Article

pubs.acs.org/JPCC

Pore Size Determination in Ordered Mesoporous Materials Using

Powder Xray Diraction
Yosuke Ishii, Yoshiki Nishiwaki, Ayar Al-zubaidi, and Shinji Kawasaki*
Department of Materials Science and Engineering, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555, Japan
S Supporting Information
*

ABSTRACT: We demonstrated in the present investigation

that, by analyzing the small-angle powder XRD pattern, we
successfully determined not only the pore-to-pore distance but
also the pore diameter of the mesoporous materials having a
quasi two-dimensional hexagonal pore structure. It was found
that the pore diameter values determined by this method were
in good accordance with those derived from nitrogen gas
adsorption measurement (KrukJaroniecSayari method) for
several kinds of mesoporous silicas and carbons. Furthermore,
owing to the advantage of this determination method that it is
applicable to the wet sample, we applied this method to the
mesoporous sample immersed in the liquid whose bulk density
is known to evaluate the density of framework materials. The derivation of the theoretical formula of the small-angle XRD
pattern of the mesoporous materials is also described in this paper.

1. INTRODUCTION
Ever since the discovery of surfactant-template synthesis
methods, ordered mesoporous materials have generated
tremendous interest.1 In addition to the commonly known
MCM-41 type silicas, various kinds of mesoporous materials
with dierent structural symmetries210 and framework
compositions1117 have been synthesized over the last 20
years. Because of their unique and controllable nanostructure,
ordered mesoporous materials are expected to be used in
various elds of application, such as catalysts,1821 adsorbents,21,22 drug derivery,23,24 sensors,24,25 and energy conversion
and storage.2631 Needless to say, the structural characterization of ordered mesoporous materials is essential in
researching these applications. Direct observations using
transmission electron microscopy (TEM), gas adsorption
desorption isotherm analysis, and small-angle powder X-ray
diraction (XRD) are commonly used structural characterization methods for ordered mesoporous materials. Of these
techniques, TEM observation is the most direct and most
commonly used method. In addition to the normal 2D
transmission micrographs, 3D structural images can also be
obtained using a recently developed electron tomography
technique.29 However, specialized experience is required for
exact analysis because TEM images are strongly aected by
various experimental conditions, such as focus settings, sample
thickness, and electromagnetic lens aberrations.32 Furthermore,
the TEM method is unsuitable for statistical analysis, because
the images contain only local information from a selected area.
On the other hand, the gas adsorptiondesorption method can
give bulk pore structure information. Specic surface areas
estimated by the BrunauerEmmettTeller (BET) method33
2013 American Chemical Society

