Electronic Supplementary Material (ESI) for New Journal of Chemistry. This journal is The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2014 Electronic Supplementary information Facile synthesis of Fe 3 O 4 nanoparticles on metal organic framework MIL- 101(Cr): characterization and its catalytic activity Mrinal Saikia a,b, Diganta Bhuyan a and Lakshi Saikia* a,b a Materials Science Division, CSIR-North East Institute of Science and Technology, Jorhat, Assam, India. Fax: +91 0376 2370011; Tel: +91 0376 2370081; E-mail: lakshi_saikia@yahoo.com b Academy of Scientific and Innovative Research, New Delhi, India Table of contents 1. Experimental procedure 2. Figure S1. PXRD pattern of MIL-101(Cr) & Fe 3 O 4 @MIL-101(Cr) 3. Figure S2. TGA curve in argon for MIL-101(Cr) & Fe 3 O 4 @MIL-101(Cr) 4. Figure S3. Field-dependent magnetization of Fe 3 O 4 and Fe 3 O 4 @MIL-101(Cr) 5. Figure S4. FT-IR spectra of Fe 3 O 4 @MIL-101(Cr) 6. Figure S5. Low angle PXRD pattern of recovered catalyst Fe 3 O 4 @MIL-101(Cr) 7. Figure S6. Catalyst recycling tests for Fe 3 O 4 @MIL-101(Cr) 8. Figure S7. XPS spectra of the elements in the Fe 3 O 4 @MIL-101(Cr) 9. Figure S8: TEM of MIL-101(Cr) and (b) TEM of Fe 3 O 4 @MIL-101(Cr) 10. Table S1: Comparison of catalytic activity of Fe 3 O 4 @MIL-101(Cr) with some reference materials 11. Figure S9: Distribution and size of magnetite nanoparticles on MIL-101(Cr) Experimental procedure Chemicals Cr (NO 3 ) 3.9H 2 O, terephthalic acid, FeCl 3, Fecl 2.4H 2 O, Fe 3 O 4 were purchased from Sigma-Aldrich, USA. C 2 H 5 OH, HF, NH 3, DMF were purchased from Merck, Germany. All the chemicals are used without any further purification. Synthesis of MIL-101(C r) MIL-101 was prepared according to the reported method by Férey et al. involving hydrothermal treatment of a mixture of 3mmol of Cr(NO 3 ) 3 9H 2 O, 3mmol of terephthalic acid (H 2 bdc) and 0.6ml of 5M HF (3mmol) in 15ml H 2 O at 220 0 C for 8h in a Teflon-lined autoclave bomb. After equilibration at ambient temperature, the
resulting Cr-MIL-101 solid was filtered to remove the unreacted colourless crystals of H 2 bdc and purified by double treatment with DMF at 60 0 C for 3h and then triple treatment with ethanol at 70 0 C for 2.5h. Finally the green solid was separated by centrifugation, dried in an air oven at 70 0 C overnight and kept it in a vacuum desiccator. Synthesis of Fe 3 O 4 @ MIL-101(Cr) The nanocomposite was synthesized by adding 1mmol of FeCl 2.4H 2 O and 2 mmol FeCl 3 to an aqueous suspension (100ml) containing 0.5g of MIL-101. The suspension was then vigorously stirred and degassed with nitrogen for 1h, followed by addition of NH 3 solution (15ml) to form black suspension. The resulting black solid was filtered off, repeatedly washed with double distilled water until the P H becomes neutral. After air dried the composite was designated as Fe 3 O 4 @MIL-101. The Fe content (20wt %) in the composite has been calculated from ICP-AES technique. General procedure for Fe 3 O 4 @MIL-101 (Cr) catalyzed oxidation reaction of benzyl alcohol 40 mg Fe 3 O 4 @MIL-101 nanocomposite was added to a mixture of 1mmol of benzyl alcohol, 4mmol of tertbutyl hydroperoxide (TBHP, 70%). The reaction mixture was subsequently heated at 70 0 C in a round bottom flask for 12h under solvent free condition. After completion of the reaction the catalyst was separated from the reaction mixture with the help of a magnet. The