DMF, 99.8%), sulfuric acid (H2SO4, 95%), hydrochloric acid (HCl, 37%), and formic acid (HCO2H, 95%) were purchased from Aldrich Chemical Co. Anhydrous methanol (MeOH, 99.8%) and dichloromethane (CH2Cl2, 99.5%) were obtained from EMD Millipore Chemicals. All other chemicals were purchased from local vendors and all chemicals were used without further purification. UiO-66, UiO-67, DUT-52, and MOF-808-P were synthesized according to the published procedures. 1-5 Thermal gravimetric analysis (TGA) was performed using a TA Q500 thermal analysis system under air flow. Fourier transform infrared (FT-IR) spectra were recorded on a Bruker Vertex 70 spectrometer using the attenuated total reflectance (ATR) sampling method. Solution 1 H and 13 C nuclear magnetic resonance (NMR) spectra were acquired on a Bruker Advance II-500 MHz NMR spectrometer. Typically, reo-mof-1 and reo-mof-1a (15 mg) were digested in 500 μl of DMSO-d6 containing HF (10 μl). The mixture was then sonicated for 10 minutes before 1 H NMR measurement. Scanning electron microscope (SEM) observation was performed using a HITACHI FE SEM S4800. N2 adsorption measurements were performed using a Micromeritics 3Flex Surface Characterization Analyzer. A liquid N2 bath was used for the measurements at 77 K. Elemental analysis was performed using a LECO CHNS-932 analyzer. The gas chromatography (GC, model: Agilent System 19091s-433) equipped with a flame ionization detector (FID) was used to determine the yield of catalytic reactions. Toluene was used as an internal standard to quantify the yield of catalytic reactions. Powder X-ray Diffraction Analysis and structure solution. Powder X-ray data were collected using a Bruker D8 Advance employing Ni-filtered Cu Kα (λ = Å). The system was equipped with an anti-scattering shield that prevents incident diffuse radiation from hitting the detector. S-3

4 Section S2 Scanning Electron Microscope (SEM) Images of reo-mof-1 and reo-mof-1 A Figure S1. Scanning electron microscope (SEM) image of reo-mof-1. S-4

5 Figure S2. Scanning electron microscope (SEM) image of reo-mof-1a. S-5

6 Section S3 Powder X-ray Diffraction Patterns at Different Mixed-linker Conditions Figure S3. PXRD pattern for as-synthesized reo-mof-1 (red) is compared to the simulated patterns for reo-mof-1 (black) and DUT-52 (blue). S-6

7 Figure S4. PXRD patterns of MOFs prepared using a different ratios of H3SNDC/H2NDC. The gradual increase in the relative intensity of two diffraction peaks at low angle (highlight in green, 2θ = 3.75 and 5.29 ) was observed by increasing in the amount of H3SNDC. S-7

8 Figure S5. Simulated PXRD patterns of fcu net with different site occupancy of the Zr-based cluster at the body-centered position. The relative intensity of two diffraction peaks at low angle (highlight in green, 2θ = 3.75 and 5.29 ) gradually decreases with an increase in the percentage of the missing clusters. This trend implies that reo-mof-1 (reo topology) is obtained by the defectcontrolled synthesis. S-8

9 Section S4 Structural Solution of reo-mof-1 Determination of unit cell parameters. The analysis of the diffraction data for as-synthesized reo-mof-1 (pattern indexing and Pawley refinement) was performed with the program Materials Studio ver. 7.0, Accelrys Software Inc. A background correction was performed using a 40- parameter Chebyschev polynomial function. Precise unit cell length (a = Å) was determined by Pawley refinements. The Bravais lattice of reo-mof-1 is determined to adopt the cubic system with Pm-3 space group (No. 200), which was later confirmed by Rietveld refinements. Structural Modeling of reo-mof-1. Several modeled structures were generated to determine the structure of reo-mof-1 using the Materials Visualizer module of Materials Studio ver. 7.0 software. Comparing the profile of simulated diffraction patterns with experimental one, the modeled framework in reo net shows good agreement with the experimental pattern. In this structure, 8-coordination inorganic clusters, Zr6O8(H2O)8(CO2)8, are linked by HSNDC 2- linkers. For Rietveld refinements, the pores of reo-mof-1 were filled with oxygen atoms to represent the residue electron density from guest molecules. Indeed, this method has been done on similar materials. 6,7 Finally, the full profile pattern fitting (Rietveld method) was performed against the experimental powder pattern of reo-mof-1 with 2θ = This gave the satisfactory result with the fitting that converged at reasonable residual values (Rwp = 6.4%, Rp = 4.13%) and the final unit cell parameters (a = Å). The fractional atomic coordinates, refined cell parameters and crystal structure information of reo-mof-1 after the Rietveld fitting is shown in Table S1. S-9