and pore-size distributions calculated by the BarrettJoyner

Halenda (BJH) method34 are often employ structural
information obtained from gas adsorptiondesorption isotherm analysis. In addition to these classical methods, more
sophisticated analysis such as nonlocalized density functional
theory simulation (NLDFT)3538 and grand canonical Monte
Carlo calculations (GCMC)3941 have also been used in recent
years. However, structure parameters obtained by the gas
adsorptiondesorption methods are strongly dependent on
their calculation models. Moreover, structural ordering cannot
be determined by gas adsorptiondesorption methods alone.
Small-angle powder XRD is often used to counter this
disadvantage of gas adsorptiondesorption methods. From
the XRD peak positions, structural symmetry and the distances
between adjacent pores can be determined.
Although structure analysis based on XRD peak positions is a
commonly used method for ordered mesoporous materials,
quantitative discussions of XRD peak intensities have not often
been reported. Feuston et al. reported model structures for
MCM-41 silica materials obtained from molecular dynamics
(MD) simulations.42 In their report, XRD pattern simulations
were also performed using optimized atomic coordination
obtained from the MD calculations. They mentioned that the
XRD peak intensities are highly dependent on mesopore
diameter and unit cell size. However, no general relationship
between XRD peak intensity and mesopore diameter was
discussed in their paper. Furthermore, XRD pattern calculation
Received: June 10, 2013
Revised: August 2, 2013
Published: August 6, 2013
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2. EXPERIMENTAL METHODS
2.1. Sample Preparation. 2.1.1. Synthesis of SBA-15
Mesoporous Silica. SBA-15 mesoporous silica was synthesized
as reported by Zhao et al.51 In this procedure, we used
tetraethoxysilane (TEOS) as a silica precursor and triblock
copolymer Pluronic P123 (EO20PO70EO20; BASF) as a
structure directing template. First, 4.0 g of Pluronic P123 was
dissolved in a solution of 30 g of water and 120 g of 0.2 M HCl
aqueous solution, and stirred at 60 C for 30 min. Then, 8.5 g
of TEOS was added to the solution. After stirring the mixture
for 10 min, it was kept at 35 C for 20 h without stirring. Then,
the mixture was aged at 80 C for 72 h. The generated solid
product was ltered, washed with water and ethanol, and dried
in an oven at 140 C for 4 h. To remove the Pluronic P123
template, the sample was heated in an electric furnace at 550 C
for 4 h under air. In order to avoid mesostructure collapse, the
heating and cooling rates were xed at 5 C min1. After the
heat treatment, the obtained mesoporous silica was ground into
a ne powder with an agate mortar. For convenience, the
obtained product was designated as MPS1 in this paper.
2.1.2. Synthesis of MCM-41 Mesoporous Silicas. MCM-41
mesoporous silica ber samples were synthesized using
tetrabutoxysilane (TBOS) as a silica precursor and cetyltrimethylammonium bromide (CTAB) as a structure directing
template.52 First, 2.25 g of CTAB was dissolved in a solution of
32.5 g of water and 125 g of 5 M HCl aqueous solution and
stirred at room temperature for 30 min. Then, 2.7 g of TBOS
was dripped into the solution and kept at 50 C for 10 days
without stirring. The resultant solid bers were ltered, washed
with water and ethanol, and dried in an oven at 80 C for 12 h.
The obtained mesoporous silica was ground into a ne powder
with an agate mortar. In order to remove the CTAB template,
two types of post-treatments were performed for the assynthesized samples: one was a solvent extraction method and
the other was a combustion method. In the solvent extraction
method, the as-synthesized silica was reuxed with ethanol in a
Soxhlet extractor for 30 h. After the extraction, the sample was
dried in an oven at 80 C for 12 h. The obtained product was
designated as MPS2. On the other hand, in the combustion
method, the as-synthesized silica was heated in an electric
furnace under O2 ow (50 ccm) at 500 C for 5 h. The heating
and cooling rates were xed at 5 C min1 to avoid
mesostructure collapse. The obtained product was designated
as MPS3.
2.1.3. Synthesis of Mesoporous CarbonSilica Composite.
The mesoporous carbonsilica composite sample was synthesized using the triconstituent coassembly method proposed by
Liu et al.53 In this procedure, we used phenolformaldehyde
resin (resol) as a carbon source, TEOS as a silica precursor, and
triblock copolymer Pluronic F127 (EO106PO70EO106; BASF) as
a structure directing template. First, 0.5 g of Pluronic F127 was
dissolved in a solution of 32.0 g of ethanol and 4.0 g of 0.2 M
HCl aqueous solution, and stirred for 15 min. Then 8.0 g of
TEOS and 20.0 g of 20 wt % resols ethanolic solution were
added in the solution. After stirring the mixture for 2 h, it was
transferred into PTFE dishes. The dishes were maintained at 40
C for 24 h to evaporate ethanol. Subsequently they were kept
at 100 C for 24 h to attain thermo-polymerization. The
polymerized product was carbonized by heating in an electric
furnace under N2 ow (30 ccm) at 900 C for 1 h following
elimination of Pluronic F127 by heating at 400 C for 2 h. The
heating and cooling rates were xed at 1 C min1 to avoid

based on MD optimization is not suitable for routine analysis,

because the MD simulation requires signicant computational
expense. Owing to the dramatic improvements of computational technology, the problem of calculation cost is gradually
fading out in recent years. However, the MD-based method is
still not easy to use, because the method requires sophisticated
skill and knowledge to perform molecular calculation.
Fortunately, such an elaborate MD simulation process may
be not indispensable for XRD pattern calculation. Schmidt
demonstrated that reasonable XRD pattern simulation can be
performed even without optimization of the atomic position in
the model structure.43 This means that the detailed atomic
coordination does not have a signicant eect on XRD pattern
calculation for ordered mesoporous materials. In the meantime,
Imperor-Clerc et al. demonstrated an XRD pattern simulation
for SBA-15 silica materials using a simpler structural model.44
In their paper, the solid framework structure (amorphous silica
region) was approximated by a uniform electron density matrix
instead of by exact atomic congurations. According to their
theory, the XRD peak intensity of hkl lines (Ihkl) are calculated
from a unit cell form factor (F(q)) as follows:
Ihkl = KMhkl

|F(qhkl)|2
qhkl 2

(1)

