10834 J. Am, Chem. Soc.

1992, 114, 10834-10843

obtained from successive Fourier difference maps coupled with isotropic the Organic Division of the American Chemical Society.
least-squares refinement. Hydrogen atoms were modeled in idealized
positions with fixed isotropic thermal parameters. Final Fourier differ- Supplementary Material Available: Tables of data collection
ence maps exhibited no unusual features. A summary of crystal structure parameters, positional and anisotropic thermal parameters for
data is given in Table IV. non-hydrogen atoms, selected interatomic distances and angles,
and idealized atomic parameters for hydrogen atoms for 9,10,
Acknowledgment. Financial support from the National Science and 11 (24 pages); listing of observed and calculated structure
Foundation is gratefully acknowledged. Todd L. Underiner thanks factor amplitudes for 9,10, and 11 (24 pages). Ordering infor-
the Dow Chemical Foundation for a fellowship administered by mation is given on any current masthead page.

A New Family of Mesoporous Molecular Sieves Prepared with

Liquid Crystal Templates
J. S. Beck,*f J. C. Vartuli,*f W. J. Roth,* * M. E. Leonowicz,* * C. T. Kresge,* *
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

K. D. Schmitt/ C. T-W. Chu/ D. H. Olson/ E. W. Sheppard/ S. B. McCullen/

J. B. Higgins/ and J. L. Schlenker+

Contribution from the Mobil Research and Development Corporation, Central Research
Downloaded via UNIV OF READING on July 14, 2018 at 21:20:43 (UTC).

Laboratory, Princeton, New Jersey 08543, and Paulsboro Research Laboratory, Paulsboro,
New Jersey 08066. Received June 30, 1992

Abstract: The synthesis, characterization, and proposed mechanism of formation of a new family of silicate/aluminosilicate
mesoporous molecular sieves designated as M41S is described. MCM-41, one member of this family, exhibits a hexagonal
arrangement of uniform mesopores whose dimensions may be engineered in the range of ~ 15 A to greater than 100 A. Other
members of this family, including a material exhibiting cubic symmetry, have been synthesized. The larger pore M41S materials
typically have surface areas above 700 m2/g and hydrocarbon sorption capacities of 0.7 cc/g and greater. A templating mechanism
(liquid crystal templating—LCT) in which surfactant liquid crystal structures serve as organic templates is proposed for the
formation of these materials. In support of this templating mechanism, it was demonstrated that the structure and pore dimensions
of MCM-41 materials are intimately linked to the properties of the surfactant, including surfactant chain length and solution
chemistry. The presence of variable pore size MCM-41, cubic material, and other phases indicates that M41S is an extensive
family of materials.

Introduction a hexagonal array of uniform mesopores. MCM-41 has been

Two classes of materials that are used extensively as heterog- synthesized with uniform channels varying from approximately
enous catalysts and adsorption media are microporous (pore di- 15 A to greater than 100 A in size. The larger pore materials
ameters <~20 A) and mesoporous (~ 20-500 A) inorganic typically have surface areas above 700 m2/g and hydrocarbon
solids.1 11The utility of these materials is manifested in their
microstructures which allow molecules access to large internal
surfaces and cavities that enhance catalytic activity and adsorptive (1) IUPAC Manual of Symbols and Terminology, Appendix 2, Part 1,
capacity. A major subclass of the microporous materials is mo- Colloid and Surface Chemistry, Pure Appl. Chem. 1972, 31, 578.
lecular sieves. These materials are exemplified by the large family (2) See, for example: (a) Meier, W. M.; Olson, D. H. Atlas of Zeolite
Structure Types, 3rd. ed. revised; Butterworth-Heineman & Co.: Guildford,
of aluminosilicates known as zeolites in which the micropores are 1992. (b) Szostak, R. Molecular Sieves Principles of Synthesis and Iden-
regular arrays of uniformly-sized channels.2 Considerable syn- tification', Van Nostrand Reinhold: New York, 1989.
thetic effort has been devoted to developing frameworks with pore (3) Dessau, R. M.; Schlenker, J. L.; Higgins, J. B. Zeolites 1990, 10,
diameters within the mesoporous range, the largest synthesized 522-524.
to date being AlP04-8/ VPI-5,4 and cloverite5 which have pore (4) Davis, M. E.; Saldarriaga, C.; Montes, C.; Garces, J.; Crowder, C.
Nature 1988, 331, 698-699.
diameters within the 8-13 A range. Cacoxenite, a natural fer- (5) Estermann, M.; McCusker, L. B.; Baerlocher, C.; Merrouche, A.;
roaluminophosphate, has been structurally characterized as having Kessler, H. Nature 1991, 352, 320-323.
~14 A channels that approach the mesoporous size range.6 (6) Moore, P. B.; Shen, J. Nature 1983, 306, 356-358.
(7) Iler, R. K. The Chemistry of Silica', J. Wiley & Sons, Inc.: 1979.
Mesoporous materials are typically amorphous or paracrystalline (8) Wefers, K.; Misra, C. Oxides and Hydroxides of Aluminum', Alcoa
solids, such as silicas7 or transitional aluminas8 or modified layered Technical Paper No. 19, Revised, Alcoa Laboratories, 1987.
materials such as pillared clays and silicates.9-13 The pores in (9) Pinnavaia, T. J. Science 1983, 220, 365-371.
these materials are generally irregularly spaced and broadly (10) (a) Vaughan, D. E. W.; Lussier, R. J. In Proceedings of the 5th
International Conference on Zeolites', Rees, L. V. C., Ed.; Hyden, 1980; pp
distributed in size.10 Despite these efforts, mesoporous molecular 94-100. (b) Meier, W. M. In Studies in Surface Science & Catalysis',
sieves with regular, well-defined channel systems have remained Murakami, Y., Iijima, A., Ward, J. W., Eds.; Elsevier Science: 1986; Vol.
elusive. 28, p 13.
Recently, a new family of mesoporous molecular sieves desig- (11) Vaughan, D. E. W. ACS Symp. Ser. 1988, 368, 308-325.
nated as M41S has been discovered.14 MCM-41, one of the (12) (a) Landis, M. E.; Aufdembrink, B. A.; Chu, P.; Johnson, I. D.;
Kirker, G. W.; Rubin, M. K. J. Am. Chem. Soc. 1991,113, 3189-3190. (b)
members of this extensive family of mesoporous sieves, possesses Yanagisawa, T.; Shimizu, T.; Kazuyuki, K.; Kato, C. Bull. Chem. Soc. Japan
1990, 63, 988-992.
*
Mobil Research and Development Corporation, Central Research Labo- (13) Tindwa, R. M.; Ellis, D. K.; Peng, G. Z.; Clearfield, A. J. Chem. Soc.,
ratory. Faraday Trans. 1 1985, 81, 545-548.
'Mobil Research and Development Corporation, Paulsboro Research (14) Kresge, C. T.; Leonowicz, M. E.; Roth, W. J.; Vartuli, J. C.; Beck,
Laboratory. J. S. Nature 1992, 359, 710-12.

