Electrostatic vs covalent bond in modified Jeffamine: effect on the phase behaviour and on the templating of mesoporous silica

Transcription

1 Eletroni upplementry Mteril (EI) for oft Mtter This journl is The Royl oiety of Chemistry 3 upporting Informtion Eletrostti vs ovlent ond in modified Jeffmine: effet on the phse ehviour nd on the templting of mesoporous sili Ndi Cnilho, Andree Ps *, Mélnie Emo, Mrie-José téé nd Jen-Lu Blin Figure. MALDI TOF spetr of (,) ED9, (,d) mono-oleoyl Jeffmine nd (e,f) di-oleoyl Jeffmine.

2 Eletroni upplementry Mteril (EI) for oft Mtter This journl is The Royl oiety of Chemistry 3 Tle. X-Ry diffrtion dt for 54. wt% of OOJ t in wter t C indexed to the spe group Im3m with lttie prmeter = 7.4 nm hkl (h²+k²+l²) / d os (nm) d l (nm) * I os vvs s s * I os re the oserved intensities, whih re rnged from vvs (extremely strong) to s (strong). Tle. X-Ry diffrtion dt for 43 wt% of OOJ ov-t in wter t C indexed to the spe group Im3m with lttie prmeter = 8.4 nm hkl (h²+k²+l²) / d os (nm) d l (nm) * I os vvs m s * I os re the oserved intensities, whih re rnged from vvs (extremely strong), s (strong) to m (medium).. (). () I (.u.).7.9 I (.u.) Figure. AX diffrtion ptterns otined for () 54.wt% of OOJ t nd () 43 wt% of OOJ ov-t in wter t C. I / φv (.u.) I / φv (.u.) I/Φ v (.u.) 3 wt% OOJ ov 5 wt% OOJ ov wt% OOJ ov, 3 wt% OOJ ov-t 5 wt% OOJ ov-t wt% OOJ ov-t, 5 wt% OOJ ov 5 wt% OOJ ov-t 5 wt% OOJ t, Figure 3. Experimentl AX dt (normlized with regrd to the volume frtion of surftnt) of 3, 5, wt% of OOJ ov () nd OOJ ov-t (). Experimentl nd pproximted (GIFT) AX dt (normlized with regrd to the volume frtion of surftnt) of OOJ ov, OOJ ov-t nd OOJ t t onentrtion of 5 wt% in wter in log-log representtion ().

3 Eletroni upplementry Mteril (EI) for oft Mtter This journl is The Royl oiety of Chemistry 3 Clultion of the struturl prmeters: For the Im3m ui phse, the reltion etween the ell prmeter (= d ) nd the hydrophoi rdius R is determined from: V VB + αv W 4ν πr = () where α stnds for the numer of wter moleules per surftnt moleule, υ is the numer of mielles per ui lttie, (υ = for Im3m phse), V B, V, V W respetively stnd for the molr volumes of the hydrophoi prt of the surftnt, the surftnt nd wter (V W = 8 m³/mol). V B vlues were lulted y onsidering tht the hydrophoi prt onsists in lkne hin nd poly (oxypropylene), PPO units, wheres the hydrophili prt ontins the polyoxyethylene, PEO units. These prmeters hve een lulted nd the vlues re detiled in Tle 4. The ross-setionl re n then e dedued from the following reltion, where N A is the Avogdro's numer: 3 VB = N R A () imilrly, the struturl prmeters of the hexgonl phse were determined from geometril onsidertions. The Brgg distne d of the hexgonl phse n e relted to the hydrophoi rdius R y: VB π 3 = V + αv d W R (3) The ross-setionl re, onsidered s for ui phse, t the polr-nonpolr interfe lying etween PEO nd PPO, n e dedued in the sme wy from the following reltion: V N R B = (4) A Tle 3. Vrition of the struturl prmeters in funtion of α, the numer of wter moleules per surftnt moleule for OOJ ov-t nd OOJ t in the Im3m phse OOJ ov-t OOJ t lph (nm) R (nm) (nm²) Tle 4. Molr volumes of the hydrophoi prt of the surftnt, V B nd of the surftnt V for ll studied systems. (onsidering d EO =.3 g/m 3, d lkyl =.9 g/m 3 nd d PO = g/m 3 ) V B (m³/mol) V (m³/mol) OOJ ov OOJ ov-t OOJ t

