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Pitfalls in the characterization of nanoporous and nanosized materials
Claudia Weidenthaler*
Received 3rd August 2010, Accepted 15th November 2010
DOI: 10.1039/c0nr00561d
Published on 13 January 2011 on http://pubs.rsc.org | doi:10.1039/C0NR00561D

With the advent of highly sophisticated analytical tools, numerous physical methods are nowadays
available for comprehensive characterization of inorganic matter and, as special cases, of porous and
nanosized materials. Intelligent experimental setup and correct evaluation of the experimental data can
provide helpful insights into the chemical and physical properties of such materials. However, scanning
of literature reports shows that in many cases evaluation and interpretation of experimental data are
erroneous. As a result, the description of a new material can be useless or even worse, misleading.
Wrong evaluation is even more critical if mechanistic theories are based on such data. Characterization
of porous and/or nanosized materials is mainly performed by gas adsorption, X-ray powder diffraction,
electron microscopy and surface spectroscopy. For correct interpretation of experimental data one
should be aware of certain pitfalls. The present paper summarizes prominent faults and may show how
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they can be avoided. It is supposed to provide some hand-on knowledge on correct analysis of
materials. Addressed are primarily non-experts and researchers being new to the field of
characterization of inorganic nanosized or nanoporous materials.

1. X-Ray diffraction
1.1 Broadening of X-ray diffraction peaks by small crystalline
domains

Analysis of the broadening of Bragg reflections is a very conve-

Max-Planck-Institut f€
ur Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470
M€
ulheim an der Ruhr, Germany. E-mail: weidenthaler@mpi-muelheim.
mpg.de; Fax: +49 208 3062989; Tel: +49 208 3062181
Claudia Weidenthaler studied
Mineralogy at the University of
W€ urzburg, where she received
her doctorate in 1995 for her
crystallographic studies on the
structures of different zeolite
materials. After this she worked
as staff researcher in the
department of crystallography
at the University of Bremen. In
1998 she joined the group
of Ferdi Sch€uth at the Faculty of
Chemistry at the University of
Claudia Weidenthaler Frankfurt. Since 1999 she has
a position as senior researcher at
the Max-Planck-Institut f€ ur
Kohlenforschung in M€ ulheim an der Ruhr. Her research focuses on
the characterization of structure-property relationships of novel
functional materials, especially by diffraction and spectroscopic
methods.
nient way to determine the size of crystalline domains from
powder diffraction data. Albeit it seems to be a very simple
correlation between peak broadening and the size of crystalline
domains, it is a rather complex and demanding subject. This
chapter will give a brief introduction into the determination of
crystal size domains from powder diffraction data. Nowadays,
powerful algorithms can be used for the analysis of microstruc-
ture properties. Even though these highly sophisticated methods
are available, most of the times the classical Scherrer method is
applied for evaluation of crystallite sizes.1 For this reason this
review will focus mainly on problems and limitations with respect
to the Scherrer equation and its unreflected application. For
further reading the textbooks on microstructure analysis by
Snyder et al.2 and Mittemeijer and Scardi3 are highly recom-
mended. For a polycrystalline powder sample consisting of large,
strain-free and perfect crystallites, the diffraction peaks of the
powder pattern would be extremely narrow. Due to instrumental
factors and materials properties, diffraction lines get broadened.
The different materials properties leading to peak broadening
can be summarized as follows:
 size of crystalline domains
 strain
 shape of the crystalline domains
 size distribution
 dislocations

792 | Nanoscale, 2011, 3, 792–810 This journal is ª The Royal Society of Chemistry 2011