0002-7863/92/1514-10834S03.00/0 &copy; 1992 American Chemical Society

A New Family of Mesoporous Molecular Sieves J. Am. Chem. Soc., Vol. 114, No. 27, 1992 10835

sorption capacities of 0.7 cc/g and greater. Other members of Table I. Preparation of Surfactant Solutions
this family, including a cubic phase and other less well defined
surfactant cation
phases, have been identified. C„H2fl+1(CH3)3N+
A liquid crystal templating mechanism (LCT) in which sur- n = surfactant" (g) water* (g)
factant liquid crystal structures serve as organic templates has
8 11.60 34.80
been proposed for the formation of these materials.14 Related
9 12.25 36.75
mechanisms have been proposed for a number of systems in which 10 12.89 38.67
inorganic structures of widely varying morphologies are deposited 12 14.18 42.54
in the presence of preformed micellar arrays or micellar structures, 14 15.47 46.43
as, for example, in the biochemical formation of bones and shells15 16 16.77 50.23
from 40 different materials. However, in the biological system, 0
Each surfactant quantity represents 0.05 mol of surfactant; surfac-
the deposition of inorganic species is dynamically controlled, and *
tant/silica mole ratio = 0.5. Water was adjusted to make each sur-
products are dense structures whose ultimate morphology does factant 25 wt % in water.
not mimic the vesicle structures per se but mimics the biologically
controlled “shape” of the vesicle array. Steigerwald16 has used
termine the pore diameters of the products with pore diameters up to
reverse micellar systems of Aerosol OT to form HgSe, CdSe, and
about 60 A. In the pore regime above 60 A in diameter, the Kelvin
CdTe particles. The proposed mechanism involved crystallization
equation was applied.19
of the inorganic materials within the isolated micelles dispersed Temperature programmed amine desorption (TPAD) data were ob-
in hydrocarbon. Isolated micelles led to discrete particles. tained on a DuPont series 9000/951 thermal analyzer under He with
Herein we describe the synthesis, physical properties, and automatic titration of evolved base with sulfamic acid.20
proposed mechanism of formation of M41S materials. Solid-state C-NMR spectra were obtained on a 200 MHz JEOL/
Tecmag spectrometer, and solution C-NMR spectra were obtained either
Experimental Section on a 360 MHz Chemagnetics NMR or a 60 MHz JEOL/Tecmag in-
Materials. Silica sources were sodium silicate, N brand, 27.8% silica, strument. Si-NMR spectra were obtained in 9.5 mm zirconia rotors at
P.Q. Corp.; HiSil, Pittsburgh Plate Glass; UltraSil, North American 39.64 MHz spinning 4-4.2 KHz using 90° pulses at 1200-s intervals with
Silica Co.; tetramethylammonium silicate (0.5 TMA/Si02, 10% wt sil- high-power proton decoupling. Between 36 and 72 pulses (12-24 h) gave
ica), SACHEM, Inc.; and tetraethyl orthosilicate, Aldrich. The qua- high quality spectra. Usually MAS Si-NMR of trimethylsilylated ma-
ternary ammonium surfactant compounds (C„H2lt+|(CH3)3NX, X = Cl terials is obtained using cross polarization (CP) techniques to enhance
or Br) were obtained from Armak Chemicals, Kodak, Akzo Chemical, sensitivity. CP is nonquantitative, and thus, single pulse excitation was
and American Tokyo Kasei. The C|6H33(CH3)3N0H/C1 solution was used. Approximately 1200 s between pulses were needed for complete
prepared by batch exchange of a 29% by weight aqueous C16H33(C- relaxation of the Q4 silicons of MCM-41. This is midway between the
H3)3NC1 solution with IRA-400(OH) exchange resin, Rohm and Haas. hours to days needed for dense phases such as quartz and the 1-5 min
The effective exchange of hydroxide for chloride ion was ~30%. A for zeolites. The Q4 relaxation time for MCM-41 is very similar to that
C12H25(CH3)3N0H/C1 solution was prepared by batch exchange of a of both amorphous silicas and crystalline SAPOs. Air was used as the
50% by weight C|2H25(CH3)3NC1 solution (14% aqueous/36% isopropyl drive gas to obtain as much benefit as possible from 02 paramagnetic
alcohol) in a similar matter. Sources of aluminum were sodium alu- relaxation.21 DSS (sodium 2,2-dimethyl-2-silapentane-5-sulfonate) and
minate (technical grade), EM Science; aluminum sulfate, George Caine TMS (tetramethylsilane) were used as shift standards for solution and
Chemical Company; and Catapal alumina, Condea. Trimethylsilyl solid-state experiments, respectively.
chloride [(CH3)3SiCl] and hexamethyldisiloxane [((CH3)3Si)20] were Synthesis. Examples of typical preparations of the MCM-41 materials
obtained from Aldrich. Sulfuric acid (96.1%) was obtained from J. T. are listed below. The number in parentheses in the material designation,
Baker Chemical Company. All chemicals were used as received. e.g. (40), indicates the X-ray powder diffraction d-spacing, of the calcined
Instrumentation. X-ray powder diffraction data were obtained on material, in angstroms (A) of the first diffraction line (rounded to the
either a Scintag XDS 2000 diffractometer using Cu Ka radiation and nearest even A unit). This nomenclature is used because MCM-41
an energy dispersive detector or on the X7A beamline at Brookhaven materials can be prepared in a wide range of pore sizes, yet having
National Synchrotron Light Source. High resolution transmission elec- essentially the same structure. We have rounded the d-spacing to the
tron microscopy (TEM) images and electron diffraction patterns were nearest even A unit.
obtained on a JEOL 200 CX or a JEOL 2010 transmission electron A. Synthesis of MCM-41 (40) Using C16H33(CH3)3NOH/Ci. Two
microscope operated at 200 kV. Samples were examined either as mi- hundred grams of the C16H33(CH3)3N0H/C1 solution were combined
crotomed sections or as grain mounts. Images from thin sections and thin with 2 g of Catapal alumina, 100 g of tetramethylammonium silicate
grain edges were recorded under various focus conditions. Diffraction solution, and 25 g of HiSil with stirring. This mixture was placed in a
information from M41S materials is limited to relatively large d-spacings, static autoclave at 150 °C for 48 h. After cooling to room temperature,
and the diffracted intensities are much weaker than the unscattered the resulting solid product was recovered by filtration on a Buchner
beam. Images show contrast reversal upon going through Gaussian focus, funnel, washed with water, and dried in air at ambient temperature. The
as expected from the appearance of the electron diffraction pattern. X-ray diffraction pattern of the as-synthesized material exhibited a high
Furthermore, no reversal in image contrast is observed at large under- intensity peak having a d-spacing of 43 A and several lower angle peaks
focus conditions. These characteristics suggest that a weak phase object having d-spacings consistent with hexagonal indexing of hkO reflections.
approximation is reasonable for the interpretation of these images. Ac- The as-synthesized product was then calcined at 540 °C for h in flowing
1

cording to this interpretation, the light areas in the images correspond nitrogen, followed by 6 h in flowing air. X-ray diffraction revealed a high
to a lack of scattering matter (pores), and the dark areas are concen- intensity first peak having a d-spacing of 40 A (representing a lattice
trations of scattering material (walls). Scanning electron microscopy contraction after calcination of about 3 A) and several lower angle peaks
(SEM) was performed on a JEOL JXA-840 Scanning Electron Micro- having d-spacings with retention of the hexagonal hkO indexing (Figure
scope using conventional sample preparation and imaging techniques. 1). The lattice contraction for MCM-41 materials varied depending on
Benzene sorption data were obtained on a computer-controlled 990/ synthesis conditions. This calcined material is designated MCM-41(40).
951 DuPont TGA system. The calcined sample was dehydrated by Found in the as-synthesized product (wt %): C, 35.4; N, 2.08; Al, 1.08;
heating at 350 or 500 °C to constant weight in flowing He. Benzene Si, 19.83; Ash (1000 °C), 46.9%. Found in the calcined product (wt %):
sorption isotherms were measured at 25 °C by blending a benzene sat- C, <0.5; N, <0.09; Al, 2.59; Si, 39.85; Ash (1000 °C), 92.3%.
urated He gas stream with a pure He gas stream in the proper propor- B. Synthesis of Siliceous MCM-41 (<40 A). Forty grams of water,
tions to obtain the desired benzene partial pressure. Argon physisorption 18.7 g of N-brand (sodium silicate, 28.7% silica), and 1.2 g of sulfuric
measurements were conducted on a physisorption apparatus as previously acid were combined with stirring. After allowing the resulting mixture
described.17 The method of Horvath and Kawazoe18 was used to de- to stir for 10 min, the appropriate surfactant (C„H2„+1(CH3)3NBr, n =
8, 9, 10, 12, 14, 16) template solution was added (see Table I), and the