4 Eletroni upplementry Mteril (EI) for oft Mtter This journl is The Royl oiety of Chemistry d Brgg,, R (nm), (nm²) 7 5 d Brgg R OOJov T ( C) Figure 4. Vrition of d sping nd struturl prmeters s funtion of the temperture for OOJ ov t wt % in wter. 9 8 d Brgg,, R (nm), (nm²) 7 5 OOJov-t d Brgg R T ( C) Figure 5. Vrition of d sping nd struturl prmeters s funtion of the temperture for OOJ ov-t t 5 wt % in wter. 8 d Brgg,, R (nm), (nm²) 4 d Brgg R OOJ t T( C) Figure. Vrition of d sping nd struturl prmeters s funtion of the temperture for OOJ t t wt % in wter. 4

5 Eletroni upplementry Mteril (EI) for oft Mtter This journl is The Royl oiety of Chemistry 3 I(q) (.u.) d e 3 q (nm) Figure 7. AX pttern evolution of the sili mterils prepred with 5 wt% OOJ ov t different molr rtio (surftnt/tmo) R: ().9, ().4, ()., (d).5, (e).75. All syntheses were performed during 48 h t 5 C nm Adsored volume (m 3 /g-tp) dv/dd (m 3 /g-nm - ) nm 4.5 nm 4.7 nm Reltive pressure (p/p ). 5 Pore dimeter (nm) Figure 8. Nitrogen dsorption/desorption isotherms (left) nd the pore dimeter (right) of sili mterils prepred from OOJ ov t different molr rtio R: ( ).9, ( ).4, ( )., ( ).5, ( ).75. All syntheses were performed during 48h t 5 C. Tle 5. ummry of the speifi re ( BET ) nd porous volume (V p ) vlues of the sili mterils prepred during 48 h t 5 C with 5 wt% OOJ ov t different molr rtio (surftnt/tmo) R R BET V p (m /g) (m 3 /g)

6 Eletroni upplementry Mteril (EI) for oft Mtter This journl is The Royl oiety of Chemistry 3 I(q) (.u.) d q, nm - Figure 9. AX pttern evolution of the sili mterils prepred with OOJ t in different retion onditions of surftnt onentrtion, R rtio nd hydrotherml synthesis temperture: () 5 wt%, R.5, RT, ().5 wt%, R.5, RT, () wt%, R.5, RT, (d) 5 wt%, R., RT in omprison with (e) 5 wt%, R., 5 C. e 5. Adsored Volume (m 3 /g-tp) dv/dd (m 3 /g-nm - ) nm.3 nm 9.4 nm Reltive pressure (p/p ) Pore dimeter (nm) Figure. Nitrogen dsorption/desorption isotherms (left) nd the pore dimeter (right) of the sili mterils prepred with OOJ t in different retion onditions of surftnt onentrtion, R rtio nd hydrotherml synthesis temperture: ( ) 5 wt%, R.5, RT, ( ).5 wt%, R.5, RT, (-) wt%, R.5, RT, ( ) 5 wt%, R., RT, ( ) 5 wt%, R., 5 C. Tle. ummry of the speifi re ( BET ) nd porous volume (V p ) vlues for the OOJ t -sed mesoporous sili mterils. Retion onditions BET V p (m /g) (m 3 /g) 5 wt% OOJ t, R.5, RT wt% OOJ t, R.5, RT wt% OOJ t, R.5, RT wt% OOJ t, R., 5 C wt% OOJ t, R., RT

7 Eletroni upplementry Mteril (EI) for oft Mtter This journl is The Royl oiety of Chemistry 3 I(q) (.u.) d 3 q, nm - Figure. AX pttern evolution of the sili mterils prepred from OOJ ov-t in different retion onditions : () 5wt%, R., 4 C; () 5wt%, R., 5 C; () 5wt%, R., RT; (d) 5wt%, R.3, RT; (e) wt%, R.5, RT; (f) wt%, R.7, RT. e f nm 5. Adsored Volume (m 3 /g-nm - ) 4 3 dv/dd (m 3 /g-nm - ) nm 5. nm. nm.. nm Reltive pressure (p/p ). 5 5 Pore dimeter (nm) Figure. Nitrogen dsorption/desorption isotherms (left) nd the pore dimeter (right) of sili mterils prepred from OOJ ov-t in different retion onditions: ( ) 5wt%, R., 4 C; ( ) 5wt%, R., 5 C; ( ) 5wt%, R., RT; ( ) 5wt%, R.3, RT; (-) wt%, R.5, RT; ( ) wt%, R.3, RT. Tle 7. ummry of the speifi re ( BET ) nd porous volume (V p ) vlues for the OOJ ov-t -sed mesoporous sili mterils. Retion onditions BET V p (m /g) (m 3 /g) 5 wt% OOJ ov-t, R., 4 C wt% OOJ ov-t, R., 5 C.75 5 wt% OOJ ov-t, R., RT wt% OOJ ov-t, R.3, RT 583. wt% OOJ ov-t, R.5, RT 5.47 wt% OOJ ov-t, R.7, RT