 twinning and stacking faults
 antiphase domains.
The list shows that not only the size of small crystallites but
also several other microstructural properties can lead to broad-
ening of reflections. A very crucial point for a reliable particle size
determination is thus consideration of such additional factors
and/or their exclusion. The physical reason for reflection
broadening can be explained by a rather sophisticated mathe-
matical approach based on diffraction conditions in reciprocal
space but for simplicity it will be explained here via the simpler
approach based on the Bragg equation. Due to the three-
dimensional periodic arrangement of atoms in a crystal structure,
a crystal will diffract monochromatic radiation in three-dimen-
Published on 13 January 2011 on http://pubs.rsc.org | doi:10.1039/C0NR00561D
sional space. The angles at which diffraction occurs depend on
the size and the symmetry of the unit cell. The intensity distri-
bution of the diffraction maxima is mainly dependent on the
position of the atoms in the unit cell and the scattering properties
of these atoms. To predict diffraction phenomena and to express
the relationship between the position of reflections and the
wavelength of the radiation, father and son Bragg developed the
famous Bragg relation.4–9 Crystal structures are built up by
a periodic arrangement of atoms (Fig. 1).
The atoms can be interconnected in all three directions by
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imaginary planes representing different electron densities.
Lattice planes of a given lattice are planes (or family of parallel
planes) whose intersections with the lattice are periodic. All
lattice planes can be described by a set of indices (Miller indices
hkl) and the distance d between two parallel planes is called the
interplanar spacing. Regarding to Snell’s law, the angle q of the
incident beam and the angle of reflection are equal. For
a constructive interference, it is mandatory that the waves
reflecting from the different planes are in phase, requiring a path
length difference of an integer multiple of l. From Fig. 2 it can be
seen that wave 2 has to travel a longer distance (ABC) than wave
1. Constructive interference occurs only if the phase lag for the
distance ABC is an integer n of the wavelength l. If the phase lag
is not an integral integer of l (e.g. 0.5l), destructive interference
will occur and the diffraction intensities will be canceled out.
Maximum amplitude or constructive interference is obtained
at angles q (eqn (1))
nl ¼ 2dhklsin q (1)
with n ¼ integer determined by a given order, l ¼ wavelength,
q ¼ angle of the incident beam, and d ¼ interplanar distance
Fig. 1 Periodically arranged atoms lying on different sets of parallel
lattice planes, the distance between parallel planes is called the inter-
planar spacing d.
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Fig. 2 Bragg’s law can be derived from the geometrical relation between
the interplanar spacing d and the diffraction angle q. For simplification,
the atoms in this figure are omitted.
between a set of parallel lattice planes described by the Miller
indices (hkl).
In large, perfect crystals, there is always a ‘‘deeper’’ lattice
plane for which a path length distance of 0.5l is valid. In case
that the angle q between the incoming beam and the lattice plane
is deviating from the Bragg relation there is always a lattice plane
to be found in the crystal which cancels out the deviating scat-
tering. This produces sharp Bragg reflections at defined diffrac-
tion angles. However, for small crystals with finite dimensions,
there might not always be a plane which could cancel out this
scattering contribution. The relation between the broadening of
reflections and the finite size of crystalline domains is clearly
described by Jenkins and Snyder.10 As an example: if the incident
beam is deviating 10% from the Bragg angle, the phase lag ABC
would be 1.1l. The sixth plane down from the surface will be
exactly out of phase (phase lag 5.5l) and will therefore cancel out
the reflection from the first plane. For small deviations from the
Bragg angle, say, a deviation of 0.01% corresponding to 1.0001l,
the wave of the first layer will be canceled out by layer number
5001. For small crystallites it could thus happen that plane
number 5001 is not present and the slightly deviating wave will be
not cancelled out. If this is the case then an intensity contribution
will appear at somewhat lower q angle and, thus, will lead to
a broadening of the reflection. The relation between the thickness
of a crystallite, Lhkl, number of lattice planes, N, and the inter-
planar distance, dhkl, is given by (eqn (2)):
Lhkl ¼ Ndhkl (2)
Crystals having sizes larger than roughly 100 nm do not
contribute to the broadening of reflections. Such crystals have
a sufficiently large number of lattice planes to ensure that waves
not fulfilling the Bragg equation will be extinguished. Even
though computer programs used for calculation of particle sizes
from reflection broadening may yield numbers up to several
thousand nanometres, only values up to about 100 nm should be
seriously discussed for laboratory diffractometer data. The lower
limit of detection of this method is between 1 and 3 nm,
depending on the structural properties, scattering behavior of the
material analyzed, and the instrument/radiation source used.
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 View Online

Fig. 3 shows calculated powder patterns of platinum assuming

different crystallite sizes. Pattern (a) represents platinum con-
sisting of crystallites larger than 100 nm. Pattern (b) shows the
broadened pattern of platinum with crystallite sizes of about
10 nm. From pattern (c) it can be seen that crystallite sizes
smaller than 3–2 nm result in extensively broadened reflections,
that they cannot be distinguished from the background. At this
point one should consider that the integrated intensities of the
Bragg reflections are always constant, independent of the crys-
tallite sizes. While the reflections broaden with smaller particle
size, absolute intensities thus have to decrease for a given integral
intensity.
Published on 13 January 2011 on http://pubs.rsc.org | doi:10.1039/C0NR00561D

1.2 Crystal size determination

Unfortunately, quite often the term ‘‘particle size’’ is used inap-

propriately in combination with size determination from
broadened X-ray reflections. The terms ‘‘grain’’, ‘‘particle’’, or
‘‘agglomerate’’ should not be mixed up with the term ‘‘crystal-
lite’’. The object shown in Fig. 4a consists of one single crystalline
domain (i.e., a coherently scattering domain) with sizes of
10 nm  10 nm along the two shown dimensions. Such a domain
with a three-dimensional periodically ordered arrangement Fig. 4 (a) Single crystallite and (b) three differently oriented crystallites
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complies with a perfect ‘‘single crystallite’’. Size determination form an agglomerate.