where K is a scaling factor used to adjust the peak intensities to

match the experimentally observed intensities, Mhkl is a
multiplicity factor for the hkl line, qhkl is the magnitude of the
scattering vector for the hkl line (here, qhkl is calculated using
Braggs law), and 1/qhkl2 is the Lorentz factor for powder
diraction. The form factor was calculated from a Fourier
transform of the electron density distribution in the unit cell.
Similar uniform electron density matrix model was also adapted
for MCM-41 silica materials by Solovyov et al.45 Since the XRD
data provide direct structural information without any semiempirical parameters or assumptions, the XRD method has
been used for discussing the relevance of pore-size distribution
data obtained by gas adsorptiondesorption isotherm analysis.46,47 By modifying the unit cell form factor, theoretical
XRD patterns of more complicated structures, such as a
mesoporous material that contains complex pore-surface
structures44,48 or 3D cage-like mesoporous silicas49 can also
be calculated in the same manner. Furthermore, in situ XRD
observations of the gas adoption-desorption process in ordered
mesopores were also performed based on this calculation
method.49,50 However, we believe that the XRD pattern
calculation using eq 1 may be problematic because the range
of pore ordering (i.e., coherent length, crystallite size) was not
precisely considered. XRD pattern calculation based on eq 1
would be correct only for innitely ordered mesopore samples.
Since the XRD peak width, which is indicative of crystallite size,
of mesoporous materials is usually broad (i.e., crystallites are
small), such an innitely ordered pore description may be
unreasonable. Therefore, we would like to propose a modied
XRD calculation model for ordered mesoporous materials in
this paper. In our model, the degree of interference between
unit cells (i.e., crystallite size eect) was treated by convoluting
the unit cell form factor function with a Laue-type interference
function. In order to test the validity of our method, various
types of ordered mesoporous samples having 2D-hexagonal
symmetry were synthesized, and their XRD patterns were
compared with theoretically calculated patterns.
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Figure 1. (A) Schismatic structure of the ordered mesoporous material examined in this study. Cylindrical mesopores (diameter, D = 2R; length, L)
are 2D hexagonally aligned and form an ordered crystalline nanostructure. The structural backbone (wall region) consists of a uniform amorphous
matrix (density, 1). (B) Calculation scheme of the unit cell form factor (F(q)).

proposed by Kruk, Jaroniec, and Sayari (BJHKJS method55)

was also used in this study. In the BJHKJS calculation, a
modied Kelvin equation developed for N2 adsorption on silica
samples with cylindrical mesopores (eq 4) and a HarkinsJura
type equation (eq 5) were used to calculate rK and t,
respectively.

mesostructure collapse. After the carbonization, the obtained

mesoporous carbonsilica composite was ground into a ne
powder with an agate mortar. The obtained product was
designated as MPCS.
2.2. Characterization. The nanostructures of the obtained
samples were observed using a JEOL z2500 transmission
electron microscope operated at 200 kV. The removal of
surfactant molecules used as a structure directing template was
conrmed by thermogravimetric (TG) analysis using a
Shimadzu TGA-50 instrument. The TG analysis also
determined the carbonsilica ratio of the MPSC sample.
Nitrogen adsorptiondesorption isotherms at 77 K were
measured using a Shimadzu Gemini 2375 instrument. Prior
to the isotherm measurements, the samples were heat treated at
200 C under vacuum (<3 Pa) for at least 1 h to remove
adsorbed moisture. The specic surface areas (SBET) were
estimated using the BrunauerEmmettTeller (BET) method33 and the adsorption data in the relative pressure (P/P0)
range from 0.05 to 0.16. The total pore volumes (Vtotal) were
calculated using the Gurvich rule at P/P0 = 0.97. The s-plot
method was used to estimate the micropore (Vmicro) and
mesopore (Vmeso) volumes. In the s analysis, adsorption
isotherm data for the LiChrospher Si-1000 silica reported by
Jaroniec et al.54 was used as the reference adsorbent. The poresize distributions were calculated based on an analysis of the
adsorption branch of the isotherms using the BarrettJoyner
Halenda (BJH) method.34 In the BJH calculation, the Kelvin
radius (rK) and statistical lm thickness of the N2 adsorbed
layer (t) were estimated using the Kelvin equation (eq 2) and
the Halsey equation (eq 3), respectively.
rK =

2VL
RT ln(P /P0)

5 1/3
t = 3.54

ln(P /P0)

2VL
+3
RT ln(P /P0)

(4)

0.3968
60.65
t=

0.03071 log(P /P0)

(5)

rK =

The primary mesopore diameter estimated by the KJS method

is designated as DKJS in this paper.
Powder XRD measurements were carried out using a Rigaku
Nano-Viewer diractometer, equipped with a two-dimensional
(2D) imaging plate detector (Rigaku R-AXIS IV++), using Cu
K radiation ( = 1.54 ) as an incident beam. The XRD
measurements were performed in transmission geometry.
Lindemann glass capillary tubes ( = 0.5 mm) were used as
a sample container, and the typical exposure time was 30 min.
For MCM-41 (MPS2 and MPS3) samples, powder XRD
measurements using synchrotron radiation were also performed
to obtain high-quality diraction patterns. The synchrotron
XRD measurements were performed using beamline BL-18C at
the Photon Factory (PF) in the High Energy Accelerator
Research Organization (KEK), Tsukuba, Japan. The synchrotron radiation beams emitted from an electron storage ring
operated at 2.5 GeV were monochromatized by a Si (111)
double-crystal monochromator and collimated by a pinhole
collimator 100 m in diameter. The incident X-ray wavelength
for these measurements was = 0.613 . Each diraction
pattern was collected using a 2D imaging plate detector (200
mm 250 mm) located 500 mm behind the sample position.
The typical exposure time was 5 min. Lindemann glass capillary
tubes ( = 1.0 mm) were used as a sample container. Prior to
the measurements, the incident X-ray wavelength and the
distance from the sample to the imaging plate detector were
calibrated using the XRD peaks of a CeO2 powder by the
double cassette method.56 Prior to further analysis, the obtained
XRD intensities Iobs(2) were corrected for polarization factor
p(2), geometric factor for the 2D at plate detector G(2) =
cos3 2,57 dark current noise of the detector Idark, transmission