(15) Heuer, A. H.; Fink, D. J.; Laraia, V. J.; Arias, J. L.; Calvert, P. D.;
Kendall, K.; Messing, G. L.; Blackwell, J.; Rieke, P. C.; Thompson, D. H.; (19) Gregg, S. J.; Sing, K. S. W. Adsorption, Surface Area, and Porosity,
Wheeler, A. P.; Veis, A.; Caplan, A. I. Science 1992, 255, 1098-1105. 2nd ed.; Academic Press, Inc.: 1982.
(16) Steigerwald, M. L. J. Am. Chem. Soc. 1988, 110, 3046-3050. (20) Kerr, G. T.; Chester, A. W. Thermochim. Acta 1971, 3, 113-124.
(17) Borghard, W. S.; Sheppard, E. W.; Schoennagel, H. J. Rev. Sci. (21) (a) Cookson, D. J.; Smith, B. E. J. Magn. Reson. 1985, 63, 217-218.
Instrum. 1991, 62, 2801-2809. (b) Klinowski, J.; Carpenter, T. A.; Thomas, J. M. J. Chem. Soc., Chem.
(18) HorvSth, G.; Kawazoe, K. J. Chem. Eng. Jpn. 1983, 16, 470-475. Commun. 1986, 956-958.
10836 /. Am. Chem. Soc., Vol. 114, No. 27, 1992 Beck et al.

Table II. Amount of Mesitylene (MES) Added To Synthesize the

Desired Pore Size MCM-41 as Determined by Argon Physisorption
Ar pore size 40 45 50 65
amt of MES added (g) 0 6 9 22

resulting gel was allowed to stir for 0.5 h. (In order to make a direct
comparison between surfactants, each reaction was carried out at
equivalent surfactant/silica mole ratio (0.5) and each surfactant was
added as a 25 wt % aqueous solution.) Twenty grams of water were then
added to the gel. The gels were heated at 100 °C for 144 h. The
resulting solid products were recovered and processed to a calcined form
using the method described above.
C. Synthesis of Aluminosilicate MCM-41 (<40 A). For the
C,2HjS(CH3)3N+ Directed Preparation. Sodium aluminate (8.3 g) was
added slowly to a solution containing 184 g of a C12H25(CH3)3N0H/C1
solution diluted with 480 g of water. Fifty grams of Ultrasil silica, 200
g of a tetramethylammonium silicate solution, and 26.4 g of a tetra-
methylammonium hydroxide solution (25 wt %) were then added with
stirring. This combined mixture was then loaded into an autoclave and
heated with stirring at 100 °C for 24 h. The resulting solid product was is consistent with the characterization data.
recovered and processed to a calcined form using the method described Characteristics of Hexagonal Phase MCM-41. The trans-
above.
mission electron micrographs in Figure 2 show the regular, hex-
For the Ci4H2»(CH3)3N+ Directed Preparation. Sodium aluminate
(4.2 g) was added slowly to a solution containing 16 g of C14H29- agonal array of uniform channels for various MCM-41 (n) ma-
terials with pore sizes from 20 to about 100 A. The number in
(CH3)3NBR in 100 g of water. One hundred grams of tetramethyl-
ammonium silicate solution, 25 g of HiSil silica, and 14.2 g of a tetra- parentheses in the material designation, e.g. (40), indicates the
methylammonium hydroxide solution (25 wt %) were then added with X-ray powder diffraction d-spacing, of the calcined material, in
stirring. This combined mixture was then loaded into an autoclave and angstroms (A), of the first diffraction line rounded to the nearest
heated with stirring at 100 °C for 24 h. The resulting solid product was even A unit. The transmission electron micrograph of preparation
recovered and processed to a calcined form using the method described A, described above, is represented in Figure 2b. The MCM-41
above.
preparations with pore sizes greater than 40 A were synthesized
For the C16H33(CH3)3N+ Directed Preparation. Two hundred grams
of the C|SH33(CH3)3NOH/CI solution were combined with 4.2 g of using reaction mixtures with added auxiliary organics (see below).
sodium aluminate, 100 g of a tetramethylammonium silicate solution, and
The hexagonal structure, with each pore surrounded by six
25 g of HiSil. This mixture was placed in an autoclave with stirring at neighbors, is present in all samples. The most regular hexagonal
120 °C for 24 h. The resulting solid products were recovered and pro- arrangement of uniform pores is usually observed for the smaller
cessed to a calcined form as described above. pore size materials (<40 A), which were produced in the absence
D. Synthesis of MCM-41 Materials (>40 A) Prepared with the of any auxiliary organic, with regularity decreasing as the pore
Auxiliary Organic Mesitylene. Eighty grams of the C16H33- size increases.
(CH3)3N0H/C1 were combined with 1.65 g of sodium aluminate. Forty Synchrotron X-ray powder diffraction data for a sample of
grams of a tetramethylammonium silicate solution and 10 g of HiSil were MCM-41 (40) are shown in Figure 1. The observation of 3-5
then added. While the gel was stirred at room temperature, the auxiliary
peaks which can be indexed on a hexagonal lattice is typical of
organic mesitylene (MES) was added as the last ingredient (the quantity MCM-41 materials.
of MES added ranged from 0-22 g, corresponding to a MES/Si02 mole
ratio of 0-2.5). See Table II for the amount of MES added to produce The BET surface area of the MCM-41 (40) (preparation A)
the desired pore size MCM-41. The gel was then loaded into an auto- was 1040 m2/g with exceptionally high sorption capacities (by
clave and heated to 105 °C with stirring. After 4 h of heating, the weight, 49% n-hexane at 40 Torr (at 21 °C) and 67% benzene
reaction was quenched with cold water, and the contents were removed. at 50 Torr (at 25 °C)). Figure 3 shows the benzene sorption
The resulting solid products were recovered and processed to a calcined isotherm of this material, along with an isotherm for zeolite Y,
form as described above. and of an amorphous silica for comparison. The isotherm for the
Trimethylsilylation of MCM-41. In a typical experiment, 0.50 g of mesoporous molecular sieve exhibits a sharp inflection charac-
MCM-41(40), 10 g (CH3)3SiCl (TMSC1), and 15 g of ((CH3)3Si)20 teristic of capillary condensation within uniform pores, where the
(HMDS) were refluxed overnight with magnetic stirring under N2. The
volatiles were stripped on a rotary evaporator, and the dry powder was p/po position of the inflection point is related to the diameter of
washed 2 or 3 times with 10 mL of reagent grade acetone with centri- the pore.1819 Argon physisorption data both confirm the uni-
fuging. Material recovery was typically >98%. formity and indicate the pore size (~40 A) of this MCM-41 (40)
sample. Figure 4 illustrates the Horvath-Kawazoe plot of the
Results argon physisorption for the MCM-41 (40) sample indicating a
The M41S materials described herein may be synthesized from narrow pore size distribution (width at half height = 4 A) similar
a variety of silica sources and can be prepared in either silicate to those of molecular sieves and unlike those of amorphous ma-
or aluminosilicate forms. As illustrated in the examples above, terials.
these materials may be prepared over a broad time/temperature Surfactant Chain Length Variation in the Synthesis of MCM-41.
regime. The as-synthesized M41S products are easily isolated When quaternary ammonium surfactants (C„H2n+1(CH3)3N+)
from hydrothermal syntheses by filtration and water washing. with different alkyl chain lengths (n = 8,9,10,12,14, 16) were
These materials typically contain large amounts of surfactant after used, MCM-41 materials exhibiting different XRD spacings were
thorough water washing. Carbon to nitrogen atomic ratios of the obtained. The effect of surfactant chain length on MCM-41
as-synthesized materials are consistent with the surfactant re- products on both the location of the first X-ray diffraction lines
maining intact throughout the synthesis. This observation will (<fI00) of the calcined products (siliceous and aluminosilicate) and
be discussed further in the NMR results. The final silicate and approximate pore size as determined by argon physisorption is
aluminosilicate, mesoporous materials are obtained by calcination illustrated in Table III. The approximate pore size calculated
in N2 and air. The nature of the surfactant, including its carbon by argon physisorption should be less than the repeat distance (oq)
chain length, aqueous concentration, the surfactant/silicon mole as determined by X-ray diffraction (hexagonal a0 = 2dl00/V3)
ratio, and reaction conditions are all critical factors in determining because the repeat distance includes the pore wall. This difference
the nature of the product. between these two determinations gives an indication of the pore
Characterization data for the M41S family of mesoporous wall thickness. Variations in this wall thickness depending on the
molecular sieves are discussed below. MCM-41 has been the surfactant chain length system may be a result of the synthetic
species most investigated. We propose a synthesis mechanism that conditions. However, these variations are most likely due to the
A New Family of Mesoporous Molecular Sieves J. Am. Chem. Soc., Vol. 114. No. 27. 1992 10837

