LETTERS TO NATURE

Ordered mesoporous molecular 40 torr, 49 wt% n-hexane at 40 torr, and 67 wt% benzene at
50 torr. The pore volume of this sample is 0. 79 cm 3 g -t. The
sieves synthesized by a liquid- range of pore volumes for MCM-41 samples is 0.7-1.2 cm 3 g- 1 .
Figure 3 shows N 2 adsorption isotherms for this material and
crystal template mechanism for an amorphous mesoporous silica. The morphology of MCM-
41 depends on synthesis conditions, but it is possible to obtain
C. T. Kresge*, M. E. Leonowicz*, W. J. Roth*, relatively large ( -2 J.Lm) hexagonal prisms of MCM-41, as seen
in the scanning electron micrograph in Fig. 4.
J. C. Vartuli* & J. S. Beckt
Mobil Research and Development Corporation,
*Paulsboro Research Laboratory, Paulsboro, New Jersey 08066, USA
t Central Research Laboratory, Princeton, New Jersey 08543, USA

MICROPOROUS and mesoporous inorganic solids (with pore

diameters of s.;;20 A and -20-500 A respectively) 1 have found
great utility as catalysts and sorption media because of their large
internal surface area. Typical microporous materials are the crys-
talline framework solids, such as zeolites2 , but the largest pore
dimensions found so far are -10-12 A for some metallophos-
phatesJ--5 and -14 A for the mineral cacoxenite6 • Examples
of mesoporous solids include silicas7 and modified layered
materials8 - 11 , but these are invariably amorphous or paracrystal-
line, with pores that are irregularly spaced and broadly distributed
in size 8•12 • Pore size can be controlled by intercalation of layered
silicates with a surfactant species 9•13 , but the final product retains,
in part, the layered nature of the precursor material. Here we
report the synthesis of mesoporous solids from the calcination
of aluminosilicate gels in the presence of surfactants. The
material 14' 15 possesses regular arrays of uniform channels, the
dimensions of which can be tailored (in the range 16 Ato 100 A
or more) through the choice of surfactant, auxiliary chemicals
and reaction conditions. We propose that the formation of these
materials takes place by means of a liquid-crystal 'templating'
mechanism, in which the silicate material forms inorganic walls
between ordered surfactant micelles.
Members of this family of materials, designated MCM-41,
were first observed in electron micrographs of products from
hydrothermal reactions of aluminosilicate gels in the presence
of quaternary ammonium surfactants. We prepared the MCM-41
molecular sieve characterized here as follows: 200 g of a
solution containing 26 wt% hexadecyltrimethylammonium ion, as
C 16 H 33 (CH 3 ) 3 N+OH/Cl ( -30% hydroxide), was combined with
2 g of Catapal alumina, 100 g of tetramethylammonium silicate
solution (10% Si0 2 , ratio of tetramethylammonium to Si0 2 = 1)
and 25 g of a precipitated silica (HiSil), with stirring (molar
ratio of C 16 H 33 (CH 3 ) 3 N+ to Si ~ 1). This mixture was placed in
a static autoclave at 150 oc for 48 hours. After cooling it to room
temperature, we recovered the solid product by filtration on a
Buchner funnel, washed it with water and dried it in air at
ambient temperature. The as-synthesized product was then cal-
cined at 540 oc for one hour in flowing nitrogen, followed by
six hours in flowing air. The as-synthesized product contains
over 40 wt% of the original surfactant as reflected by its composi-
tion (molar): 1 N, 19.6 C, 4.7 Si, 0.27 AI. In general, no special
precautions (heating rate, atmosphere) are needed during the
temperature ramping (from ambient temperature) and calcina-
tion processes.
Transmission electron microscopy (Fig. 1a) shows the regular
hexagonal array of uniform channels characteristic of MCM-41.
A representative electron diffraction pattern (Fig. 1b), with the
MCM-41 in the same orientation, confirms the periodicity of
the structure. For the sample described above, an interplanar
spacing d 100 =40 A was observed. In the corresponding powder
X-ray diffraction pattern of the bulk sample (Fig. 2), the four
FIG. 1 a, Representative transmission electron micrograph of MCM-41. This
peaks observed in the low-angle 20 region can be indexed on
image was obtained with a JEOL 200CX transmission electron microscope
a hexagonal unit cell with a= 45 A (2d 100 / J3). Generally, both operated at 200 kV from a thin section prepared by ultramicrotomy. The
electron and X-ray diffraction patterns show only a few low- instrument has an interpretable resolution of 4.5 A and an effective 2-A
order members of the hkO subset of hexagonal reflections. The objective aperture was used to enhance image contrast. b, Representative
BET surface area of the preparation is~ 1,000 m 2 g- 1 with excep- electron micrograph of MCM-41. Selected area electron diffraction pattern
tionally high sorption capacities of >50 wt% cyclohexane at indexed as the hkO projection of a hexagonal unit cell with a =45 A.