(2)

(3)

where rK is expressed in , is the surface tension of the liquid

N2 (8.88 103 J m2), VL is the molar volume of the liquid N2
(3.468 1025 3 mol1), R is the ideal gas constant (8.8314
1020 J 2 K1 mol1 m2), and T is the absolute temperature of
adsorption (77 K). t is expressed in . In this paper, the
primary mesopore diameter determined by the BJH method is
designated as DBJH. Since the traditional BJH method tends to
underestimate mesopore diameter,35,55 a modied BJH method
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where a is a unit cell lattice constant that represents the interval

of adjacent mesopore centers. The multiplicity factors of h0, hh,
and hk (h k, k 0) diraction peaks become 6, 6, and 12,
respectively.
The form factor F(q) can be calculated on the basis of the
structure model shown in Figure 1A. In this study, we
considered a shifted unit cell (indicated by II in Figure 1A),
instead of the commonly used version (indicated by I in Figure
1A). As shown in Figure 1B, F(q) may be expressed as follows:

factor, and background scattering from a blank capillary and air

Iback(2) as follows:
I0
1
{Iobs(2 ) Idark }
p(2 )G(2 ) Is

Icorr(2 ) =

I0
{Iback(2 ) Idark }
Ib

(6)

where Icorr(2), I0, Is, and Ib are the corrected XRD intensity,
incident X-ray intensity, X-ray intensity after transmission
through the sample, and X-ray intensity after transmission
through the blank capillary, respectively. All XRD measurements were performed at room temperature.

F(q) = 1f1 (q)Fmatrix(q) 1f1 (q)Fcylinder(q)

where Fmatrix(q) and Fcylinder(q) represent structure factors of the

uniform matrix and of the cylinder (radius, R; length, L),
respectively. The structure factors could be calculated from a
Fourier transform of the atomic (or more principally electron
density) distribution. Since the Fourier transform of a constant
value, that representing the uniform matrix, becomes a delta
function (q), the Fmatrix(q) terms would be replaced by zero,
except for in the q = 0 case. Therefore, eq 11 can be rewritten
as

3. THEORETICAL BASIS
3.1. Theoretical XRD Pattern for Ordered Mesoporous
Materials with 2D-Hexagonal Symmetry. In this section,
we theoretically derive powder X-ray diraction patterns of
ordered mesoporous materials with 2D-alingned cylindrical
pores. Here, we assume the structure model shown schematically in Figure 1A. In this model, empty cylindrical mesopores
(radius, R; length, L) are hexagonally aligned in a uniform
amorphous matrix (density, 1; average atomic X-ray scattering
factor, f1(q)).
The diraction intensity from a nonoriented powder
crystalline sample, I(q), would be calculated using a unit cell
form factor F(q) in the following manner:
I(q) |F(q)|2 L(q)

F(q) = 1f1 (q)Fcylinder(q)

f1 (q) =

2
w

(7)

Fcylinder(q) =

L /2

4
a

h2 + hk + k 2
3

(14)

where r(z, r, ) is the positional vector in the cylinder.

Through further calculations, as described in the Supporting
Information, eq 14 becomes the following expression:
(9)

Fcylinder(q) = Fcylinder(q , q ) = 2R2

where w is the full-width-at-half-maximum, is the Gaussian/

Lorenz ratio, and qhkl is the scattering vector at the Braggs
angles of the hkl line. Note that such pseudo Voigt type peak
prole functions are often used in Rietveld renements for
powder XRD analysis. In the meantime, for 2D-hexagonally
aligned mesoporous materials, only l = 0 (i.e., hk0) diraction
lines are observed. Therefore, diraction indices are represented by two digits in the following parts. In this time, the
scattering vector at the Braggs angles of the hk line qhk can be
expressed as
qhk =

exp(iqr) dv

z=L/2 r=0 =0 r exp(iqr) d dr dz

2 1

q qhkl
2

1 + 4
w
w

(13)

q qhkl 2
ln 2

exp 4 ln 2
w

+ (1 )