Table III.Effect of Surfactant Chain Length on MCM-41 Pore

Size, XRD dl00 Peak Location, Hexagonal Unit Cell Parameter. a0,
and Benzene Uptake
surfactant total benzene
chain length XRD 4,„„ uptake
C„H^,(CH3)3N+ Ar pore (wt %)
n =
d-spacing
(A) (t size (A) at 50 Torr

Siliceous Products
8 27 31 18 16
9 28 32 21 37
10 29 33 22 32
12 29 33 22 36
14 33 38 30 54
16 35 40 37 64

Aluminosilicate Products
12 31 36 43
14 34 39 34 40
Figure 3. Benzene adsorption isotherms of MCM-41(40), zeolite Y, and 16 39 45 38 61
amorphous silica at 25 °C. "a0 =
2<f|O0/v'3.
precision of the pore size calculation. Nevertheless, the data
indicate that MCM-41 pore diameter generally increases with prepared with a MES/C|6H33(CH3)3N+ ratio of 2.0. (See Table
surfactant chain length under comparable reaction conditions. II for synthetic data.)
This suggestion is supported by the benzene sorption data of the Figure 7 shows the benzene sorption isotherms for the several
siliceous products (Figure 5) which generally show a shift in the materials prepared with the auxiliary organic. All show the large
capillary condensation point to higher benzene partial pressure sorption capacity characteristic of MCM-41. The isotherms show
for materials prepared with increasing surfactant chain length. a gradual shift in capillary condensation to higher benzene pressure
This shift is indicative of the filling of larger pores. Furthermore, with increasing mesitylene content. The material formed with
the total benzene uptake was generally found to increase with the highest MES/C,6H33(CH3)3N+ ratio, 1.5, shows only the very
surfactant chain length. beginnings of capillary condensation at the highest benzene
Addition of Auxiliary Organics to MCM-41 Synthesis Mixtures. pressure examined (60 Torr, p/p0 = 0.6). However, argon iso-
The typical MCM-41 reaction mixture was also modified by the therms clearly show capillary condensation for these larger pore
addition of an auxiliary organic, mesitylene (MES) (synthesis D). size materials. Both pore size and pore volume increase with
The molar ratio of MES to C!6H33(CH3)3N+ in this study ranged increasing d100.
from 0 to 2.5. Incremental addition of MES resulted in a pro- Larger pore materials were prepared from modified reaction
portional increase in d-spacing of the X-ray dm peak. This mixtures having MES/C16H33(CH3)3N+ ratios greater than 3.
increase was accompanied by retention of the hexagonal rela- Additional water and longer reaction times were used in these
tionship with the X-ray diffraction pattern of each material ex- preparations. The products display X-ray powder diffraction
hibiting 3-4 peaks related by hexagonal symmetry. As shown patterns exhibiting a single broad line in the extreme low angle
in Figure 6, a plot of MES/C|6H33(CH3)3N+ mole ratio versus region (28 < 1°) or sometimes only enhanced intensity in the
both dl00 and pore size, as determined by argon physisorption, extreme low angle region because our instruments cannot measure
results in a linear correlation within this range of reactant ratios. reliably diffraction below 10 28. However, TEM examination
Figure 2c is a transmission electron micrograph of the material shows that these materials are MCM-41 with a range of d[00
10838 J. Am. Chem. Soc., Vol. 114. No. 27. 1992 Beck et al.

4
Sorption
Arbitrary
Units 3

10 20 30 40 50

Pore Diameter, A
Figure 4. Horvath-Kawazoe pore size distributions for MCM-41 (40), zeolite Y, and amorphous silica.

Figure 7. Benzene adsorption isotherms of MCM-41 materials prepared

Figure 5. Benzene adsorption isotherms for siliceous MCM-41 materials with addition of mesitylene auxiliary organic (X = OH/C1).
prepared with varying surfactant chain length (n 8, 9, 10, 12, 14, and
=

16, X =
Br).
75 -
75

70“ d-spacing 70

65- r 55

< eo^j
”
50
?
Ti S 50”
O
7 55

7 50
o
O
5 7 45

I 40
40-j
O pore size ;
35-' 7 35

30- 30
"i—i—i—|—iiii—| i i i I ] i i—i—r—|—r
0.5 1 1.5 2 2.5 Temperature (°C)
Moles of Meeltylene/Motee of Surfactant
Figure 8. Thermal gravimetric analysis (solid) and temperature pro-
Figure 6. Powder X-ray diffraction </100 spacing and Horvdth-Kawazoe grammed amine desorption (dashed) of an as-synthesized MCM-41 (40)
pore size as a function of mesitylene/surfactant molar ratio. made using Ci6H33(CH3)3N+ and containing 2.8% Al. The heating rate
was 20 °C/min.
between 85 and 120 A (for example, Figure 2d illustrates a
material with ca. 100 A pores). These materials display somewhat uniform, controllable sized mesopores.
irregular, yet essentially hexagonal, pore arrangements. In Tbermogravimetric Analysis. Temperature programmed amine
agreement with these results, argon physisorption derivative uptake desorption analysis, TP AD, of as-synthesized aluminum containing
curves are significantly broader for these larger pore materials MCM-41 (40) was carried out from room temperature to 900 °C
indicating a wider pore size distribution. It is, thus, apparent that under flowing He with titration of the evolved base.20 The dif-
MCM-41(nA) materials comprise an extensive family having ferential weight loss and base evolution curves are shown as Figure
A New Family of Mesoporous Molecular Sieves J. Am. Chem. Soc., Vol. 114, No. 27, 1992 10839

80.0 60.0 40.0 20.0 0.0

" "
i" ...........
-80.0 -100.0
it,
l
n ',
,|,'''
-120.0
i'',
-140.0
i '',

ppm
ppm
Figure 10. Comparative 71.53 MHz magic angle spinning Si-NMR
Figure 9. Single pulse (lower) and cross polarization (upper) 50.18 MHz
spectra of siliceous samples of amorphous silica (upper), MCM-41 (40)
magic angle spinning, H-l decoupled, C-NMR spectra of an MCM-41 -

