This journal is The Royal Society of Chemistry 212 Silica SOS@HKUST-1 Composite Microspheres as Easily-Packed Stationary Phase for Fast Separation dham hmed, a Mark Forster, a Rob Clowes, a Darren radshaw, b Peter Myers, a and Haifei Zhang a* a Department of Chemistry, University of Liverpool, Oxford Street, Liverpool, L69 7ZD, UK. Email: zhanghf@liv.ac.uk b Department of Chemistry, University of Southampton, Highfield, Southampton, SO17 1J, UK. Supporting Information 1
Intensity This journal is The Royal Society of Chemistry 212 16 12 Cu(NO 3 ) 2 SOS-SH SOS-SH@Cu 2+ SOS-SH@HKUST-1 8 4 1 2 3 4 5 Position [2 o ] Figure S1. PXRD patterns of the SOS-SH particles, as-purchased Cu(NO 3 ) 2, Cu 2+ immobilised on SOS-SH particles, and the SOS-SH@HKUST-1 composite particles. Figure S2. The SEM image showing the poor growth of HKUST-1 on SOS particles without firstly immobilizing Cu 2+. 2
Weight (%) Weight (%) Weight (%) This journal is The Royal Society of Chemistry 212 Figure S3. The SEM images of SOS-COOH@HKUST-1 composite microspheres at different magnifications. 1 1 9 8 9 8 7 7 6 6 5 5 4 4 3 2 4 6 8 1 Temperature ( o C) 3 2 4 6 8 1 Temperature ( o C) 1 9 C 8 7 6 5 4 3 2 4 6 8 1 Temperature ( o C) Figure S4. () TG curve of the HKUST-1 synthesized in the absence of SOS particles. Gradual mass loss until 325 o C (weight 85%), then rapid decomposition until 395 o C (weight 54%), slow mass loss again until weight 39.4% at 8 o C. () TG curve of the SOS- COOH@HKUST-1 particles. Slow mass loss until 32 o C (weight 93%), rapid decomposition until 428 o C (56%), and then gradual loss to 8 o C with weight 42.3%. (C) TG curve of the SOS-COOH particles. Slow mass loss until 24 o C (weight 97.5%), quick mass loss until 33 o C (83.2%), rapid decomposition until 395 o C (58%), and then the weight percentage stable at 39.2% at 8 o C. ecause the decomposition of HKUST-1 and SOS-COOH happened in the overlapping temperature range, it was difficult to calculate the loading of HKUST-1 on SOS particles. 3
Weight% This journal is The Royal Society of Chemistry 212 C D 5 Quantitative results 4 3 2 1 C O Si S Cu E F Figure S5. SOS-COOH@HKUST-1: () The SEM image and the selected area for element analysis; () The element spectrum for the selected area; (C) Mapping of Cu for the selected and larger area, indicating the uniform distribution of HKUST-1 on SOS-COOH particles; (D) The weight ratio of elements calculated by the instrument software. The sample was coated with u. So u was removed for the calculation. SOS-COOH particles: (E) The SEM image and the selected area; (F) The elemental spectrum for the selected area. This sample was coated with u as well. Comparing spectrum () and (F), one can clearly see the presence of Cu, consistent with the observation of HKUST-1 on SOS-COOH particles. 4
This journal is The Royal Society of Chemistry 212 Figure S6. The SEM images at higher magnification showing the HKUST-1 crystalline particles on the SOS-COOH particle surface. () The sample prepared using 25 mmol Cu(NO 3 ) 2 without washing as detailed in method 1. () The sample in () washing once after immobilization of Cu 2+ ions. (C) The sample in () washing twice after immobilization of Cu 2+ ions. 5
This journal is The Royal Society of Chemistry 212 C Figure S7. Synthesis of SOS-NH 2 @HKUST-1 particles with method 1. HKUST-1 was formed on the SOS particles (SEM images & ). ET surface area was 367 m 2 /g. The PXRD pattern (C) shows the formation of pure phase HKUST-1. 6
Intensity This journal is The Royal Society of Chemistry 212.8.6.4.2. 5 1 15 2 25 3 35 4 Wavenumber (cm -1 ) 1 µm Figure S8. () The FTIR spectrum shows strong peaks around 171 cm -1 and 1736 cm -1, demonstrating the successful functionalization of smooth silica spheres with COOH groups. () The SEM shows the morphology of synthesizing HKUST-1 with smooth silica particles via Cu 2+ immobilization and solvothermal synthesis. 7
