129Xe NMR spectroscopy of supported ionic liquids

Supporting information 129Xe NMR spectroscopy of supported ionic liquids Cindy-Ly Tavera-Méndez a, Paola Agüero-Gamboa a, Ziwen Zhai b, György Hantal c, Florian M. Wisser a,d, Ana-Sunčana Smith c,e, Thomas M. Koller b†, Martin Hartmann a,d, Dorothea Wisser a* a Erlangen Center for Interface Research and Catalysis (ECRC), Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Egerlandstraße 3, 91058 Erlangen, Germany. b Institute of Advanced Optical Technologies − Thermophysical Properties (AOT-TP), Department of Chemical and Biological Engineering (CBI) and Erlangen Graduate School in Advanced Optical Technologies (SAOT), Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Paul-Gordan-Straße 8, 91052, Erlangen, Germany. c PULS Group, Institute for Theoretical Physics, Centre for Computational Advanced Materials and Processes, Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), IZNF, Cauerstraße. 4, Erlangen 91058, Germany. d Interdisciplinary Center for Functional Particle Systems (FPS), Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Haberstraße 9a, 91058 Erlangen, Germany. e Group for Computational Life Sciences, Division of Physical Chemistry, Ruđer Bošković Institute, Zagreb, Croatia. * Corresponding author: [email protected], phone: +49 9131 85 27452 Table S1 Used Chemicals Chemical Supplier Purity Application Hydrochloric acid VWR 35.1% SBA-15 synthesis Pluronic 123 MW=5800 Sigma-Aldrich >95% SBA-15 synthesis Tetraethyl orthosilicate Sigma-Aldrich >95% SBA-15 synthesis Methanol Thermo scientific 99.8% SBA-15 synthesis Ethanol VWR 99.5% MCM-41 synthesis Cetyltrimethylammonium bromide BASF 99.5% MCM-41 synthesis Ammonium hydroxide solution Merck 32% MCM-41 synthesis Dichloromethane Sigma-Aldrich >99.8% SILP synthesis 1-Ethyl-3-methylimidazolium acetate Proionic >98% SILP synthesis 1-Ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide Proionic >99.9 % SILP synthesis 1-Ethyl-3-methylimidazoliumchloride Sigma-Aldrich >99% SILP synthesis 2,2-dimethyl-2-silapentane-5-sulfonate sodium (DSS) Sigma-Aldrich >99% 1H, NMR reference Argon 5.0 Linde 99.999% Schlenk line, glovebox Xenon N40 Air Liquide 99.99% 129Xe NMR Table S2. Pressure ramp for dichloromethane removal via rotatory evaporation. Pressure (MPa) Rotation (rpm) Time (min) Bath temperature (K) 9.5x10-2 50 30 313 8.5x10-2 50 30 7.0x10-2 70 30 3.0–5.0x10-4 70 60 Figure S1. High Pressure Xenon NMR set-up modules: 500 MHz 1H-19F/15N-31P PFG switchable broadband Varian probe (a), sapphire NMR tube with an aluminium tube holder (b), and gas manifold for evacuation and controlled dosing of Xenon gas (c). Figure S2. Detailed flow diagram of the High-Pressure Xenon NMR set-up. Table S3 Components of the High-Pressure Xenon NMR set-up Label Description Supplier Reference Nr. GV-1, PM1, PR-1, PM-2 Single stage brass gas regulator, Working pressure 0.4-4 MPa. Linde FDR-200-40-140 NV-1/3 Needle valve serie L (1/4 in.) Swagelok SS-4L NV-4 Integral-bonnet needle valve (1/4 in.) Swagelok SS-1RS4 PM-3 Digital manometer 99.5% MCM-41 synthesis PM-4 Digital manometer LEO1 Keller 303075.0023 QC-1 Quick connect fittings with CoreFlex hose (1/8 in.) Swagelok SS-QC4-D-200, SS-QC4-B-200, SS-BT2TA2TA2-200CM RV-1 Proportional relief valve; Max. Pressure 4.5 MPa Swagelok 129Xe NMR Figure S3. 