from XRD reflections is sensitive to exactly such ‘‘coherently
scattering domains’’. In contrast to a single crystal, a ‘‘grain’’,
‘‘agglomerate’’, or ‘‘particle’’ might consists of several crystallites
as illustrated in Fig. 4b. The shown agglomerate, consisting of
several smaller crystalline domains, has a mean size of about
10 nm. X-Ray reflection broadening, however, is sensitive to the
sizes of the smaller single crystalline domains. If the sizes of
respective particles (grains, agglomerates) are determined by
methods such as electron microscopy (EM) or dynamic light
scattering (DLS), their total sizes will be assessed (about 10 nm)
which are significantly larger than those of the individual crys-
talline domains as determined by XRD line broadening.
Another reason why occasionally different sizes of particles are
determined by electron microscopy and XRD is shown in Fig. 5.
A crystal coated by a thick amorphous layer in total forms
a particle being much larger than the crystalline part in the
center. In such a case, the size of the crystalline domain, as
determined by XRD, and that of the whole particle, as deter-
mined by electron microscopy or DLS, are different. However, if
high resolution TEM is used, amorphous rim and crystalline core
can be distinguished in many cases.
It should always be considered critically, what kind of infor-
mation the different methods that are used for the determination
of particle sizes actually provide and what type of size they assess.
Powder diffraction data consider the size of coherently scattering
domains. Aggregation of two or more domains forming larger
agglomerates will not change the size of the individual single
domains. Other methods might be not able to distinguish
between agglomerates of smaller crystallites and large single
crystalline domains. Light scattering and, in some cases, TEM

Fig. 5 Illustration of a ‘‘particle’’ consisting of a crystalline core and an

Fig. 3 Calculated powder patterns of platinum, simulated for different amorphous surface layer (grey color). The size of the crystallite is 10 nm
crystallite sizes: (a) 100 nm, (b) 10 nm and (c) 1 nm. and the overall size of the particle is about 12 nm.

794 | Nanoscale, 2011, 3, 792–810 This journal is ª The Royal Society of Chemistry 2011

are limited to this respect. In diffraction experiments, relatively
large amounts of a given sample are analyzed, and the results
therefore are generally very representative for the whole sample.
In contrast to that, electron microscopy provides very local
information. TEM is only applicable to rather thin samples. For
this reason, usually only those parts of a given sample are
investigated which are thin enough to allow an electron beam to
pass through. Therefore, larger particles are easily overlooked,
even though they might represent a major part of the sample.
TEM images are thus often not representative for a whole
sample.
The microstructure of crystalline solids, especially crystallite
size and strain due to lattice distortions, governs important
Published on 13 January 2011 on http://pubs.rsc.org | doi:10.1039/C0NR00561D
physical properties of materials. Already in 1918 Scherrer dis-
cussed that small-sized crystallites cause broadening of diffrac-
tion lines.1 The observation that the integral breadth of
a reflection is inversely proportional to the apparent size was the
basis for the so-called integral breadth methods. Based on earlier
work,11,12 Stokes and Wilson identified lattice strain as another
source of broadening.13 Deviation of the interplanar distances
from the regular values causes line broadening, the degree of
which differs for different (hkl)-classes of reflections. There are
two classical approaches to obtain information about the
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microstructure from powder diffraction data. Both relate the
determined parameters with defects and strain or crystallite size.
The first approach is based on the expression of the measured
pattern as a Fourier series.14 The observed diffraction profile h(x)
is a convolution of the contribution f(x) from the sample, which
contains the information about the microstructure, and an
instrument function g(x). Stokes adapted the Fourier deconvo-
lution method to obtain the corrected intensity distribution of
a diffraction peak and therewith the pure physically broadened
line profile from the measured pattern.14 For deformed metals
and alloys, Averbach and Warren15–18 developed an algorithm,
which separates the two main sources of broadening, i.e., size and
strain. Williamson and Hall proposed a method for deconvolu-
tion of size and strain broadening by analyzing the peak width as
a function of 2q.19 The method can be applied to separated, well-
resolved diffraction lines, and it is based on pattern deconvolu-
tion methods. Simplified integral-breadth methods (such as
Scherrer or Williamson–Hall) assume either a Gaussian function
for strain-broadening or a Lorentzian function for size-broad-
ened profiles. The implementation of a Voigt function to the
integral breadth methods has been shown to be an improve-
ment.20,21 A limitation of the classical Warren–Averbach and
Williamson–Hall methods is that strain anisotropy effects are not
considered. Modified Williamson–Hall methods allow taking the
dislocation strain field into account.22–24
For many decades, the size of crystallites or crystalline
domains has been determined by application of the Scherrer
equation (eqn (3)):
kl
Lhkl ¼ (3)
b cos q
with L: volume averaged crystallite size, k: Scherrer constant
(depends on the crystallite shape, the way in which L and b are
defined, and on the size distribution. The constant is the ratio by
which the apparent size must be multiplied to give the true size),
l: wavelength, b: integral breadth, and q: angular peak position.
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In using the Scherrer algorithm, there are four major mistakes
which can be made:
 using full-width-at-half-maximum, FWHM, instead of
integral breadth b
 ignoring the contribution of the instrumental setup as
a source of additional peak broadening
 evaluating peaks which consist of overlapping Bragg reflec-
tions
 ignoring the contribution of stress, strain, dislocations, twins
or stacking faults to the broadening of reflections.
There are two different definitions for the width of a reflection
that must be not confused, if crystallite size analysis should be
precise (Fig. 6). The conventional FWHM describes the width of
the diffraction peak in radians, at half height between the
background and peak maximum. The integral breadth b repre-
sents the total area under the peak profile divided by the intensity
at maximum (eqn (4)). It can be regarded as the width of a rect-
angle having the same area and the same height as the peak.
ð
Idq
b¼ (4)
Imax
with I: integrated intensity and Imax: intensity at the maximum.25
As already mentioned, most profiles can be described by
a Pseudo-Voigt function, a convolution of Gauss and Lorentz
functions (Fig. 12, eqn (5)):
pV(x) ¼ hL(x) + (1  h)G(x) (5)
with a mixing factor h, 0 < h < 1.
The convoluted profile can take any shape between the pure
Gaussian profile (h ¼ 0) and pure Lorentzian profile (h ¼ 1)
(Fig. 7).
The relations between the integral breadth b and FWHM for
Lorentz and for Gauss functions are (eqn (6) and (7)):
Lorentzian peak shape:
Fig. 6 FWHM: width of the peak at ½ of its maximum intensity.
Integral breadth b is defined by the width of a rectangle having the same
area and the same height as the peak.
Nanoscale, 2011, 3, 792–810 | 795