710 NATURE · VOL 359 · 22 OCTOBER 1992

© 1992 Nature Publishing Group
 LETTERS TO NATURE

0 hkl d(A) BOO

Adsorbed
~
100 39.8 700 De sorbed
110 22.9
200 19.8
600
210 14.9
500

400

300
EL 200
0 f-
t;i (/)
100
I
~ 0>
'ii) 0
c
(lJ
2 4 6 8 "'E 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
.!::'..
c hkl d(A) '0
CD
.0
33.0
N
<')
<')
211
220 28.6 0
(/)
1,200
321 21.7 '0
400 20.3 ctl Adsorbed
420 18.1 CD 1,000 Desorbed
332 17.3 E
=>
16.5
~
422
431 15.9 800

600

400

2 4 6 8 10 200

Degrees 2e
0 ~r::::r:::r::::L::~~
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
FIG. 2 a, Representative X-ray diffraction pattern of MCM-41. The pattern
Relative pressure (p/p0 )
was obtained from a Scintag PAD automated diffraction system using 0-0
geometry, Cu Ka radiation (A =1.5418 A) and an energy-dispersive detector. FIG. 3 a, N2 adsorption isotherm for MCM-41. b, N2 adsorption isotherm for
b, Representative X-ray diffraction pattern of cubic (/a3d) phase. Inset is amorphous silica (BET surface area 306m 2 g- 1 ). These isotherms were
expansion of region 20 = 3-5°. obtained on a Micromeritics Digisorb 2600 adsorption instrument using
standard procedures. The isotherm for this MCM-41 shows the inflection
characteristic of capillary condensation within the pores, where the pi Po
The nature of the ordering in the walls of MCM-41-that is, (relative N2 pressure) position of the inflection point is related to the diameter
the degree to which the atoms are precisely ordered-is not fully of the pore being filled 26 ·27 -40 A. The significant adsorption at lower pi Po
( -200 cm 3 g- 1 ) is most probably due to monolayer coverage of the walls
understood. We have not detected any X-ray diffraction peaks
and not to the presence of microporous phases.
with a non-zero I component. The large, regular pore channels
of these materials would, however, make the hkO reflections
dominate, resulting in little scattering intensity along the c-axis. with the surfactant remaining intact. Another way of altering
The pore diameter of MCM-41 can be varied by changing the pore diameter of MCM-41 is to add auxiliary hydrocarbons,
the alkyl chain length of the cationic surfactants used in such as alkylated benzene (for example 1,3,5-trimethylbenzene),
the synthesis procedure. For example, by substituting to the synthesis mixture 16 • The incremental addition of 1,3,5-
the dodecyltrimethylammonium ion (C 12 H 25 (CH 3 lJN+) for trimethylbenzene results in the concomitant increase of d 100 and
hexadecyltrimethylammonium ion, we produced a sample of the pore diameter. Hexagonal phases with pore diameters up
MCM-41 with 30-A pore diameter. The C/N molar ratio for to -100 A have been characterized.
as-synthesized C 12 -based MCM-41 is 15, which is consistent The microscopy and diffraction results presented above are

FIG. 4 Scanning electron micrograph of a MCM-41

sample. This micrograph was obtained on a JEOL
JXA-840 scanning electron microscope using con-
ventional sample preparation and imaging tech-
niques.