1
2
fSi (q) + fO (q)
3
3

where f Si(q) and f O(q) represent the atomic scattering factors

of Si and O, respectively. Although practical values of atomic
scattering factors have been tabulated in the International
Tables for Crystallography,58 the fa (q) term would be ignored
in practical calculations since the atomic scattering factors of
light atoms (such as Si, O, and C) are approximately constant
in the small-angle region. In the meantime, Fcylinder(q) would be
expressed as follows:

where q is the magnitude of the scattering vector (q = 4 sin /

), is the scattering angle, is the X-ray wavelength, L(q) is
the Lorentz factor for powder diraction (L = 1/(sin2 cos )),
Mhkl is the multiplicity factor of the hkl diraction line, and
Ghkl(q) is the Laue function representing the interference
between unit cells. Since the exact form of the Laue function is
not appropriate for numerical calculations, Ghkl(q) was
approximated by a pseudo Voigt function in this study. The
pseudo Voigt function is the sum of a Gaussian prole and a
Lorenz prole, and can be expressed as
Ghkl(q) =

(12)

Taking mesoporous silica as an example, f1(q) may be

expressed as

MhklGhkl(q)
h,k ,l

(11)

J1 (qR ) sin(q L /2)

qR

q L /2
(15)

where J1 is the rst order Bessel function of the rst kind, q is

the q component perpendicular to the direction of the c axis,
and q is the q component parallel to the direction of the c axis.
Because most mesoporous materials have very large L values,
the term sin(qL/2)/(qL/2) behaves like a delta function,
(q). This means that diraction peaks can be observed only
when q 0 (i.e., |q| q). This is consistent with the wellknown experimental axiom that only l = 0 diraction lines are
observed in 2D-hexagonal mesoporous materials. In this case,
eq 15 can be further simplied to the following expression:

(10)
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practical expression that represents the relationship between

structural features (mesopore diameter D and lattice constant
a) and XRD peak intensities. As discussed in section 3.2, the
diraction intensity at the hk Braggs angle qhk, Ihk is expressed
as follows:

J1 (qR )
q

(16)

Because the mesopore channels in real materials are not

perfectly oriented, and their positions uctuate as illustrated in
Figure S1(A), additional terms are required for practical XRD
pattern tting. In this work, in order to consider the uctuation
of mesopore positions, eq 7 was multiplied by the Debye
Waller factor (D(q; ) = exp(2q2/2); , mean-square
displacement), assuming a Gaussian displacement of pore
center positions. In addition to the uctuation in pore position,
(i) uctuation in pore radius R as illustrated in Figure S1(B)
and (ii) deformation of pore structure as illustrated in Figure
S1(C) would also be considered as described in the Supporting
Information (section B and C). Since the mesoporous samples
used in this study have very narrow pore-size distributions and
well-formed circular pore-cross sections, the factors (i) and (ii)
are not considered in the following discussions.
Thus, theoretical XRD patterns of ordered mesoporous
materials with 2D-hexagonal symmetry can be calculated by the
following equation:
I(q) = s fa (q)

RJ1(qR )
q

Ihk Mhk fa (qhk )

qhk

L(qhk )D(qhk ; )

(18)

Therefore, the peak intensity ratio of hk to hk can be written

2
Ihk
Mhk J1(qhk R ) L(qhk ) D(qhk ; )
=
Ih k
Mh k J1(qh k R )2 L(qh k ) D(qh k ; )

(19)

As shown in the Supporting Information, the term L(qhk)/

L(qhk) in eq 19 may be expressed as
L(qhk )
L(qh k )

h2 + hk + k2
h2 + hk + k 2

(20)

in the small-angle region. From eq 10, qhkR becomes

qhk R = 2

L(q)D(q; )

h2 + hk + k 2
3

(21)

where is the mesopore diameter normalized by a ( = 2R/a =

D/a). Therefore, if we can assume that the uctuation of
mesopore position is negligible, eq 19 can be rewritten as

MhkGhk(q; a; w; )
h,k

RJ1(qhk R )

(17)

where s is a scaling factor. For example, the theoretical XRD

pattern of a mesoporous silica sample (a = 11.0 nm, R = 3.0
nm) would be calculated as shown in Figure 2.
3.2. Relationship between Lattice Constant and
Mesopore Diameter. Although theoretical XRD patterns of
ordered mesoporous materials can be calculated using eq 17,
the relationship between mesopore structure and the XRD
pattern may be dicult to understand because the equation
contains many parameters. In this section, we derive a more

2
Ihk
Mhk J1(2 g /3 ) g
=
Ih k
Mh k J1(2 g /3 )2 g

(22)

g = h2 + hk + k 2

(23)

g = h2 + hk + k2

(24)

Equation 22 indicates that the relative diraction intensities at

the Braggs angles are essentially determined only by the
(=D/a) value. Figure 3 shows the relationship between and
the diraction peak intensities. In this graph, the intensity of the
10 diraction line was normalized to 1. Since the unit cell lattice
constant a is directly determined from the peak positions, the
mesopore diameter D can be estimated from the value
determined by analysis of the diraction intensity using Figure
3.
Note that if the uctuation of mesopore position (Debye
Waller factor) is not negligible, the diraction peak intensities
will decrease with increasing q value. We should also note that
Ihk (diraction intensity at qhk) is not proportional to the peak
area of the hk line Ahk, because the exact shapes of the
diraction peaks are modulated by the F(q) shape. The
dierence between Ihk and Ahk becomes non-negligible when
the diraction peaks are broad. Therefore, pattern tting using
eq 17 is required for a rigorous structure assessment.