resulting mixture was analyzed by GC. Characterization Wide angle powder x-ray diffraction (PXRD) was performed on Rigaku, Ultima IV X-ray diffractometer from using Cu-Kα source (λ = 1.54 Å). Low angle PXRD measurement was carried out on Philips X // Pert PRO X-ray diffractometer. Thermal analysis was carried out with TA SDT Q600 machine. Specific surface area, pore volume, average pore diameter were measured with the Autosorb-1 (Quantachrome, USA). Field-emission scanning electron microscopy (FESEM, Hitachi S-4800) was applied to investigate the size and morphology of Intensity (a.u.) (c) Intensity(a.u.) (b) 20 40 60 80 2-Theta (deg) 2 3 4 5 6 7 8 9 10 11 2-Theta (deg) Fig. S1 PXRD patterns of low angle PXRD pattern of MIL-101(Cr), (b) low angle PXRD pattern of Fe 3 O 4 @MIL-101(Cr), (c) wide angle PXRD pattern of Fe 3 O 4 @MIL-101(Cr)
the sample and EDS mapping was done in Oxford XMax 20 equipment. Field dependent magnetization of the samples was measured in ADE MAGNETICS instrument. The Fe content of the composite was determined by Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES) using Perkin Elmer, OPTIMA 2000 instrument. FT- IR spectra (4000 400 cm -1 ) were recorded on KBr discs in a Perkin Elmer system 2000 FT-IR spectrophotometer. The XPS analysis of the samples was carried out on a VG Microtech Multilab ESCA 3000. Weight(%) 100 96 92 88 84 (b) 80 0 100 200 300 400 500 600 700 800 900 Temperature( 0 C) Fig. S2 Thermogravimetric curves of MIL-101(Cr), (b) Fe 3 O 4 @MIL-101 (Cr) Magnetization(emu g -1 ) 800 700 600 500 400 300 200 100 0-100 -200-300 -400-500 -600-700 -800 (b) -15000-10000 -5000 0 5000 10000 15000 Applied field(oe) Fig. S3 Magnetization curve for Fe 3 O 4 @MIL-101 (Cr), (b) Fe 3 O 4
(b) Transmittence(%) 4000 3500 3000 2500 2000 1500 1000 500 Wavenumber(cm -1 ) Fig. S4 FT-IR Spectra of MIL-101(Cr), (b) Fe 3 O 4 @MIL-101(Cr) 4 6 8 10 2 Theta Fig. S5 Low angle PXRD pattern of recovered catalyst. Red, first cycle; blue, second cycle; black, third cycle 100 Conversion Selectivity 90 80 70 60 50 40 30 20 10 0 Fresh Cycle 1 Cycle 2 Cycle 3 No. of Run Fig. S6 Catalyst recycling tests for Fe 3 O 4 @MIL-101
36000 Cr2p 26000 24000 C1s 22000 34000 20000 32000 18000 16000 30000 14000 12000 28000 10000 26000 570 575 580 585 590 595 600 Binding energy(ev) 8000 276 278 280 282 284 286 288 290 292 294 296 298 Binding energy(ev) 70000 O1s 80000 75000 Fe2p 3/2 Fe2p 1/2 60000 70000 50000 65000 40000 60000 55000 30000 50000 45000 20000 40000 10000 522 524 526 528 530 532 534 536 538 540 542 544 Binding energy (ev) 35000 705 710 715 720 725 730 735 740 745 Binding energy (ev) Fig. S7 XPS spectra of elements in Fe 3 O 4 @MIL-101(Cr), Chromium (blue), Carbon (green), Iron (red) and Oxygen (black) (b) (c) Fig. S8: TEM of MIL-101(Cr), (b) Fe 3 O 4 @MIL-101(Cr) and (c) Individual Fe 3 O 4 with SAED pattern
Table S1: a Performance of different catalyst in the oxidation of benzyl alcohol to benzaldehyde in presence of TBHP under solvent free condition Entry Catalyst a Conversion (%) Selectivity (%) 1 Au/CoO x 34.0 85.2 2 Au/CaO 40.8 85.9 3 Au/Fe 2 O 3 29.6 88.7 4 Mg Al HT b 20.2 99.3 5 Mg Fe LDH c 19.4 97.7 6 d Fe 3 O 4 @MIL-101(Cr) 44 98 b HT=hydrotalcite phase c LDH= layered double hydroxides d Present study 50 45 40 35 Distribution(%) 30 25 20 15 10 5 0 3 4 5 6 7 8 9 10 11 Particle Size(nm) Fig. S9: Distribution and size of magnetite nanoparticles on MIL-101(Cr)