NATURE · VOL 359 · 22 OCTOBER 1992 711

© 1992 Nature Publishing Group
LETTERS TO NATURE
Hexagonal
FIG. 5 Schematic drawing of the liquid-crystal templating array
mechanism. Hexagonal arrays of cylindrical micelles form
(possibly mediated by the presence of silicate ions). with the
polar groups of the surfactants (light grey) to the outside.
Calcination
Silicate species (dark grey) then occupy the spaces between
the cylinders. The final calcination step burns off the original ~
organic material, leaving hollow cylinders of inorganic
material.
MCM-41

strikingly similar (R. M. Dessau and C. D. Chang, personal 5. Estermann. M .. McCusker. L. B.. Baerlocher, C., Merrouche, A. & Kessler, H. Nature 352, 320-323
communication) to those obtained 17 - 19 from lyotropic liquid- 6.
(1991)
Moore. P. B. & Shen. J. Nature 306, 356-358 (1983).
crystal phases which are produced in surfactant-water mixtures. 7. ller, R. K. The Chemistry of Silica (Wiley, New York. 1979)
These phases are ordered arrays of surfactant aggregates which 8. Pinnavara. T. J. Science 220, 365-371 (1983).
9. Landis. M. E. eta/. J Am. chem. Soc. 113, 3189-3190. 1991.
occur at specific amphiphile concentrations 20·21 . One such phase, 10. Vaughan. D. E. W. & Lussier. R. J Proc. 5th int. Conf Zeolites (ed. Rees, L. V. C.) 94-100 (Heyden.
the 'middle' or 'H 1' phase, produces transmission electron micro- London. 1980).

scope images 22 analogous to those of MCM-41. The H 1 phase 11. Vaughan. D. E. W. Am chem Soc. Symp. Series 368, 308-325 (1988).
12. Tindwa, R. M.. Ellis, D. K .. Peng, G. Z. & Clearfield. A. J. chem. Soc. Faraday Trans. 1, 81, 545-548
is a hexagonal array of cylindrical micelles in which the hydro- (1985)
13. Yanagrsawa. T .. Shimizu. T .. Kazuyuki. K. & Kato. C. Bull. Chem. Soc. Jpn 63, 988-992 (1990).
phobic hydrocarbon chains are gathered in the centre and the 14 Kresge. C. T .. Leonowicz. M. E.. Roth. W. J. & Vartuli. J. C. U.S. Patent No. 5.098.684 (1992): U.S.
polar groups are arrayed on the surface, in contact with a Patent No. 5.102.643 (1992)
continuous region of water surrounding the micelles 20 . The 15. Beck. J S. et a/. U.S Patent No. 5.108.725 (1992)
16 Beck. J. S. U.S. Patent No. 5.057. 296 (1991).
repeat dimensions of the MCM-41 prepared as described above 17 Ekwa/1, P. Advances in Liquid Crystals. Vol. 1 (ed. Brown. G. H.) (Academic, New York, 1971).
are consistent with those determined for hexadecyltrimethylam- 18. Ekwall. P.. Mandell. L. & Fontell. K. Liquid Crystals (ed. Brown. G. H.) 325-334 (Gordon and Breach.
London. 1969).
monium-based liquid crystals, where cylinder-to-cylinder repeat 19. Luzzati. V. Biological Membranes (ed. Chapman. D.) 71-123 (Academic. New York. 1968).
distances of -40 A have been observed 20 . 20 Tiddy. G. J. T. Phys. Rep. 57, No. 1. 1-46 (1980)
21. Wrnsor. P. A. Chem. Rev. 68, No. 1. 1-40 (1968).
The observed dependence on alkyl chain length and the 22. Goodman. J. F. & Clunie, J. S. Electron Microscopy of Liquid Crystals. Liquid Crystals and Plastic
influence of auxiliary organic molecules on the resultant inor- Crystals. Vol. 2 (eds Gray. G. W. & Winsor. P. A.) 1-23 (Wiley. New York. 1974).
ganic product are also consistent with two phenomena observed 23. Speght. P. P. A .. Skoulros. A. E. & Luzzati. V. Acta cryst 14, 866-872 "(1961)
24. Komarov. V. S. & Kuznetsova. T. F. Vesti Akad Navuk BSSR No. 2, 22-27 {1978).
for liquid crystals. The diameter of hexagonal liquid-crystal 25. Luzzati. V. & Speght. P. P. A. Nature 215, 701-704. 1967.
phases prepared with anionic surfactants depends on the alkyl 26. Gregg, S. J. & Sing, K. S. W. Adsorption. Surface Area. and Porosity, 2nd Edn {Academic. New