129Xe zero chemical shift (0) determination Figure S4. Nitrogen adsorption isotherms (a), pore size distribution (PSD) calculated with the BJH model on the desorption branch, SAXS spectra (c) and SEM images (d) of calcined SBA-15 used as SILP support Table S4: Textural properties of synthesized supports. Support SBET (m2 g−1) Vtot (cm3 g−1) Vmic (cm3 g−1) WPSD (nm) SBA-15 855 1.13 0.10 6.8 SBET: BET surface area; Vtot: total pore volume determined at p/p0 = 0.98; Vmic: micropore volume determined by the t-plot method; WPSD: average pore width from the pore size distribution. Figure S5. 129Xe NMR spectra of xenon adsorbed on SBA-15 Figure S6. Xenon dissolved in bulk [C1C2ImH][NTf2] (green) and [C1C2ImH][OAc] (red). Table S5. Mole fractions xXe of Xe in [C2C1ImH][NTf2] and [C2C1ImH][OAc] determined by transient gasabsorption method in this work at temperature T and pressure p.a [C2C1Im][NTf2] + Xe [C2C1Im][OAc] +Xe T / K p / MPa xXe T / K p / MPa xXe 294.20 4.60 0.155 293.77 4.25 0.0591 323.15 4.52 0.122 323.10 4.15 0.0522 a Estimated uncertainties for T, p, and xXe are 0.1 K, 10 kPa, and 10%, respectively. All uncertainties are based on a confidence level of more than 95% (k = 2). Figure S7. Bar diagram for the experimental solubilities xXe of Xe in [C2C1ImH][NTf2] and [C2C1ImH][OAc] determined in this study at p from (4.15 to 4.6) MPa and T of (294 and 323) K. Table S6. Mole fractions xXe of Xe in [C2C1ImH][NTf2] and [C2C1ImH][OAc] determined in our computer simulations at temperatures T = 277 K and 295 K, and pressure p.a [C2C1Im][NTf2] + Xe [C2C1Im][OAc] +Xe T =277 K T = 295 K T = 277 K T = 295 K p / MPa xXe p / MPa xXe p / MPa xXe p / MPa xXe 0.35  0.01 0.050  0.006 0.37  0.01 0.051  0.004 0.35  0.02 0.012  0.001 0.41  0.01 0.015  0.001 0.53  0.02 0.075  0.006 0.64  0.05 0.078  0.003 0.57  0.02 0.013  0.001 0.67  0.02 0.013  0.001 a Estimated uncertainties represent standard errors based on block averaging. Table S7. Linear regression parameters for temperature-dependent 129Xe NMR chemical shifts of the xenon adsorbed on an IL film resonance (Xe@IL) on 15% ionic liquid loading (αIL) [C1C2ImH][OAc]-SILP and [C1C2ImH][NTf2]-SILP.s SILPs Slope / ppm*K-1 Intercept / ppm R2 [C1C2ImH][OAc] series -0.55 196.7 0.9167 [C1C2ImH][NTf2] series -0.56 197.4 0.9766 Figure S8. Temperature-dependent 129Xe NMR chemical shifts of the xenon adsorbed on an IL film resonance (Xe@IL) on 15% ionic liquid loading (αIL) [C1C2ImH][OAc]-SILP (red) and [C1C2ImH][NTf2]- SILP (green). Figure S9. Experimental data (symbols) and virial fit (solid line) for Xe isotherms of SBA-15 (a) and, [C1C2ImH][OAc]-SILP (b) and [C1C2ImH][NTf2]-SILP (c), supported on SBA-15 with an ionic liquid loading (αIL) of 10%, at 263 K, 278 K and 293 K. Table S8. Fitting parameters from virial analysis for xenon isotherms of SBA-15, [C1C2ImH][NTf2]-SILP and [C1C2ImH][OAc]-SILP at 293 K, 278 K and 263 K. Support: SBA-15 IL Loading Isotherm temperatures a0 a1 a2 b0 b1 Reduced 2 R2 H0ads /kJ*mol-1 0% 263 K / 278 K -2411.1 669.1 -104.2 13.15 -1.55 2.9x10-5 0.99998 -20.05 263 K / 293 K -2323.8 603.1 -103.8 12.82 -1.29 6.8x10-5 0.99996 -19.32 278 K / 293K -2237.8 594.5 -118.8 12.52 -1.24 4.2x10-5 0.99995 -18.61 [C1C2ImH][NTf2] supported on SBA-15 IL Loading Isotherm temperatures a0 a1 a2 b0 b1 Reduced 2 R2 H0ads /kJ*mol10% 263 K / 278 K -2751.4 2458.2 -529.1 15.03 -7.15 1.1x10-4 0.99993 -22.88 263 K / 293 K -2641.3 2360.8 -522.8 14.62 -6.79 2.1x10-4 0.99987 -21.96 278 K / 293K -2522.1 2279.6 -524.5 14.21 -6.51 1.3x10-4 0.99992 -20.97 [C1C2ImH][OAc] supported on SBA-15 IL Loading Isotherm temperatures a0 a1 a2 b0 b1 Reduced 2 R2 H0ads /kJ*mol10% 263 K / 278 K -2518.6 1735.4 -314.9 14.18 -5.04 6.1x10-5 0.99996 -20.87 263 K / 293 K -2470.5 1739.8 -321.0 13.99 -5.04 8.3x10-5 0.99995 -20.54 278 K / 293K -2404.9 1632.4 -285.9 13.77 -4.71 9.3x10-5 0.99994 -20.00