(middle), and zeolite-Y (lower). Samples were calcined at 500 °C under

(40) synthesized with C16H33(CH3)3N+. The spectral width was 10 kHz,
the spinning rate was 4.25 kHz, and the decoupler field 50 kHz. The flowing N2 before obtaining the spectra which were obtained spinning
at 5.000 kHz, using 90-deg pulses at 300-s intervals.
cross polarization spectrum was obtained using 432 1-ms single contacts
at 1-s intervals. The single pulse spectrum was obtained using 888 90-deg
choice of CP conditions. Figure 10 illustrates the Si-NMR of
pulses at 3-s intervals with gated high power decoupling.
siliceous MCM-41, amorphous silica, and zeolite Y for comparison.
8. At least two peaksare observed in these scans. The maxima Quantitative analysis was not possible since the peaks were broad
for weight loss and (CH3)3N evolution do not exactly correspond and overlapping and could only be resolved using nonquantitative
suggesting decomposition and desorption are not simultaneous. CP techniques. However, deconvolution of the CP-MAS Si-NMR
If the weight loss maxima are assigned to “low”-temperature and of calcined and uncalcined MCM-41 suggested about 20 ± 10%
“high”-temperature changes, the molecular weight of the decom- and 40 ± 20% of the silicon atoms, respectively, were silanols (Q3),
posing species is calculated to be 312 g/mol for the low-tem- similar to the results for amorphous silicas before and after heating
perature and 339 g/mol for the high-temperature species. This to 500 °C.23
is reasonably close to the sum of the molecular weights (283 Trimethylsilylation of MCM-41. Silanol silylation via reaction
g/mol) expected for decomposition of C16H33(CH3)3N+ to hex- with chlorotrimethylsilane has been reported for a number of
adecene (224 g/mol) and trimethylamine (59 g/mol). silanol containing materials including amorphous silica,24 kenyaite,
The bimodal amine desorption probably results from the as- and magadiite.25,26 For amorphous silica, 20-40% of the silicon
sociation of C16H33(CH3)3N+ with siloxy groups and Bronsted atoms are silanols, but only about 9% of the silicon atoms (50-25%
sites, the latter from the aluminum. The siloxy groups are stronger of the silanols) appear to be accessible for silylation. For kenyaite
bases (silanols are weaker acids) and should promote Hoffmann and magadiite all of the 16-20% silanols can be derivatized (the
elimination at lower temperature. If this is the case, the low- silanol peaks are well resolved in these materials so the initial
temperature peak corresponds to about 14% of the silicons being silanol concentration can be determined from Si-NMR on the
silanols, similar to the 14.6% found after calcination by tri- untreated material). Silicon atoms in a trimethylsilyl (TMS)
methylsilylation (see below). The high-temperature peak, if as- moiety show peaks at ~12 ppm in the Si-NMR. After tri-
sociated with aluminum, would correspond to 2.8% Al, which is methylsilylation a Q3 silanol is converted to a silicon atom sur-
in excellent agreement with the 2.9% Al reported in the elemental rounded by four other silicons (Q4), and thus takes on the typical
analysis of the sample. shift of -100 to -120 ppm and often is indistinguishable from Q4
NMR Studies of MCM-41. Solid-state C-NMR spectra of silicon atoms. In terms of stoichiometry, the TMS silicon atom
several as-synthesized MCM-41 materials were obtained. Intact concentration is equal to the original silanol concentration, so its
C16H33(CH3)3N+ was identified by comparison of the peaks ob- peak area relative to the total of Q4 silicons after derivatization
tained with those found for C16H33(CH3)3N+ in solution. Typical is the percent of silanol silicon atoms or at least the percent
spectra are shown in Figure 9. The spectra are striking for the converted.
sharpness of the peaks. The organic cross-polarizes very poorly, There is reasonable agreement between the concentration of
and normal, single pulse experiments give very good spectra. The silanols found in the trimethylsilylated material, as determined
hydrocarbon ends of the C16H33(CH3)3N+ are so mobile that they by Si-NMR, and the amount of C16H33(CH3)3N+ from TP AD.
show essentially no intensity in the CP spectra. The sharpness This suggests the silanols may be present primarily as charge
of the peaks alone might be due to ordering in the solid, but the balancing siloxy similar to the silanols in ZSM-5 at Si/Al2 > 40
cross-polarization behavior is more likely the result of molecular (with tetrapropylammonium bromide as template27).
mobility of the type associated with surfactants in micellar arrays.
The fact that the polar ends of the surfactant molecules can be
cross polarized shows that the surfactant is not present as a (23) Sindorf, D. W.; Maciel, G. E. J. Am. Chem. Soc. 1983, 105,
1487-1493.
“solution” species, again consistent with the presence of a micellar (24) (a) Sindorf, D. W.; Maciel, G. E. J. Phys. Chem. 1982, 86,
array. 5208-5214. (b) Sindorf, D. W.; Maciel, G. E. J. Phys. Chem. 1983, 87,
Si-NMR spectra of MCM-41 closely resemble those of 5516-5521. (c) Sindorf, D. W.; Maciel, G. E. J. Am. Chem. Soc. 1983,105,
3767-3776.
amorphous silica22 suggesting a broad range of Si-O-Si (T-O-T) (25) (a) Yanagisawa, T.; Kuroda, K.; Kato, C. Reactivity Solids 1988, 5,
bond angles in this material. In both cases the spectra can be 167-175. (b) Yanagisawa, T.; Kuroda, K.; Kato, C. Bull. Chem. Soc. Jpn.
separated into three very broad peaks (MCM-41: -92.4, -101.7, 1989, 61, 3743-3745.
-110.5; amorphous silica: -90.6, -99.8, -109.3) by appropriate (26) (a) Rojo, J. M.; Sanz, J.; Ruiz-Hitzy, E.; Serratosa, J. M. Z. Anorg.
Allg. Chem. 1986, 540/541, 227-233. (b) Ruiz-Hitzky, E.; Rojo, J. M.
Nature 1980, 287, 28-30.
(22) Maciel, G. E.; Sindorf, D. W. J. Am. Chem. Soc. 1980, 102, (27) Dessau, R. M.; Schmitt, K. D.; Kerr, G. T.; Woolery, G. L.; Alemany,
7606-7607. L. B. J. Catal. 1987, 104, 484-486.
10840 J. Am. Chem. Soc., Vol. 114, No. 27, 1992 Beck et al.

reflections (the cylindrical shell model has only hkO reflections)

have calculated relative intensities less than 1% of the strong 100
reflections. Based on these results, as well as additional model
studies and theoretical calculations, we conclude that diffraction
intensities from any model with a hexagonal array of large cyl-
indrical pores with relatively thin pore walls will exhibit a similar
pattern. Thus, for these materials, diffraction intensities are of
limited use in determining the structural nature of the pore walls.
Additional insight into the nature of the pore walls may be
obtained from the 29Si-NMR data. The very broad MAS 29Si-
NMR resonance (Figure 10) indicates a broad range of T-O-T
angles in the pore walls32 as indicated above. This is consistent
with a framework that lacks precise repeats of Si positions at the
second nearest neighbor (T-T) length scale.
Microscopy. Microscopy reveals that the particle morphology
of MCM-41 materials is variable, but it is possible to obtain
discrete hexagonally shaped particles. (These materials were
Figure 11. HorvSth-Kawazoe pore size distribution for MCM-41 (40)
and silylated version. prepared with the dodecyltrimethylammonium cation.) Figure
12 (parts a and b) illustrate smaller particles with distinct hex-
agonal morphology (0.05-0.2 qm) which were imaged at higher
Table IV. Comparison of Experimental MCM-41 Relative X-ray
Intensities with Calculated Intensities for Framework and Cylindrical magnifications. These smaller hexagonal particles were relatively
Shell Wall Models easy to find, although they did not constitute the majority of
particles observed in this size range. In each of these images,
exptl framework cylindrical hexagonal arrays of micropores are evident, and rows of pores are
hkl MCM-41 data wall model" shell model
parallel to the hexagonal particle edges. In one such preparation,
100 100 100 100 these particles are large enough, over 2 pm in diameter, for the
110 1.8 11 2
hexagonal morphology to be easily observed in the SEM (Figure
200 1.6 10 4
210 0.2 7 1
12c). These large hexagonal particles exhibit a range of surface
textures from smooth through pitted. Although these large
300 b 1 <1
220 b 1 <1 particles are too thick for electron beam penetration in the TEM,
310 b 2 <1 we have observed fringes and pore structure around thin edges

"81 (7) is chosen because its a0 cell parameter is closest to that ob- (Figure 12d). Large areas of hexagonal pore packing are easily
tained from the MCM-41 (40) preparation.28 6 Not observed. imaged in thin areas of these particles.