Fig. 7 (a) Pure Gaussian profile and (b) pure Lorentzian profile.
p 
b¼ FWHM
2
Gaussian peak shape:
Published on 13 January 2011 on http://pubs.rsc.org | doi:10.1039/C0NR00561D
rffiffiffiffiffiffiffiffiffiffiffi
p
b¼ FWHM
4 ln 2
In the case of peak broadening due to small crystallite sizes, the
profiles have a dominant Lorentzian contribution. In such cases,
FWHM and b will have significantly different values, and using
FWHM in the Scherrer equation results in wrong particle sizes
(Fig. 8). The integral breadth b is larger than FWHM, and as
a consequence, crystallite sizes are overestimated using FWHM.
Quite often it is not considered that also the diffraction
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instrument contributes to the broadening of reflections. The
measured profile H(x) is the result of the convolution of the
sample-induced broadening F(x) and the instrument-induced
broadening G(x) (eqn (8)):
H(x) ¼ F(x)  G(x)
While we are interested only in the contribution of the sample
to the broadening of the reflections, the measured reflection
profile has to be corrected for the instrumental contribution. The
latter is determined by measuring a reference material, such as
LaB6 or silicon, consisting of crystallites with sizes large enough
not to cause peak broadening. For a reliable analysis the use of
suitable computer programs is recommended.
The next example illustrates how significantly the consider-
ation of the instrumental contribution affects the calculated
crystallite sizes. For deconvolution of size and strain contribu-
tions to the entire profile, a profile fit was performed. The profile
fit allows a deconvolution of the peak shapes into Gaussian and
Lorentzian contributions. For size evaluation, only the
Fig. 8 Peak with a pronounced Lorentzian peak shape illustrating the
two different peak widths FWHM and integral breadth b.
796 | Nanoscale, 2011, 3, 792–810
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Lorentzian contributions are considered. During the fitting also
integral breadths b and FWHM have been determined.
Without consideration of instrumental broadening, the
average crystallite size of a nanosized Cr2O3 sample (Fig. 9) was
determined to be 20 nm. After consideration of the instrumental
contribution, a mean crystallite size of 15 nm was determined.
This corresponds to an error of the results of about 25%, which
underlines how important it is to consider the instrumental
contribution properly.
As discussed above, using FWHM instead of the integral
(6) breadth leads to much larger apparent crystallite sizes than
actually are present. In the case of the Cr2O3 example, using
FWHM results in a mean crystal size of 48 nm whereas using the
integral breadth b results in a mean size of 15 nm.
(7) The further discussion will show that for this specific example
also the latter value is not correct, because a significant distri-
bution of crystallite sizes has to be considered here. The effect of
crystallite size distribution will be discussed in more detail in the
next chapter.
1.3 Crystal size distribution
The Scherrer approach assumes a homogeneous size of the
crystalline domains. This can lead to wrong results for crystallite
sizes if a broad distribution from small to large crystallites occurs
within one sample. The evaluation of the shape of the tails
already gives a qualitative impression about the distribution of
(8) crystallite sizes. Small crystals contribute to the flanks of the
reflections whereas larger crystals contribute more to the peak
center. How significant peak profiles can vary, depending on
whether the sample is monodisperse or polydisperse, is shown by
the simulated diffraction peaks in Fig. 16. The powder pattern
for a monodisperse sample consisting of 4 nm platinum crystals
exhibits broadened peaks (Fig. 10a) while the diffraction peak of
a sample consisting of 65 nm crystals is less broad (Fig. 10b). The
analysis of such profiles would be straightforward. However, the
picture looks different if the crystal sizes are polydisperse
(Fig. 10c). If a sample consists of a mixture of very small and
larger crystallites, the resulting peaks exhibit a very special shape.
Ignoring the fact that the crystallite sizes are polydisperse would
lead to a wrong mean crystallite size. Without applying appro-
priate analysis programs, it is very difficult to identify a size
Fig. 9 Section of the powder diffraction pattern of Cr2O3. The pattern
shows the measured data (dotted line), the fitted data (solid line) and the
difference curve (bottom).
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Published on 13 January 2011 on http://pubs.rsc.org | doi:10.1039/C0NR00561D
Fig. 10 (a) Monodisperse sample with crystal size of 4 nm, (b) mono-
disperse sample with crystal size of 65 nm, (c) polydisperse sample with
a mixture of crystals of sizes 4 nm and 65 nm, and (d) polydisperse sample
representing a mixture of crystals of 4 nm and 11 nm sizes.
distribution if the sizes of the different fractions are not much
different (Fig. 10d).
Coming back to the Cr2O3 sample of which the XRD reflec-
tions are shown in Fig. 9, inspection of TEM images shows that
in this sample a broad size distribution is present (Fig. 11). The
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sample consists of both large bulky crystals (A) and regions with
an ordered, porous structure (B) (Fig. 11a). The latter region
itself is formed of small crystals of Cr2O3 (C) which are arranged
in such a way that large pores of about 10 nm are formed
(Fig. 11b). The corresponding powder pattern of the sample
shows a very pronounced Lorentzian peak shape (Fig. 9). For
such type of samples, estimation of the domain sizes from the
powder diffraction data by the simple Scherrer formula would
lead to a mean crystallite size which would be absolutely mean-
ingless. More elaborated evaluation algorithms have to be used,
which consider a given size distribution.
Why size distribution should be carefully considered is shown
for nanosized Co3O4 (Fig. 12). Both powder patterns correspond
to nanocrystalline Co3O4 samples. As discussed above, the shape
of the peaks already indicates that size distribution has to be
considered. The use of the simple Scherrer algorithm is not
sufficient as shown in the following. Using the integral breadth of
the reflections for the calculation of the mean size results in 7 nm
for sample A and 4 nm for sample B. The TEM image of sample
A (Fig. 13) shows that the result for this sample is not correct
Fig. 11 (a) TEM image showing an overview of the Cr2O3 sample with
regions of bulk Cr2O3 (A) and of nanostructured Cr2O3 (B). (b) One
individual crystalline domain is marked by the circle (C) (sample and
TEM images provided by H. T€ uys€
uz).
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Fig. 12 XRD patterns of Co3O4 (a) sample A and (b) sample B.
since the Scherrer formula does not consider the very broad size
distribution. For sample B the size distribution is rather homo-
geneous and the size obtained by XRD line broadening corre-
sponds well with the TEM results (Fig. 13).
Modern algorithms for line-broadening analysis allow the
analysis of both the mean apparent domain size and the size
distribution. Fourier based methods consider all information
contained in a peak profile. They consider instrumental broad-
ening and broadening caused by strain effects and allow deter-
mination of the distribution of crystallite sizes.15–18 The line
profiles of two catalysts with different size distributions are
shown in Fig. 14.26 The reflection profile of a Pt catalyst sup-
ported on SiO2 is broad and flat (Fig. 14a) indicating a narrow
size distribution, while the profile of Pd on carbon is more
narrow and tall at the center (Fig. 14b) indicating a broad size
distribution.
Fourier transform methods are based on the extraction of the
sample-induced broadening F(x) from the Fourier transform of
the measured profile H(x) and instrumental contribution G(x)
(see eqn (8)). The Fourier coefficients C(n,L) [¼A(n,L) + iB(n,L)
with n: Fourier harmonic number and L: the order of reflection]
of a profile can be expressed as product of real, order indepen-
dent size coefficients ALS and complex, order-dependent distor-
tion coefficients ALD. Considering only the cosine coefficients,
a separation between size and strain effects is applied. Averbach
and Warren15 assumed that the cosine coefficient AL of the line
profile is the product of size, ALS, and strain, ALD, Fourier
coefficients (eqn (9)):
A(n) ¼ ASLAD
L (9)
From the plot of the computed Fourier coefficients ALS for the
(111) reflections of the metal catalysts versus the thickness L
Fig. 13 TEM images of samples A (left) and B (right).
Nanoscale, 2011, 3, 792–810 | 797

