Supporting Information
Experimental
Preparation of MCF.
Sample S1 was prepared according to Lettow1 and Zhao et al.2 2.0 g (0.4 mmol) PEOPPO-PEO triblock copolymer P123 was first dissolved in 75 mL of 1.6 M HCl. 1.85 mL TMB
(TMB:P123 mass ratio 0.8) was added and stirred for 1 h, and then 4.25 g (21 mmol) of TEOS
was added drop-wise as the silica source. This mixture was stirred for 24 hours and maintained at
35-40°C. Following this, the reaction mixture was transferred to a teflon-lined autoclave and
aged for 24 h at 100°C. The solids were collected by filtration and dried in air for at least 24 h,
and the resulting powder was calcined at 500°C for 6 h to produce the mesoporous silica
material.
Preparation of MTS.
As prescribed by Ottaviani et al.,3 the following components were added under stirring in
the following sequence: distilled H2O; CTAB; NaOH; TMB; SiO2 with molar ratio:
20:0.1:0.25:5:1. Following each addition, the mixture was allowed to equilibrate by stirring for 1
min. The final mixture was stirred for 30 min at room temperature and transferred to an
autoclave to heat for 5 h at 70°C. The materials were then filtered, washed with distilled water,
and dried at 115°C. Lastly, the MTS were calcined for 8 h at 550°C to eliminate organic matter.
Preparation of SBA-16.
Our SBA-16 materials were prepared according to Kleitz et al.4 The molar composition
of the reaction mixture was varied in the range of 0.0035 F127/ xTEOS/ yBuOH/ 0.91 HCl/ 117
H2O, with x = 0.5 − 3 and y = 0 − 3 . Specifically, 5.0 g (0.4 mmol) PEO-PPO-PEO triblock
copolymer F127 was dissolved in 240 g distilled water and 10.5 g hydrochloric acid (35 wt %).
After complete dissolution, a) 18.50 mL or b) 12.84 mL of butanol was added at once at 45°C
1
and stirred for 1 h. a) 24.0 g or b) 21.6 g of TEOS was then added. This synthesis was carried out
in a closed flask and then transferred to a polypropylene bottle, where the mixture was aged at
100°C for 24 h under static conditions. The white precipitate was filtered hot and dried at 100°C
for 24 h. To remove the organic template, the materials were briefly washed with EtOH/HCl and
calcined at 550°C for 6 h. a) yielded a pore diameter of 9.0 nm while b) gave a pore diameter of
6.6 nm.
SBA-15 synthesis.
SBA-15 materials were prepared according to Zhao et al.2 In a typical synthesis, 4.0 g of
P123 was dissolved in 150 mL of 1.6 M HCl at 35°C. 8.5 0 g TEOS was added drop-wise and
the mixture was stirred for 24 hours and maintained at 35-40°C. Following this, the reaction
mixture was transferred to a teflon-lined autoclave and aged for 24 h at 100°C. The solids were
collected by filtration and dried in air for at least 24 h, and the resulting powder was calcined at
500°C for 6 h to produce the mesoporous silica material.
2
Table S1: Properties of pure C10H8, 2-C10H7CH3, 2-C10H7OCH3, and 2-C10H7Cl obtained
from DSC curves. Z = molecules per unit cell.
C10H8
2-C10H7CH3
2-10H7OCH3
2-C10H7Cl
a
b
Melting
Temp
∆Hsl
(K)a
(J g-1)a
352.5
147.18
307.8
82.85
346.5
152.60
331.0
85.21
Freezing
Temp
∆Hsl
(K)a
(J g-1)a
339.3
145.80
300.6
83.66
322.8
139.30
326.3
83.03
Crystal Structure Datab
Crystal
Space Group
System
Z
monoclinic
P21/c
2
monoclinic
P21/c
N/A
monoclinic
P21/c
4
monoclinic P21/c (Form II)
4
P21/a (Form I)
2
From DSC thermograms
From references5-9
Table S2: Mass and thickness t, porous volumes and transition enthalpies measured by DSC and N2
sorption for sample C1 in three separate trials.
Trial
1
2
3
avg
mass (mg)
0.45
0.26
0.41
-
t (nm)
0.7
0.6
0.5
0.6
Vp (cm3 g-1)
0.90
1.07
0.90
0.96
3
V N 2 (cm3 g-1)
1.03
1.03
1.03
1.03
∆H (J g-1)
101
76
91
89
a)
b)
Figure S1: Nitrogen adsorption-desorption isotherms of (a) spherical mesopores and (b)
cylindrical mesopores. S1 and S2 are offset by 500 and 300 cm3g-1, respectively, and C1 and C2
are offset by 300 and 110 cm3g-1, respectively.