chain length of the surfactant 20 ·21 . Organic species may be York. 1982).
27. Barrett. E. P.. Joyner. L. G. & Halenda. P. P. J Am. chem. Soc. 73, 373-380 (1951).
solubilized inside the hydrophobic regions of micelles, causing
an increase in micelle diameter 21 ' 23 . Chemicals added to surfac- ACKNOWLEDGEMENTS. We thank the technical staff of the Paulsboro and Central Research
Laboratories. Mobil Research and Development Corporation. for discussions. In particular, we thank
tant solutions can increase the porosity of amorphous adsor- C. D. Chang, R. M. Dessau and H. M. Princen for alerting us to references and for discussions. D. T.
bants24. Geston and K. G. Simmons for assistance, J. 8. Higgins and N. H. Goeke for the scanning electron
micrograph, J. L. Schlenker for assistance in X-ray diffraction pattern indexing and Mobil Research
These similarities suggest that these mesoporous molecular and Development Corporation for its support.
sieves are formed by a 'liquid-crystal templating' mechanism.
In this mechanism (Fig. 5), inorganic material occupies the
continuous solvent (water) region to create inorganic walls
between the surfactant cylinders. It may be that encapsulation
occurs because anionic aluminosilicate species enter the solvent Anthropogenic influence on the
region to balance the cationic hydrophilic surfaces of the micel-
les. Alternatively, it may be the introduction of the aluminosili-
distribution of tropospheric
cate species themselves that mediates the hexagonal ordering.
Once an ordered array is established, subsequent thermal pro-
sulphate aerosol
cessing is used to remove the organic material and produce a
J. Langner*, H. Rodhet, P. J. Crutzen:j:
stable mesoporous molecular sieve.
Although other workers 13 have produced mesoporous silicates & P. Zimmermann+
with high surface areas, the mechanism used has been the
intercalation of a guest (such as hexadecyltrimethylammonium *Swedish Meteorological and Hydrological Institute, S-601 76 Norrkiiping,
Sweden
chloride) into a layered host (such as kanemite). The mesopores
t Department of Meteorology, Stockholm University, S-106 91 Stockholm,
of these materials are not an ordered regular array (as observed Sweden
in MCM-41 ). The final product retains, in part, the layered :j: Max-Planck Institute for Chemistry, P.O. Box 3060, D-6500 Mainz,
nature of the kanemite precursor. Furthermore, the concentra- Germany
tions, reagents, pH and reaction conditions are not conducive
for liquid-crystal formation and templating. HUMAN activities have increased global em1sswns of sulphur
Additional strong evidence for the proposed liquid-crystal gases by about a factor of three during the past century, leading
templating mechanism is the discovery of another member of to increased sulphate aerosol concentrations, mainly in the North-
this famili 4' 15 that mimics a liquid-crystal structure 25 . A rep- ern Hemisphere. Sulphate aerosols can affect the climate directly,
resentative powder X-ray diffraction pattern of a silicate by increasing the backscattering of solar radiation in cloud-free
molecular sieve with cubic symmetry (la3d) is given in Fig. 2. air, and indirectly, by providing additional cloud condensation
The cubic phase is prepared by increasing the molar ratio of nuclei 1-4. Here we use a global transport-chemistry model to
C 16 H 33 (CH 3 ) 3 N+ to Si to values greater than one. 0 estimate the changes in the distribution of tropospheric sulphate
aerosol and deposition of non-seasalt sulphur that have occurred
since pre-industrial times. The increase in sulphate aerosol con-
Received 1 May: accepted 1 September 1992. centration is small over the Southern Hemisphere oceans, but
1. IUPAC Manual of Symbols and Terminology Pure appl. Chem. 31, 578 (1972) reaches a factor of 100 over northern Europe in winter. Our
2. Meier. W. M. & Olson. D. H. Atlas of Zeolite Structure Types, 2nd Edn (Butterworths. London, 1988).
3. Davrs. M. E.. Saldarriaga. C.. Montes. C.. Garces. J & Crowder. C. Nature 331, 698-699 (1988).
calculations indicate, however, that at most 6% of the
4 Dessau. R M.. Schlenker. J L. & Higgins. J B. Zeolites 10, 522-524 (1990). anthropogenic sulphur emissions is available for the formation of
712 NATURE · VOL 359 · 22 OCTOBER 1992
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