Fig. 14 (a) Pt/SiO2 catalysts with a narrow distribution of crystallite
sizes and (b) Pd/carbon catalyst with a wide distribution of crystallite
sizes. (Reproduced from ref. 25 with the permission of IUCr.)
Published on 13 January 2011 on http://pubs.rsc.org | doi:10.1039/C0NR00561D
Fig. 15 (a) Pt on SiO2 and (b) Pd on carbon. (Reproduced from ref. 25
with the permission of IUCr.)
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perpendicular to the diffracting planes hkl (Fig. 15) several size
parameters can be obtained.
The intercept of the initial slope on the L axis gives the surface-
weighted mean crystallite size (D0 ). The area DD’E represents the
variance of the size distribution function. For the graph in
Fig. 15a a narrow distribution results, and for the graph in
Fig. 15b a broad one. The mean crystallite sizes for both catalyst
compounds, determined by 3 different methods, are summarized
in Table 1. The values D0 are obtained by Fourier methods, Db
corresponds to the value obtained from the integral breadth, and
DFWHM was based on FWHM.
The double Voigt methods of analyzing peak broadening were
first introduced by Langford and further developed by Balzar
providing much the same information that one could obtain
from the Fourier methods.20,27,28 The peaks are fitted using the
Voigt function which allows us to determine Lorentz and Gauss
contributions to each peak. This approach allows also correction
for instrumental broadening. Structure independent methods for
crystallite size determination from line profile analysis do have
restrictions if reflections of different crystalline phases or several
Bragg reflections overlap. This problem can be overcome if
whole-powder pattern fitting (WPPF) methods are used. WPPF
Table 1 Mean crystallite sizes for two different types of supported
catalysts determined by different methods: D0 by Fourier methods, Db by
the Scherrer equation using the integral breadth b, and DFWHM by the
Scherrer equation using FWHM. (Reproduced from ref. 25 with the
permission of IUCr)
Catalyst D0 /nm Db/nm DFWHM/nm
Pt on SiO2 5.3 6.0 5.9
Pd on carbon 4.3 7.2 13.0
798 | Nanoscale, 2011, 3, 792–810
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methods are based on arbitrary profile functions such as Voigt,
pseudo-Voigt or Pearson VII functions. Nowadays, different
algorithms are implemented in several Rietveld programs which
allow the simultaneous refinement of crystal structure and
microstructure properties. The Rietveld method relates the
integrated intensities to a crystal structure model.29,30 Hereby, the
information of each data point of a powder pattern is taken into
account. From a known crystal structure model, the entire
powder pattern can be calculated. This is not limited to a single
phase system but is also applicable to multiphase systems.
However, if the microstructure analysis is based on analytical
profile functions, Rietveld refinement has limitations. For
example if Voigt or pseudo-Voigt functions are used, the size
distribution of dispersed nanocrystalline materials cannot be
determined properly and size effects are overestimated.31
Compared to WPPF the whole powder pattern modeling
(WPPM) approach allows the refinement of microstructure
parameters by direct fitting of modeled and experimental data.
The peak profile is modeled without using arbitrary empirical
profile functions but is based on physical models. The advantages
of WPPM over WPPF and conventional line profile analyses are:
(a) all effects contributing to the line profile can be considered
and (b) physical parameters, such as the domain size, size
distribution, dislocation densities, distortions, such as faults and
twins, are directly determined from the experimental data in
terms of physical parameters without any intermediate stage of
profile fitting.32,33
1.4 Anisotropic peak broadening
While small crystallite sizes cause a more or less uniform
broadening of the entire diffraction profile, there may also occur
broadening of only individual reflections. This effect is called
anisotropic peak broadening for which various reasons, such as
(1) anisotropy of the crystal shape, (2) anisotropic strain, and (3)
stacking faults within the crystal structure, may account for.
1.4.1 Crystal morphology. In the Scherrer equation Lhkl is
defined as the volume average of the crystallite dimension in
a direction normal to the reflecting plane. The sharpness of
reflections within a pattern varies sometimes significantly. A
closer inspection of the width of single Bragg peaks representing
specific directions in a crystal can give important information
about the shape of the crystallites. The analysis of SrF2 nano-
crystals with a high aspect ratio is an example where the crystal
shape has to be considered for the determination of crystal
dimension. SrF2 crystallizes in the cubic space group Fm3m and
was prepared by Yan and co-workers.34 The crystals form
nanoneedles as shown in Fig. 16a (TEM). The powder pattern of