4. RESULTS AND DISCUSSION

First, we characterized the nanostructure of the obtained
samples using commonly used procedures. Figure 4 shows
TEM images of the MPS1 sample. Hexagonally aligned straight
channel pores were clearly observed. As shown in Figure S2,
similar porous structures were observed in the other samples
(MPS2, MPS3, and MPCS) used in this study. Nitrogen
adsorptiondesorption isotherms are shown in Figure S3(A).
In the MPS1 and MPCS samples, clear hysteresis loops

Figure 2. (a) Theoretical XRD pattern of an ordered mesoporous

material with 2D-hexagonal symmetry (a = 10.0 nm, R = 3.0 nm). The
theoretical XRD prole was calculated by multiplying (b) the squared
unit cell form factor |F(q)|2 |RJ1(qR)/q|2, (c) Lorentz factor L(q),
and (d) the sum of the peak functions (MhkGhk(q)).
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Figure 4. TEM photographs of MPS1 (A) parallel and (B)

perpendicular to the channel pore axis.

Figure 3. Diraction intensities of (a) 11, (b) 20, (c) 21, and (d) 30
peaks calculated using eq 22. The peak intensity of the 100 diraction
peak was set to 1. Panel B is a magnied view of panel A.

appeared. Their isotherm shapes were classied as type IV,

according to the IUPAC denition.59 On the other hand, no
hysteresis loops were observed in MPS2 or MPS3 samples,
probably due to their narrow mesopore diameters, which were
close to the micropore range (<2 nm). Such a lack of a
hysteresis loops feature is often reported for small pore-size
MCM-41 type materials.6062 In the adsorption branch of the
isotherms, rapid increases of adsorbed volume, which is
characteristic of capillary condensation within mesopores,
occurred around P/P0 = 0.67 (MPS1), 0.32 (MPS2), 0.28
(MPS3), and 0.61 (MPCS). Such a sharp increase indicates a
high uniformity of the mesopores. The narrow distributions of
mesopore diameter were conrmed by pore size distribution
curves calculated using the BJH method, as shown in Figure
S3(B). Figures 5 and S4 show powder XRD patterns of the
obtained samples. As illustrated in the gures, more than four
diraction peaks were observed in all samples, and these peaks
could be indexed to a 2D-hexagonal symmetry (p6mm). The
observed diraction peak positions and the peak intensity ratio
of MPS1 were quite dierent from those of MPS2. Meanwhile,
although the peak intensity ratios of MPS2 were close to those
of MPS3, the peak positions of MPS2 were located at lower
angles than those of MPS3. The relationship between
mesopore structure and the XRD pattern will be discussed
later in this paper. Lattice constant (a) values of MPS1, MPS2,
MPS3, and MPCS, estimated from the positions of 10
diraction peaks, were 10.62, 4.56, 4.33, and 11.42 nm,
respectively. According to previous reports, the mesopore
diameter (denoted here as Dgeo) could be roughly estimated

Figure 5. XRD pattern of MPS1.

from the unit cell lattice constant a and mesopore volume Vmeso
using a simple geometrical calculation, assuming a pore wall
density .55,6365 Since the existence of micropores was
conrmed by s-plot analysis (see Figure S5), we used the
following equation instead of the previously proposed one.
Dgeo

1/2
2 3 Vmeso
=
a
{1 + (Vmeso + Vmicro)}

(25)

where Vmicro is the micropore volume, and the densities of SiO2

and C were assumed to = 2.2 and 1.8 g cm3, respectively. In
this equation, we assumed that all of the micropores are
homogeneously dispersed in the wall region located between
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Table 1. Structural Parameters of the Obtained Materialsa

MPS1
MPS2
MPS3
MPCSb

a10 [nm]

SBET [m2 g1]

Vtotal [cm3 g1]

Vmeso [cm3 g1]

Vmicro [cm3 g1]

DBJH [nm]

DKJS [nm]

Dgeo [nm]

10.62
4.56
4.33
11.42

596
962
1156
365

0.64
0.75
0.81
0.39

0.43
0.70
0.78
0.35

0.07
0.02
0.00
0.03

6.4
2.8
2.6
5.4

7.3
3.6
3.4
6.3

7.5
3.7
3.6
7.6

a10, lattice constant estimated from the apparent position of 10 XRD peak; SBET, specic surface area estimated by the BET method; Vtotal, total pore
volume; Vmeso, primary mesopore volume; Vmicro, micropore volume; DBJH, primary mesopore diameter estimated by the BJH method; DKJS, primary
mesopore diameter estimated by the KJS method; Dgeo, mesopore diameter estimated by geometrical relationship shown in eq 25. bThe C/SiO2
weight ratio estimated by thermogravimetric analysis was 37.5:62.5.