4
a)
b)
Figure S2: BdB-FHH pore size distributions calculated from adsorption isotherm branches for a)
spherical mesopores and b) cylindrical mesopores.
5
b)
a)
c)
Figure S3: TEM images of a typical cylindrical SBA-15 mesopore from a) side view and b) top
view, and c) a typical spherical MTS mesopore.
b)
a)
c)
d)
Figure S4: DSC curves of pure a) naphthalene, b) 2-methylnaphthalene, c) 2methoxynaphthalene, and d) 2-chloronaphthalene upon heating and cooling.
6
Figure S5: DSC curves of bulk C10H8 and C10H8 confined in cylindrical pores. Confined phase
transitions are indicated by arrows and the transition temperatures are given.
Figure S6: DSC curves recorded for various flushing times for sample C1 filled with C10H8.
7
a)
b)
c)
Figure S7: Evolution of Hc (○) and Hb (□) as a function of the mass of C10H8 present in pore C1 for a)
Trial 1, b) Trial 2, and c) Trial 3.
8
b)
a)
Figure S8: ∆Tm plotted as a function of r
C10H7Cl.
−1
p
c)
for a) 2-C10H7CH3, b) 2-C10H7OCH3, and c) 2-
Figure S9: DSC curves recorded for various flushing times (above) and evolution of Hc (○) and
Hb (□) as a function of the mass of 2-C10H7CH3 present in pore C1 (below).
9
Figure S10: DSC curves recorded for various flushing times (above) and evolution of Hc (○) and
Hb (□) as a function of the mass of 2-C10H7OCH3 present in pore C1 (below).
10
Figure S11: DSC curves recorded for various flushing times (above) and evolution of Hc (○) and
Hb (□) as a function of the mass of 2-C10H7Cl present in pore C1 (below).
11
Figure S12: DSC curves of C10H8, 2-C10H7CH3, 2-C10H7OCH3, and 2-C10H7Cl existing in only
the contact layers.
12
Figure S13: Raman spectra of pure solid C10H7CH3 (PS), liquid C10H8 (PL), C10H8 confined in
pores (80% loading) (PL), and C10H8 coating the pore walls (CL).
13
Figure S14: Raman spectra of pure solid C10H7OCH3 (PS), liquid C10H8 (PL), C10H8 confined in
pores (80% loading) (PL), and C10H8 coating the pore walls (CL).
14
Figure S15: Raman spectra of pure solid C10H7Cl (PS), liquid C10H8 (PL), C10H8 confined in
pores (80% loading) (PL), and C10H8 coating the pore walls (CL).
References
(1) Lettow, J. S.; Han, Y. J.; Schmidt-Winkel, P.; Yang, P.; Zhao, D.; Stucky, G. D.; Ying, J.
Y. Langmuir 2000, 16, 8291-8295.
(2) Zhao, D.; Feng, J.; Huo, Q.; Melosh, N.; Fredrickson, G. H.; Chmelka, B. F.; Stucky, G. D.
Science 1998, 279, 548-552.
(3) Ottaviani, M. F.; Moscatelli, A.; Desplantier-Giscard, D.; Renzo, F. D.; Kooyman, P. J.;
Alonso, B.; Galarneau, A. J. Phys. Chem. B 2004, 108, 12123-12129.
(4) Kleitz, F.; T.-W. Kim, T.-W.; Ryoo, R. Langmuir 2006, 22, 440-445.
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(5) Bolte, M.; Bauch, C. Acta Cryst. C 1998, C54, 1862-1863.
(6) Brock, C. P.; Dunitz, J. D. Acta Crystallogr., Sect.B: Struct. Crystallogr. Cryst. Chem.
1982, 38, 2218-2228.
(7) Chanh, N. B.; Haget, Y.; Bonpunt, L.; Meresse, A.; Housty, J. Anal. Cal. 1977, 4, 233-240.
(8) Chanh, N. B.; Haget, Y.; Meresse, A.; Housty, J. Mol. Cryst. Liq. Cryst. 1978, 45, 307312.
(9) Haget, Y.; Bonpunt, L.; Meresse, A.; Chanh, N. B. Mol. Cryst. Liq. Cryst. 1983, 96, 211214.
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