the corresponding sample exhibits a very special peak pattern
with broad and narrow reflections (Fig. 16b). The relatively
sharp reflections are (200), (220), (400), (420), and (440) whereas
the other reflections such as (111), (311), (331), and (422) are
significantly broadened. Calculation of the crystal dimensions
from the broad reflections yields 3 nm, from the narrow reflec-
tions 15 nm is calculated as the crystallite size. This is due to the
high aspect ratio of the individual crystals. It is thus recom-
mended to inspect the individual reflections representative for
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Fig. 16 (a)TEM images of SrF2 nanoneedles (sample provided by
C. H. Yan) and (b) powder pattern of SrF2 nanoneedles.
a specific direction in the crystal for evaluation of the anisotropy
of the size in different directions.
1.4.2 Strain effects—Stokes and Wilson. Real crystals exhibit
structural imperfections (local distortions) which cause a non-
homogeneous strain. As an example, such imperfections can be
introduced by ball milling of powder materials. By mechanical
processing strain effects are induced which cause either a shift of
the peak positions and/or additional peak broadening (Fig. 17).
For uniform strain, the unit cell dimensions change in an
isotropic way which leads to changes of the lattice parameters
and a shift of the peaks (Fig. 17b). No reflection broadening is
associated. For non-uniform strain, systematic shifts of atoms
from their ideal position result in additional peak broadening
(Fig. 17c).
If the broadening of reflections is caused by strain effects, the
relation between ‘‘apparent’’ strain h and integral breadth as
Fig. 17 Diffraction profiles and positions if (a) no strain is applied, (b)
uniform strain is applied, and (c) non-uniform strain is applied.
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discussed by Stokes and Wilson can be applied.13 They report
that for cool worked metals the ‘‘apparent strain’’ h is given by
eqn (10):
h ¼ b(2q)cot q (10)
The relation of h with the ‘‘upper limit’’ strain 3 is given by
eqn (11):
Dd h bð2qÞ
3¼ ¼ ¼ (11)
d 4 4tan q
A deconvolution of size and strain components, having
different angular dependences, is performed by the Williamson–
Hall method.35,19 Contributions from the Scherrer domain size
and from strain effects are both considered. If the Scherrer
equation is modified in such a way that both, isotropic size and
strain, are considered, the following relation is obtained (eqn
(12)):
kl
b cos q ¼ þ 43 sin q (12)
L
If bcos q is plotted against 2sin q a straight line with slope 23
and intercept kl/L is obtained (k generally set to 0.9). The
Williamson–Hall plot shown in Fig. 18 represents iron powders
which were ball milled with different disk speeds (rpm).
From the analysis of the slope, the strain contribution, 3 or h,
is determined, and from the intercept of the line with the y-axis,
the mean domain size, L, is obtained. The evaluation of all four
curves results in a decrease of the mean size of iron crystallites
from 140 nm to about 30 nm with increased disk speed and an
increase of the strain parameter h from 0.85  103 to 6.36 
103.36
1.4.3 Stacking faults: ETS-10. Stacking faults can cause
effects in powder diffraction patterns which might lead to diffi-
culties for the interpretation. Microporous titanosilicate ETS-10
is such a candidate with significant asymmetries and broadening
of distinct reflections (Fig. 19a). A closer inspection of HRTEM
images of ETS-10 (Fig. 19b) is required to actually assign the
broad and asymmetric profiles to stacking faults.37
Fig. 18 Williamson–Hall plot for samples prepared by ball milling by
applying different disk speeds (150, 250, and 350 rpm).36
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Fig. 19 (a) Powder diffraction patterns of ETS-10, broad and strongly
asymmetric reflections that are caused by stacking faults are marked with
the arrows. (b) HRTEM of ETS-10 showing the presence of micropores
and structural disorder. (Reproduced from ref. 35 with the permission of
Wiley-VCH.)
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1.4.4 Overlapping reflections. Before discussing the effects of
overlapping reflections, some definitions might be helpful. In the
following, a distinction is made between reflections and peaks. If
the Bragg equation is fulfilled, a Bragg reflection appears at
a certain diffraction angle 2q representing one set of lattice planes
having the Miller index hkl (Fig. 20a). Depending on the
symmetry and the size of the unit cell, several Bragg reflections
can appear very close to each other. If this is the case, the
envelope of the single reflections would result in one peak
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(Fig. 20b) even though it represents several individual Bragg
reflections.
The Scherrer algorithm is sometimes applied without consid-
ering that this simple method is only applicable to single Bragg
reflections. The method yields wrong values, if a measured peak