Intensity This journal is The Royal Society of Chemistry 212 C D 5 45 4 35 3 25 2 15 1 5 1 2 3 4 5 Position (2 / o ) Figure S9. Synthesis of HKUST-1 on SOS-NH 2 particles using the method 2 procedure at room temperature with 3 times repeated synthesis. (-C) SEM images at different magnification and (D) the PXRD pattern. 8
mu This journal is The Royal Society of Chemistry 212 Figure S1. The resulting sample by preparing HKUST-1 film on the SOS-NH 2 particles at 12 o C. 25 2 3 2 15 1 1 5 1 2 3 4 5 6 Time (min) Figure S11. HPLC chromatogram on the SOS-COOH@HKUST-1 packed column for separation of toluene (1), p-xylene (2), and thiophene (3) with a mobile phase of heptane:dcm 8:2 v/v at.35 cm 3 min -1, back pressure 28 bar. 9
mu mu This journal is The Royal Society of Chemistry 212 6 4 16 14 12 1 8 6 4 2 1&2 3 2 1 2 3 Time (min) 1 2 3 4 5 6 Time (min) Figure S12. HPLC chromatograms on the () SOS-COOH particles packed column and () SOS-COOH@HKUST-1 packed column for separation of xylene isomers (injection 1µl, flow rate.35 cm 3 min -1, back pressure 145 bar) at 2 o C using heptane as the mobile phase. 1. m- xylene, 2. p-xylene, 3. o-xylene. 1
mu mu This journal is The Royal Society of Chemistry 212 Figure S13. Separation of xylene isomers with DCM-conditioned SOS-COOH@HKUST-1 column for 2 hours () and 6 hours (). 8 6 4 m-xylene p-xylene o-xylene 1 5 m-xylene p-xylene o-xylene 2 1 2 3 4 5 6 Time (min) 2 4 6 8 1 Time (min) Figure S14. Chromatograms from the individual injections of the test compounds. () The column packed with as-prepared SOS-COOH@HKUST-1 particles. () The column in () conditioned with DCM for 24 hours. 11
Intensity Intensity Intensity This journal is The Royal Society of Chemistry 212 14 12 1 8 6 Soaked in solvent DCM Toluene Soaked in DCM - ambient dried Soaked in DCM - vacuum dried 4 2 35 3 25 2 15 1 5 1 2 3 4 5 6 Soaked in solvent DCM Toluene 1 2 3 4 5 6 Position [2 / o ] Position [2 / o ] C 15 125 1 75 5 25 soaked in DCM- ambient dried soaked in DCM- vacuum dried 1 2 3 4 5 6 Position [2 / o ] Figure S15. Overlay PXRD patterns of soaked and dry SOS-COOH@HKUST-1 particles () showing identical characteristics of crystalline HKUST-1. The PXRD patterns of DCM and toluene soaked SOS-COOH@HKUST-1 () are slightly different with the obvious broad peak around 2θ 18 o arising from amorphous silica in the DCM-soaked materials. The DCMsoaked materials were dried in two ways (placed in a fume cupboard for 1 hour and thoroughly dried under vacuum). It was believed that some DCM was still trapped in the HKUST-1 with the drying in fume cupboard. The fact that the PXRD patterns are identical (C) suggests the trapping of DCM in the micropores of HKUST-1 does not cause the structure change. The solvent-soaked samples were covered with 6 µm Mylar film in transmission spinner for PXRD measurement (scan range 4 6 o, step size.131, scan time 3 minutes). 12
mu mu Pressure (bars) This journal is The Royal Society of Chemistry 212 4 3 2 1 2 4 6 8 1 Time (hours) Figure S16. The change of backpressure for the DCM-conditioned column with the time of running heptane as mobile phase. 4 35 3 25 2 15 1 5 1 4 2 3 1 2 3 4 5 6 7 8 9 1 Time (min) o-xylene p-xylene m-xylene toluene 4 35 3 25 2 15 1 5 1 2 3 4 5 6 7 8 9 1 Time (min) toluene Figure S17. The effect of toluene conditioning on the selectivity of the SOS- COOH@HKUST-1 column for separation of xylene isomers (injection 1µl, flow rate.35 cm 3 min -1 ) at 2 o C using heptane as the mobile phase. () Individual injections of (1) o- xylene, (2) p-xylene, (3) m-xylene, (4) toluene. () UV absorbance is observed for toluene. Toluene eluted as multiple trailing peaks when the column was conditioned with toluene. 13
Quantity dsorbed (cm³/g STP) Intensity This journal is The Royal Society of Chemistry 212 Figure S18. The SEM images at different magnifications ( & ) showing the SOS- COOH@HKUST-1 particles after HPLC testing. The inset in image () shows the packed column after testing. 15 3 1 2 5 1..2.4.6.8 1. Relative Pressure (p/p ) 1 2 3 4 5 Position [2 ] Figure S19. Further characterization data for the SOS-COOH@HKUST-1 particles after HPLC testing. () The isothermal plot of N 2 sorption. () The PXRD pattern. 14