10 Table S1. Atomic coordinates and refined unit cell parameters of reo-mof-1. Name reo-mof-1 Space group Pm-3 a (Å) Å Unit Cell Volume (Å 3 ) R p 4.13% R wp 6.40% Atom Name x y z Site Occupancy O O O O O O O S C C C C C C C C C C C C H H H H H Zr Zr Zr O8s O9s O10s O11s O12s O13s O14s O15s O16s O17s S-10

11 Figure S6. Space-filling model of reo-mof-1. Atom colors: Zr, blue polyhedra; C, black; O, red; S, yellow; H, white. S-11

12 Figure S7. Full range Rietveld refined PXRD patterns of as-synthesized reo-mof-1. S-12

13 Figure S8. The fcu net (DUT-52) (a) is composed of the octahedral and tetrahedral cages (c, d). When the octahedral cage in the middle of the cell and neighboring eight tetrahedral cages in the fcu net are absent, a large cuboctahedral cage (e) is observed (b). Atom colors: Zr, blue polyhedra; C, black; O, red; S, yellow; all hydrogen atoms are omitted for clarity. The large orange, yellow, and white spheres are placed in the structure for clarity and to indicate space in the cage. S-13

14 Section S5 Fourier Transform Infrared (FT-IR) Analyses Figure S9. FT-IR spectra of reo-mof-1 (black) and reo-mof-1a (blue). S-14

15 Figure S10. FT-IR spectra of reo-mof-1 and the mixed-linker samples (H3SNDC/H2NDC = 7/3 and 4/6). Three unique peaks (1180, 1458, and 1649 cm 1 ) are assigned to the sulfonate, aromatic (C=C) bending, and carboxylate stretching modes of SNDC 3 linker, which shows the decreased intensity in the spectrum of 7/3 and 4/6 samples. This indicates the presence of the lesser amount of SNDC 3 in these materials. S-15

16 Section S6 Thermogravimetric Analyses (TGA) Figure S11. TGA traces of reo-mof-1 (black) and reo-mof-1a (red). The amounts of residual metal oxide (attributed to ZrO2) for reo-mof-1 and reo-mof-1a are consistent with the expected values from their chemical formula (calcd.: 37.04%; found: 37.43% and 38.70%; found: 37.99%, respectively). S-16

17 Section S7 PXRD Patterns of Linker-exchanged Samples Figure S12. PXRD patterns of the activated reo-mof-1a and linker-exchanged samples (mixedlinker sample at H3SNDC/H2NDC = 7/3 and 4/6). These data indicate that the connectivity of linker-exchanged materials is retained after the linker exchange reaction. S-17

18 Figure S13. PXRD pattern of reo-mof-1a after immersion in water for one month (red). Simulated PXRD pattern of reo-mof-1 (black) was overlaid as a reference. S-18

19 Section S8 1 H-NMR Analysis of Digested Samples Figure S14. 1 H NMR spectrum of digested reo-mof-1. Figure S15. 1 H NMR spectrum of digested reo-mof-1a S-19

20 Figure S16. 1 H NMR spectra of mixed-linker samples (H3SNDC/H2NDC = 7/3 and 4/6). S-20

21 Section S9 77 K N 2 Uptake Measurements Figure S K N2 uptake of linker-exchanged samples (H3SNDC/H2NDC = 7/3 and 4/6). The BET (Langmuir) surface area of these samples were calculated to be 1453 (1581) and 1550 (1814) m 2 g 1, respectively. S-21

22 Figure S18. Pore size distribution of the linker-exchanged samples (H3SNDC/H2NDC = 7/3 and 4/6). N2 isotherms were analyzed by quenched solid density functional theory implementing a hybrid kernel for 77 K N2 adsorption based on a carbon model containing slit/cylinder/sphere pores. S-22