is evaluated that represents the envelope of two or more over-
lapping Bragg reflections (Fig. 20). Fig. 21a shows a part of
a powder pattern of a nanosized microporous zeolite. In fact, the
peak at about 7.9 2q consists of two overlapping Bragg reflec-
tions, i.e. the (101) and (011) reflections. Not knowing this fact
easily could result in an assignment as a single reflection, as
shown in Fig. 21b. Analogous considerations can be made for the
reflection at about 8.8 2q. Thus, calculated particle sizes would
be smaller than those of the real particles actually being present
in the sample.
The crystal size determination correctly considering both
Bragg reflections as applied in Fig. 21a results in a correct mean
crystallite size of 54 nm. If only one reflection is assumed,
a wrong crystallite size of 43 nm is obtained.
Fig. 20 (a) Single Bragg reflection at 8.5 2q, Miller index (101), and (b)
three strongly overlapping Bragg reflections, (003), (100), and (101); as
the result, a single peak is observed that comprises of three Bragg
reflections.
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Fig. 21 (a) Considering the correct number of overlapping Bragg
reflections for analysis of the peak profile and (b) wrong profile analysis
using only single Bragg reflections.
1.4.5 Summary on application of the Scherrer formula for the
analysis of particle sizes. It is important to keep in mind that
crystal sizes determined by the Scherrer formula are volume
weighted averages. The drawback of the Scherrer algorithm thus
is that it does not consider particle size distributions. If a sample
contains both large and small crystallites, then the resulting
diffraction profile represents a convolution of narrow and broad
reflections, whereby the narrow peaks dominate the profile.
Another problem arises from the fact that the Scherrer formula
does not consider contributions of microstrain and/or structural
disorder (stacking faults) to peak broadening. However, not only
sample properties are sources for broadening of the profiles, also
instrumental factors contribute to the widths of reflections.
Without correcting for the instrumental contribution, the
determined particle size is not correct. The analysis of a reference
sample, that does not show any broadening due to small parti-
cles, reveals the instrumental contribution. Unfortunately,
correction for instrumental contribution is not considered by the
simple Scherrer equation.
For a reliable analysis it is important to consider the following
points:
(a) For non-cubic systems, consideration of only one reflection
can lead to very misleading results. If the crystals are shaped as
plates or needles, usually the crystal size varies significantly in the
three crystallographic directions. For example the analysis of
predominant (h00) reflections represents the size in a-direction
but does not provide any information about the size in b- and c-
direction. On the other hand, a careful analysis of the reflections
gives additional information about the morphology of the
crystals.
(b) For low symmetry structures, the observed peaks often
represent the envelope of several overlapping Bragg reflections. If
the unit cell of the phase is unknown, it is not possible to assign
the number of Bragg reflections contributing to one peak. In this
case, only single reflections can be used for particle size deter-
mination. Assuming a single reflection instead of overlapping
reflections results in wrong values.
Generally, TEM is a very local probe and therefore TEM
images are not necessarily representative for the whole sample.
Usually, only that part of a given sample is investigated that
allows transmission of electrons which is in most cases the
thinnest part of matter. For powder samples these are the smaller
particles and larger particles and aggregates, that may be also
present in the sample, are easily overlooked. The Cr2O3 example,
shown in Section 1.3, can also be used to explain potential
differences between crystal sizes from XRD and TEM data.
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From evaluation of the XRD data we know that the sizes of the
Cr2O3 crystallites are not homogeneous but have a relatively
broad distribution. Contradictory to this the TEM image, as
shown in Fig. 11b, suggests that the size of the crystalline
domains of the mesoporous Cr2O3 sample is about 8 nm.
However, for that image the operator used a very thin piece of
the sample representing exactly the nanoporous metal oxide
structure expected. However, this image is not representative for
the whole sample for which a survey image is shown in Fig. 11a.
It shows that the sample contains nanoporous Cr2O3 consisting
of ordered networks of Cr2O3 nanoparticles next to large, bulky
Cr2O3 crystals. In general, XRD is more likely to detect all types
of phases and crystallite sizes being present in a sample due to the
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relatively large amount of sample which is investigated, whereas