structural parameters obtained by the tting are shown in

Figure 6. As shown in Figure 6, the simulated patterns well
reproduced the experimentally observed patterns. Mesopore
diameters determined by the XRD method (DXRD) were close
to DKJS, and were larger than DBJH in all samples. According to
previous reports, the traditional BJH method tends to
underestimate mesopore diameter.35,55 Our XRD analysis
data support this underestimation of the BJH method, without
making any semiempirical assumptions. Furthermore, as shown
in Table 2, the value of the MPCS sample was larger than
those of MPS1, MPS2, and MPS3. This is probably a result of
the above-mentioned structural roughness of MPCS.
By comparing Tables 1 and 2, we found that the values of afit
were smaller than a10 in all samples. This means that the
observed peak positions were somewhat dierent from those
simply predicted by Braggs law. This dierence seems to arise
from the shape of the form factor term (|F(q)|2) in eq 7. We
found that |F(q)|2 always monotonically decreases near the
Braggs 10 diraction angle, independent of a and R. Therefore,
the net shape of the 10 peak prole (the convolution of |F(q)|2
and G10(q)) should be downshifted relative to the pure G10(q)
peak, which was located at the Braggs angle. The modulation
becomes conspicuous with increasing diraction peak width. In
addition to the 10 peak, other peak positions are also
modulated by the shape of |F(q)|2. As shown in Figure S6,
the degrees of peak modulations are dierent with . A similar
modulation of XRD peak positions has been reported for
single-walled carbon nanotube (SWCNT) bundles.66 (Note
that individual SWCNTs are generally aggregated due to van
der Waals interactions to form a 2D-hexgonally aligned crystal
structure called a bundle. The XRD pattern of SWCNTs can be
calculated based on eq 7 by replacing the form factor with F(q)
= 2Rfc(q)J0(qR), where J0 is the zeroth order Bessel function
of the rst kind, fc(q) is the X-ray scattering factor of the carbon
atom, and R is the tube radius.)
Thus far, we have discussed the XRD patterns of mesoporous
materials measured in the dry state. Let us broaden our scope
to include wet conditions. For SWCNTs, it is well-known that
the XRD pattern of a water-immersed sample is completely
dierent from that of a dry sample.67 For example, the I10/I11
ratio of a water-immersed SWCNT is much smaller than that of
a dry SWCNT. However, for mesoporous materials, the peak
intensity ratio of a water-immersed sample was similar to that
of a dry sample. Although the XRD peak intensity ratio was the
same, the absolute intensity of a water-immersed wet
mesoporous sample was much smaller than that of a dry
sample. We found that the pore wall density can be estimated
from the dierence in XRD intensity between dry and wet
samples. The XRD patterns of wet mesoporous samples can be
calculated by modifying the unit cell form factor used in eq 11.
Assuming that all mesopores are homogeneously lled with

aligned mesopore channels. Equation 25 becomes equivalent to

the equations presented in previous reports55,6365 by replacing
the term (Vmeso + Vmicro) with Vmeso. The obtained structural
parameters are summarized in Table 1. The DKJS values were
very close to Dgeo, except for the MPCS sample. The mismatch
between DKJS and Dgeo in MPCS may arise from roughness of
the mesopore structure. As shown in the TEM photographs
(Figures 4 and S2) and pore size distribution curve (Figure
S3(B)), the structural roughness of the MPCS sample was
much higher than in other samples. In addition to the structural
roughness, the dierences in surface chemistry between SiO2
and C may also have aected the pore size estimation, because
such dierences are not properly considered in the BJH or KJS
calculations in this study. The Vmicro value of the MPCS may
also have a problem, because s-analysis should also be aected
by the surface properties. Here we note that the BJH or KJS
method has a potential to accommodate surface properties
through the selection of the statistical lm thickness for an
appropriate surface type. However, the accommodation is hard
for the MPCS due to its complicated chemical composition. In
contrast to the gas adsorptiondesorption methods, such
information of pore-surface is not required for the XRD
analysis method.
Next, we will discuss the details of the XRD analysis. As
mentioned in section 3.2, the structure parameter that
represents the size ratio between the lattice constant a and the
mesopore diameter D can essentially be estimated from the
XRD peak intensities using Figure 3. For example, for the
MPS1 sample, the following relationships were observed in
Figure 5: (A) I11 < I20, (B) I20 > I21, (C) I21 > I30. In order to
satisfy requirement (A), the value should be somewhere
between 0.58 and 0.73. Furthermore, 0.62 < and < 0.70 are
also required to satisfy (B) and (C), respectively. Therefore, the
value of MPS1 was estimated to be 0.62 < < 0.70 (6.6 nm <
D < 7.4 nm). In order to narrow down the estimation range of
, XRD pattern ttings were performed. Equation 17 was used
as a model function, and the modied LevenbergMarquardt
method was adopted as a nonlinear least-squares tting
algorithm. The obtained structure parameters are summarized
in Table 2. Simulated XRD patterns calculated from the
Table 2. Structural Parameters Determined by Nonlinear
Least-Square Fittings of XRD Patterna
afit [nm]
MPS1
MPS2
MPS3
MPCS