Figure 11 shows the HorvSth-Kawazoe transformed argon (32) (a) Tossell, J. A. Phys. Chem. Minerals 1984, 137-141. (b) Magi,
physisorption results on the trimethylsilylated TMS-MCM-41 and M. ; Lippmaa, E.; Samoson, A.; Engelhardt, G.; Grimmer, A.-R. J. Phys.
its calcined parent. The pore diameter decreases from 39.4 to Chem. 1984, 88, 1518-1522. (c) Newsam, j. M. J. Phys. Chem. 1987, 91,
1259-1262. (d) James, N.; Oldfield, E. J. Am. Chem. Soc. 1985, 107,
30.4 A upon conversion of the silanols to TMS groups. The 4.5 6769-6775. (e) Sherriff, B. L.; Grundy, H. D. Nature 1988, 332, 819-821.
A decrease in radius is consistent with that predicted for re- (33) Harris, R. K.; Knight, C. T. G. J. Mol. Struct. 1982, 78, 273-278.
placement of each silanol proton by a TMS group based on CPK (34) See, for example: (a) Luzzati, V. In Biological Membranes; Chap-
models.28 man, D., Ed.; Academic Press, Inc.: 1968; p 71. (b) Ekwall, P. In Advances
in Liquid Crystals; Brown, G. H., Ed.; Academic Press, Inc.: 1971; p 1. (c)
Diffraction Studies of MCM-41. The exact structural nature Ekwall, P.; Mandell, L.; Fontell, K. In Liquid Crystals; Brown, G. H., Ed.;
of the silicate/aluminosilicate framework in the pore walls of these Gordon and Breach Ltd.: 1969; p 325. (d) Winsor, P. A. Chem. Rev. 1968,
materials is uncertain. The presence of distinct hkO reflections 68, 1-40.
in the X-ray diffraction data suggests a framework with long range (35) Chang, C. D.; Bell, A. T. Catal. Lett. 1991, 8, 305-316.
(36) (a) Kerr, G. T. J. Phys. Chem. 1966, 70, 1047-1050. (b) Circ, J. J.
regularity. The hkO reflections can be indexed on a hexagonal Colloid Interfac. Sci. 1968, 28, 315-324. (c) Ueda, S.; Koizumi, M. Am.
lattice, but the observation of only hkO reflections in the exper- Mineral. 1979, 64, 172-179. (d) Guth, J. L.; Caullet, P.; Jacques, P.; Wey,
imental diffraction data (Figure 1) is unusual for material ordered R. Bull. Soc. Chim. 1980, 3-4 (part 1), 121-126. (e) Ueda, S.; Kageyama,
in three dimensions. N. ; Koiszumi, M. In International Conference on Zeolites, 6th, Reno; Olson,
D. H., Bisio, A., Eds.; Guilford: Amsterdam, 1984; pp 905-924, and refer-
It is obvious from the TEM data (Figure 2b) that concentrations ences therein, (f) Davis, M. E.; Lobo, R. F. Chem. Mater. 1992, 4, 756-768.
of scattering matter occur at about 40 A intervals along [100] (37) Barrer, R. M. In ACS Symposium Series 398, Zeolite Synthesis;
in MCM-41 (40) (preparation A). X-ray powder patterns were Occelli, M. L., Robson, H. E., Eds.; American Chemical Society: Washington,
calculated from several models for comparison with the experi- DC, 1989; pp 11-27.
mental data. We first considered zeolite framework models based (38) (a) Van Santen, R. A.; Keijsper, J. J.; Ooms, G.; Kortbeek, A. G. T.
G. Stud. Surf. Sci. Catal. 1986, 28, 169-175. (b) Groenen, E. J. J.; Kortbeek,
on the 81(n) series29 and on a series related to the NNFF models A. G. T. G.; Mackay, M.; Sudmeijer, O. Zeolites 1986, 6, 403-411. (c) Van
proposed by Barrer and Villager.30 Both these models are based den Berg, J. P.; De Jong-Versloot, P. C.; Keijsper, J. J.; Post, M. F. M. In
on a hexagonal three-dimensional tetrahedral framework. At the Studies in Surface Science & Catalysis; Grobet, P. J., Mortier, W. J., Van-
sant, E. F., Schuiz-Ekloff, G., Eds.; Elsevier Science: 1983; Vol. 37, pp 85-95.
opposite extreme, diffraction data from a pore model wherein the (d) Keijsper, J. J.; Post, M. F. M. In ACS Symposium Series 398, Zeolite
walls contained a continuous distribution of scattering matter were Synthesis; Occelli, M. L., Robson, H. E., Eds.; American Chemical Society:
calculated for a hexagonal array of cylindrical shells based on Washington, DC, 1989; pp 28-47.
equations derived by Oster and Riley.31 The results of two of (39) Tiddy, G. J. T. Phys. Rep. 1980, 57, 1-46.
these calculations were compared with experimental MCM-41 (40) Speght, P. P. A.; Skoulios, A. E.; Luzzati, V. Acta Crystallogr. 1961,
14, 866-872.
X-ray data as illustrated in Table IV. (41) Komarov, V. S.; Kuznetsova, T. F. Vestsi Akad. Navuk BSSR 1978,
An interesting result of these model calculations is the quali- 2, 22-27.
tative similarity in the diffraction intensities from different models. (42) (a) Freude, D.; Hunger, M.; Pfeifer, H.: Schwieger, W. Chem. Phys.
Lett. 1986,128, 62-66. (b) Chester, A. W.; Chu, Y. F.; Dessau, R. M.; Kerr,
Both models exhibit strong 100 reflections and several low-order G. T.; Kresge, C. T. J. Chem. Soc., Chem. Commun. 1985, 289-290. (c)
weak hkO reflections (Table IV). All higher order hkO and hkl Hunger, M.; Freude, D.; Frohlich, T.; Pfeifer, H.; Schwieger, W. Zeolites
1987, 7, 108-110. (d) Engelhardt, G.; Jerschkewitz, H.-G.; Lohse, U.; Sarv,
P.; Samoson, A.; Lippmaa, E. Zeolites 1987, 7, 289-292. (e) Brunner, E.;
(28) CPK is a registered trademark of Harvard Apparatus, Inc. Ernst, H.; Freude, D.; Hunger, M.; Pfeifer, H. In Studies in Surface Science
(29) Smith, J. V.; Dytrych, W. J. Nature 1984, 309, 607-608. & Catalysis; Grobet, P. J., Mortier, W. J., Vansant, E. F., Schuiz-Ekloff, G.,
(30) Barrer, R. M.; Villager, H. Z. Kristallogr. 1969, 128, 352-370. Eds.; Elsevier Science: 1988; Vol. 37, pp 155-165. (f) Hunger, M.; Freude,
(31) Oster, G.; Riley, D. P. Acta Crystallogr. 1952, 5, 272-276. D.; Pfeifer, H.; Schwieger, W. Chem. Phys. Lett. 1990, 167, 21—24.
A New Family of Mesoporous Molecular Sieves J. Am. Chem. Soc.. Vol. 114. No. 27. 1992 10841

Figure 12. Transmission electron micrographs (a, b. and d) and scanning electron micrograph (c) of MCM-41.