23 Section S10 Catalytic Studies for the Synthesis of 2-Phenylbenzoxazole Catalysis study. An equimolar amount of 2-aminophenol (0.055 g, 0.50 mmol) and benzaldehyde (0.053 g, 0.50 mmol) were added into a flask pre-charged with reo-mof-1a (10 mg, 1 mol% catalyst). The reaction mixture was stirred at 140 C for 6 h, during which the reaction was sampled (~1.7 mg) every 1 h. The collected sample was then dissolved in chloroform (1.2 ml) to extract all organic species, followed by the centrifugation to remove the catalyst. Toluene (internal standard) was then added to the supernatant containing the phenylbenzoxazole. Thereafter, the mixture was subjected to the GC FID or GC-MS analysis. After completion of the catalytic reaction, the reaction mixture was dissolved in 5 ml acetone. reo-mof-1a catalyst was separated out by centrifugation, which was washed with anhydrous acetone and ethanol (2 10 ml), respectively. The combined organic layers were evaporated under reduced pressure to obtain the crude product, which was purified by silica gel column chromatography (hexane/chloroform = 9/1, v/v) in order to afford the pure product. The purified material was characterized by FT-IR, 1 H NMR, and 13 C NMR spectroscopies, and GC MS analysis. S-23

24 Figure S19. GC-MS analysis: a) Chromatogram and b) MS spectrum of 2-phenylbenzoxazole product. S-24

25 Figure S20. The standard curve for calculation of the 2-phenylbenzoxazole concentration. S-25

26 Figure S21. 1 H NMR spectrum of 2-phenylbenzoxazole product. Figure S C NMR spectrum of 2-phenylbenzoxazole product. S-26

27 Figure S23. FT-IR spectrum of 2-phenylbenzoxazole product. S-27

28 Figure S24. GC yield percentage of 2-phenylbenzoxazole as a function of reaction time in the presence of various catalysts. Mixed-linker samples (H3SNDC/H2NDC = 7/3 and 4/6) were exchanged with K2NDC for 30 minutes, acidified, solvent-exchanged and activated before catalytic tests. S-28

29 Section S11 Stability of reo-mof-1 A after Catalytic Recycles Figure S25. PXRD patterns of activated reo-mof-1a (red) and reo-mof-1a after fifth catalytic cycle (blue). S-29

30 Figure S26. FT-IR spectra of activated reo-mof-1a (red) and reo-mof-1a after fifth catalytic cycle (blue) for the synthesis of 2-phenylbenzoxazole. S-30

31 Section S12 Probing the Relationship between Catalytic Activity and the Amount of Acidic Functionalities Figure S27. PXRD pattern of activated 10 min, 30 min and 14 h reo-mof-1a samples. S-31

32 Figure S K N2 isotherm of 10 min, 30 min and 14 h reo-mof-1a. The BET surface area of the samples are calculated: reo-mof-1 (34 m 2 g 1 ); 10 min reo-mof-1a (1704 m 2 g 1 ), 30 min reo-mof-1a (2104 m 2 g 1 ), and 14 h reo-mof-1a (2218 m 2 g 1 ). Extension of the linker exchange time over 30 min did not show significant enhancement of the surface areas. S-32

33 Figure S29. Pore size distribution of 10 min, 30 min and 14 h reo-mof-1a samples. N2 isotherms were analyzed by quenched solid density functional theory implementing a hybrid kernel for 77 K N2 adsorption based on a carbon model containing slit/cylinder/sphere pores. The estimated pore width around Å and Å should be corresponded to the octahedral and cuboctahedral cages, while the peak below 7.9 Å (tetrahedral cage) is not observed. The pore width around Å can be attributed to the square window of the cuboctahedral cage. A slight increase in the pore width after the linker exchange is due to the removal of bulky functionalities from the pore, while connectivity of the frameworks is not influence by the linker exchange. S-33

34 Figure S30. FT-IR spectra of 10 min, 30 min and 14 h reo-mof-1a. The FT-IR spectrum of 10 min reo-mof-1a sample exhibits the characteristic band of the carboxylate group (C=O) appears at 1649 and 1600 cm 1 (multi-peaks caused by the asymmetry of the SNDC 3 linker) attributed to the significant amount of residue HSNDC 2 /SNDC 3 maintaining inside the material after linkerexchange. In contrast, two unique peaks (1180 and 1649 cm 1 ) assigned to the sulfonate and carboxylate stretching modes of SNDC 3 linker, are absent in the spectrum of 30 min and 14 h reo-mof-1a samples indicating the lesser amount of residue SNDC 3 maintaining inside the materials after linker-exchange. S-34

35 Figure S31. 1 H-NMR spectra of 10-min, 30-min and 14-h reo-mof-1a samples. The ratios of HSNDC 2 /NDC 2 are estimated to be 0.32, 0.14 and 0.07, respectively. S-35

36 Figure S32. GC yield percentage of 2-phenylbenzoxazole as a function of reaction time in the presence of 10 min reo-mof-1a, 30 min reo-mof-1a, and 14 h reo-mof-1a samples. S-36

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