10.555(1)
4.526(2)
4.292(3)
11.359(2)

DXRD [nm]
6.95(6)
3.60(7)
3.38(9)
6.98(16)

[nm]
0.72(2)
0.39(2)
0.40(2)
1.04(2)

(=DXRD/afit) []
0.66
0.79
0.79
0.61

afit, lattice constant; DXRD, primary mesopore diameter; , meansquare displacement of mesopore position.

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Figure 6. Comparison between (a) observed and (b) simulated XRD patterns of (A) MPS1, (B) MPS2, (C) MPS3, and (D) MPCS.

water (density, 2; average atomic X-ray scattering factor,

f2 (q)), F(q) may be expressed as follows, except for the q = 0
case
F(q) = 1f1 (q)Fmatrix(q) 1f1 (q)Fcylinder(q)
+ 2 f2 (q)Fcylinder(q)
= (2 f2 (q) 1f1 (q))Fcylinder(q)

(26)

Since the observed XRD intensity is proportional to |F(q)|2, the

intensity ratio between dry and wet samples can be expressed as
follows:
f (q)
I wet
= 1 22
Idry
1f1 (q)

(27)

where Iwet and Idry are the XRD intensities of wet and dry
samples, respectively. Taking MPS3 as an example, the
experimentally observed Iwet/Idry was 0.258 (see Figure 7).
Assuming that the density of water in the mesopores is similar
to the bulk density (2 = 1.00 g cm3), 1 was calculated to be
2.26 g cm3. This value is reasonable for amorphous SiO2
(about 2.2 g cm3).65,68 However, we should note that there is
no assurance that the density of water conned in the
mesopore is similar to the bulk density, because there are
reports discussing the abnormal physical properties of
molecules conned within nanospaces.67,6977 Further research
is required to examine the exact density of water in mesopores.
Normally, such a research would be dicult because we have to

Figure 7. XRD patterns of (a) dry and (b) water-immersed MPS3.

Diraction peaks of CeO2 powder used as internal intensity standard
(the weight ratio of MPS3/CeO2 was 2:1) also shown.

distinguish conned water from bulk one. However, we expect

that our XRD method might be useful to probe the density of
liquids conned in mesopore, because the XRD peak intensity
of mesoporous samples are selectively aected by the densities
of conned liquids. By comparing XRD intensities of ordered
mesoporous samples immersed in various kinds of liquids, the
densities of the liquids conned in mesopores would be
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evaluated. This research is currently being carried out, and will

be addressed in more detail in a separate publication.

5. CONCLUSION
In this paper, we derived theoretical XRD patterns of ordered
mesoporous materials with 2D-hexagonal symmetry (p6mm).
In order to test the validity of our theory, various types of
mesoporous samples with dierent pore sizes and chemical
compositions were synthesized, and their XRD patterns were
compared with theoretically calculations. The theoretically
calculated XRD patterns agreed well with experimentally
observed patterns. We found that the exact XRD peak positions
were modulated by the form factor |F(q)|2 and were dierent
from the positions calculated using Braggs law. By analyzing
the XRD peak intensities carefully, we successfully determined
the mesopore diameter and unit cell lattice spacing without
support from other methods such as TEM or N2 adsorption
desorption analysis. We also found that the XRD analysis can
be adopted for water-immersed wet samples and that the
density of the pore wall can be estimated from the dierence
between XRD intensities of dry and wet samples.
As discussed above, we demonstrated that the XRD analysis
can be performed, even for samples immersed in water. We
believe that this XRD-based method has great potential for in
situ experiments that cannot be performed by TEM or gasadsorption methods, because the XRD method does not
require any special measurement environments or pretreatments. Therefore, we expect that the XRD analysis proposed in
this study would be used to reveal poorly understood structural
properties of mesoporous materials in various environments
(such as high pressures and high temperatures) in the near
future.

ASSOCIATED CONTENT

S Supporting Information
*

Derivation of the structure factor for cylinder. Fluctuation in

pore-radius or pore-structure. Lorentz factor in small-angle
region. Figures S1S6. This material is available free of charge
via the Internet at http://pubs.acs.org.

AUTHOR INFORMATION

Corresponding Author

*E-mail: kawasaki.shinji@nitech.ac.jp.
Notes

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS
The authors gratefully acknowledge Professor Akio Ohta
(Kanazasa University, Japan) for XRD measurements.

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