Surfactant/Silicon Ratio Studies—Isolation of Other Phases. M41S materials.14 The LCT mechanism exploits the continuous
In addition to the isolation of the hexagonal MCM-41 class, other solvent (water) region to create inorganic walls between the
materials with different geometries were synthesized. Some of surfactant liquid crystal structure. It may be that encapsulation
these were prepared by varying the surfactant to silicon mole ratio. occurs because anionic inorganic species enter the solvent region
At a C]fH])(CHj))N*/Si ratio of less than 1, the predominant to balance the cationic hydrophilic surfaces of the micelles.
product appears to be the hexagonal phase. MCM-41. As the Alternatively, perhaps it is the introduction of the inorganic species
Cl6H3}(CH])3N''ySi ratio increases beyond 1, a cubic phase can themselves that mediates the liquid crystal ordering. M41S
be produced. The diffraction data of the cubic phase are consistent formation differs from that of normal zeolite crystallization
with space group laid (see Figure 13a). As the C|6H33- principally in its timing. One model for zeolite crystallization
(CH3)3N+/Si ratio increases further another material is formed proposes silicate condensation about a template molecule or ion.
which exhibited fairly well defined XRD patterns in the as-syn- The initial ordered species may be an aggregate of water mole-
thesized form but, upon calcination, lost all XRD pattern defi- cules35 or silicate moieties.3* Subsequent growth may arise because
nition. The XRD patterns of these as-synthesized products of nucleation by this initial structure37 or assembly of a number
characteristically display multiple peaks that are higher orders of such substructures38 but growth is the consequence of the initial
of the first peak, as illustrated in Figure 13b, suggesting a lamellar silicate organization. In the LCT mechanism, we propose that
type material. At Ci6H33(CH3)3N+/Si ratios approaching 2, a silicate condensation is not the dominant factor in the formation
non M41S phase, the organic octamer, identifieid from its Si- of the structure. We suggest that the structure is defined by the
NMR, is formed [(C|6H33(CH3)3N)SiC>2 5]g.33 The cubic phase organization of the surfactant molecules into micellar liquid
and other less well defined phases that are observed indicate the crystals which serve as templates for the formation of the MCM-41
extensive M41S family of mesoporous molecular sieves. structure. For this reason, the types of materials which may be
Discussion formed are certainly not limited to silicates, nor must these ma-
The M41S materials described herein are the initial members terials necessarily have regularly repeating secondary building units
of a new family of mesoporous molecular sieves. They exhibit (SBUs) in the pore walls in order to form the regularly repeating
a periodic pore system. The pore size of at least one member, porous networks observed.
MCM-41, can be varied from ~ 18 to over 100 A in a continuous, We do not mean to imply, however, that the aqueous silicate
controllable manner. species are irrelevant to the formation of M41S. The liquid crystal
The microscopy and diffraction results presented for MCM-41 structures which form in surfactant solutions are highly sensitive
are strikingly similar to those obtained34 from surfactant/water to solution conditions. Ionic strength, counterion polarizability,
liquid crystal or micellar phases. This leads us to propose a “liquid surfactant concentration, counterion charge, temperature, and the
crystal templating” (LCT) mechanism for the formation of the addition of co-surfactants or additives like alcohols or hydrocarbons
10842 J. Am. Chem. Soc.. Vol. 114. No. 27. 1992 Beck et al.

surfactant micelles into rods. These structures are known to exist

in a hexagonal arrangement in solution.39 Inorganic silicate present
in the reaction mixtures could then form around these arrays to
produce an inorganic structure, reflecting the hexagonal micellar
array (pathway 1 of Figure 14). Figure 14 also illustrates another
possible mechanistic pathway in which the silicate influences the
formation of this liquid crystal phase (reaction pathway 2). In
either case, the resultant silicate encased hexagonal structure
produces the desired MCM-41 material. The carbon chain length
of the surfactant plays a role in determining the dimensions of
C„H,^h(CH3)3N+ micelles34 and, as we have shown, in the di-
mensions of the pores of MCM-41.
Liquid crystal phases are capable of solubilization of organic
molecules within their hydrophobic interiors.34 The hexagonal
2 4 6 8 10 phase of ethylbenzene/sodium myristate/water containing no
silicate, for example, can be swollen in proportion to the amount
of solubilized ethylbenzene.40 The effect of adding solubilizates
to surfactant solutions to increase the porosity of amorphous
alumina adsorbents has been reported.41 Our aluminosilicate
containing hexagonal systems, MCM-41, also show pore diameters
which increase in proportion to the amount of mesitylene added
to the synthesis mixture, but only if the mesitylene is added at
an early stage of the gelation process. This strongly suggests that
the liquid crystal structure is the defining structure.
The formation of the cubic phase by changing the surfactant
to silicate ratio also supports the liquid crystal templating
mechanism, since this variation in reactant composition changes
both the surfactant concentration and the ionic strength, either
of which can induce liquid crystal phase changes.34 The existence
of a lamellar phase would also be consistent with liquid crystal
phase transitions.
The presence and distribution of silanol groups in MCM-41
Degrees 2-theta materials shown by MAS Si-NMR and derivatization is also
Figure 13. Powder X-ray diffraction patterns of (a) calcined cubic ma- consistent with the proposed mechanism. Silanols are present in
terial and (b) the as-synthesized unstable lamellar material. amorphous silicas at a level which depends on calcination tem-
are all factors known to shift surfactant solutions from micellar perature.24 Silanols are often present in zeolites either as random
to any of a number of liquid crystalline phases. “Silica" itself is defects or charge balancing siloxy groups 42 In siliceous MCM-41
a complex system of molecular and polymeric anionic species materials, silanols can be expected to be present as charge bal-
whose composition and concentration can be expected to exercise ancing groups associated with the quaternary ammonium ions with
a spacing which, at least roughly, approximates the spacing of
control over the liquid crystalline phase which forms and is sub-
the surfactant molecules in the micelles.
sequently trapped by silicate condensation. Therefore, we propose
two possible pathways. One in which the liquid crystal phase is
Conclusion
intact before the silicate species are added and two in which the
addition of the silicate results in the ordering of the subsequent M41S represents a new family of mesoporous molecular sieve
silicate encased surfactant micelles. However, in either case, the materials. MCM-41, the hexagonal phase, is characterized as
resultant composition (surfactant/silicate) produces an inorganic having a uniform and controllable pore size from ~-15 to greater
material that mimics known liquid crystal phases. than 100 A, high surface area, and high hydrocarbon sorption
The liquid crystal mechanism of M41S formation suggests that capacity. These molecular sieves are formed by a mechanism in
the as-synthesized materials will have the micellar structures which surfactant liquid crystal phases are believed to serve as
included intact. As-synthesized MCM-41 materials contain templates. In support of this templating mechanism, the structure
surfactant molecules most likely still arranged in a micellar array. and pore dimensions of MCM-41 materials are intimately linked
In fact, MCM-41 materials do form with the pores containing to the properties of the surfactant, such as surfactant chain length,
surfactant and C-NMR indicates this phase is quite similar to solution chemistry and micellar solubilization of trimethylbenzene.
liquid crystalline phases. The existence of other phases, including a cubic phase, supports
The experimental data for the formation of the hexagonal this LCT mechanism and indicates that M41S is an extensive
MCM-41 are consistent with the aggregation of C^lirfl(CH])3N+ family of materials.

Hexagonal
Array

V._k_^
Figure 14. Possible mechanistic pathways for the formation of MCM-41: (1) liquid crystal phase initiated and (2) silicate anion initiated.
 J. Am. Chem. Soc. 1992, 114, 10843-10854 10843

Acknowledgment. The authors are grateful to the staff at both Pearson for their expert technical assistance. We also thank Mobil
Central and Paulsboro Research Laboratories for their invaluable Research and Development Corporation for its support. Part of
discussions and effort. In particular, we acknowledge C. D. Chang, the X-ray diffraction work was conducted on the X7A beamline
R. M. Dessau, and H. M. Princen for alerting us to references at the National Synchrotron Light Source which is supported by
in the surfactant literature and for helpful discussions on surfactant the U.S. Department of Energy, Divisions of Materials Sciences
liquid crystal phases. We thank C. Martin, S. L. Laney, K. G. and Chemical Sciences. We appreciate the assistance of D. E.
Simmons, D. T. Geston, N. H. Goeke, W. W. Solberg, and J. A. Cox at the X7A beamline.

Synthesis and Comparative Reactivity and Electronic

Structural Features of [MFe3S4]z+ Cubane-Type Clusters (M
=
Fe, Co, Ni)
Jian Zhou/ Michael J. Scott/ Zhengguo Hu/ Gang Peng/ E. Miinck,* 1§
and
R. H. Holm*f
Contribution from the Departments of Chemistry, Harvard University,
Cambridge, Massachusetts 02138, and Carnegie Mellon University, Pittsburgh,
Pennsylvania 15213. Received July 2, 1992. Revised Manuscript Received August 27, 1992

Abstract: The heterometal cubane-type clusters [CoFe3S4(Smes)4]2' (7, 80%) and [NiFe3S4(PPh3)(Smes)3]2~ (12, 57-71%)
have been prepared in good yield as Et4N+ salts by reductive rearrangement reactions of the linear cluster [Fe3S4(Smes)4]3
4"

(4, Smes = mesitylthiolate(l-)) with Co(I) and Ni(0) reactants, respectively. (Et4N)2[7] crystallizes in orthorhombic space
group Pbcn with a = 20.673 (3) k,b= 16.600 (3) A, c = 17.259 (2) A, and Z = 4. (Et4N)2[NiFe3S4(PPh3)(Smes)3]-2MeCN
was obtained in triclinic space group Pi with a = 13.138 (3) A, b = 15.461 (4) A, c = 19.622 (4) A, a = 107.12 (2)°, /3 =
94.54 (2)°, y = 108.47 (2)°, and Z = 2. The crystal structures confirm the cubane-type structures and tetrahedral coordination
at the M = Fe, Co, and Ni subsites of the [MFe3S4]2+ cores. In 7, the Co and Fe subsites are disordered and in 12 the phosphine
ligand is bound to the Ni subsite. The clusters [NiFe3S4(Smes)4]3" (10) and [Fe4S4(Smes)4]2" (6) were obtained as an ca.
1:1 mixture by the reaction of Ni(AsPh3)4 and 4. Potential and actual synthetic routes to [MFe3S4]2+ clusters are outlined.
The species 6, 7, 10 form a comparative set with equivalent structures and identical terminal ligands. These species and 12
are best distinguished by their 'H NMR spectra which manifest contact-shifted resonances that are oppositely signed for substituents
at the Fe and M = Co/Ni subsites. In 7, the Fe subsites appear to be more reactive to ligand substitution by thiol than is
the Co subsite; both subsites are substituted in the ligand redistribution system 5/7. The three-member electron transfer series
[CoFe3S4]3+/2+/1+ and [NiFe3S4]2+/1+/0 have been established. For the reversible couples [MFe3S4(Smes)4]2_/3~ the order of
potentials is M = Fe < Co (0.18 V) < Ni (0.30 V), with the indicated potential differences vs M Fe. Mossbauer spectroscopy
=

reveals that 7 and the protein-bound [CoFe3S4]2+ cluster of D. gigas ferredoxin II have equivalent electronic structures at
4.2 K. As judged by isomer shifts at 1.5 K, the [NiFe3S4]1+ core of polycrystalline 12 contains three equivalent iron sites.
However, the 4.2 K Mossbauer spectra obtained in strong applied magnetic fields show clearly that the three sites are magnetically
distinct. Interestingly, the room temperature solution 'H NMR data of 7 and 12 indicate equivalent sites. Isomer shifts imply
the fragment formulations Co2+ (5 = 3/2) + [Fe3S4]° (S = 2) and Ni2+ (S = 1) + [Fe3S4]‘~ (S = 5/2), with antiparallel spin
coupling affording the observed S = ‘/2 and 3/2 ground states, respectively. Comparison of the isomer shifts of the [NiFe3S4]1+
core with those of other [MFe3S4]1+ cubanes (M = Fe, Zn, Cd) suggests a shifted electron density from the [Fe3S4]'" fragment
to the nickel site. The close correspondence of Mossbauer and EPR parameters of synthetic clusters (7, 12) with those of
protein [CoFe3S4]2+ and [NiFe3S4]l+ clusters indicates that the latter contain the tightly bound cubane-type structures established
by X-ray diffraction for the synthetic species.

Introduction demands of three Fe3+ sites render the sulfur atoms insufficiently
The protein-bound cluster Fe3S4(S-Cys)3 is now recognized, on basic to bind divalent ions of the first transition series. Binding
the basis of its characteristic EPR, Mossbauer, and MCD spec-
troscopic properties, to occur in a relatively large number of (1) (a) Beinert, H.; Thomson, A. J. Arch. Biochem. Biophys. 1983, 222,
iron-sulfur proteins and enzymes.1,2 Its cuboidal structure 1, 333. (b) Beinert, H.; Kennedy, M. C. Eur. J. Biochem. 1989, 186, 5. (c)
Beinert, H. FASEB J. 1990, 4, 2483. (d) Cammack, R. Adv. Inorg. Chem.
illustrated in Table I, has been demonstrated by X-ray analysis 1992, 38, 281.
of three proteins.3'5 While the biological function (if any) of this (2) Holm, R. H. Adv. Inorg. Chem. 1992, 38, 1.
cluster remains obscure, it possesses at least two properties of (3) Robbins, A. H.; Stout, C. D. Proc. Nall. Acad. Sci. U.S.A. 1989, 86,
current significance in the field of metal clusters in biology. One 3639; Proteins 1989, 5, 289.
(4) Stout, C. D. J. Biol. Chem. 1988, 263, 9256; J. Mol. Biol. 1989, 205,
of these involves reactivity and the second electronic structure. 545.
Trinuclear cluster 1, when in the [Fe3S4]0,1" core oxidation (5) (a) Kissinger, C. R.; Adman, E. T.; Sieker, L. C.; Jensen, L. H. J. Am.
states, has a binding affinity for certain divalent metal ions that Chem. Soc. 1988, 110, 8721. (b) Kissinger, C. R.; Sieker, L. C.; Adman, E.
affords the cubane-type clusters 2.6'15 The situation is sum- T.; Jensen, L. H. J. Mol. Biol. 1991, 219, 693.
(6) (a) Kent, T. A.; Dreyer, J.-L.; Kennedy, M. C.; Huynh, B. H.; Emp-
marized in Table I, from which it is evident that ferredoxin proteins
tage, M. H.; Beinert, H.; Miinck, E. Proc. Natl. Acad. Sci. U.S.A. 1982, 79,
(note abbreviations) may be reconstituted in reaction 1 to a ho- 1096. (b) Beinert, H.; Emptage, M. H.; Dreyer, J.-L.; Scott, R. A.; Hahn,
mometallic (Fe4S4) or to heterometallic (MFe3S4) species. In the J. E.; Hodgson, K. O.; Thomson, A. J. Proc. Natl. Acad. Sci. U.S.A. 1983,
80, 393. (c) Kennedy, M. C.; Emptage, M. H.; Dreyer, J.-L.; Beinert, H. J.
remaining known oxidation state of 1, [Fe3S4]1+, the electrophilic Biol. Chem. 1983, 258, 11098. (d) Emptage, M. H.; Dreyer, J.-L.; Kennedy,
M. C.; Beinert, H. J Biot. Chem. 1983, 258, 11106. (e) Kent, T. A.; Emptage,
*
Harvard University. M. H.; Merkle, H.; Kennedy, M. C.; Beinert, H.; Munck, E. J. Biol. Chem.
!
Carnegie Mellon University. 1985, 260, 6871.

0002-7863/92/1514-10843S03.00/0 &copy; 1992 American Chemical Society