TEM intrinsically shows only a rather tiny fraction of a sample.
Using TEM, great care has to be taken to make sure that the
images shown are representative for the whole sample. For this,
survey scans from several fractions of the sample have to be
made. The situation becomes especially difficult, if a sample
consists of large and bulky particles through which transmission
of the electron beam is not possible. Information from these parts
of the sample is not easily accessible by TEM. Thinner parts of
such a sample, that can be investigated by TEM, are not neces-
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sarily representative of the bulkier particles. More elaborated

sample preparation methods, such as resin embedding and
cutting, ion beam thinning, and the like, have to be applied to
such samples.

1.4.6 Specific surface area: mismatch between data from gas

adsorption, electron microscopy, and powder diffraction. It is not
an unusual observation that surface areas of solids that are
calculated from crystal sizes determined by X-ray diffraction
data (XRD) are substantially different to those obtained from
gas adsorption experiments. An example will display the
mismatch between XRD and gas adsorption data. It illustrates
that determination of specific surface areas or particle sizes by
just one experimental method is often not sufficient and requires
the cross check by a second method. This is even more important
if conclusions are drawn on chemical or physical properties of
a given material. Gas adsorption determines the specific surface
area of the entire sample. It can be regarded as the summation of
the surfaces of all crystalline and amorphous particles that are
accessible to the gas. An average particle size can then be esti-
mated on the basis of geometric considerations if the specific
density of the material is known. In contrast to that, evaluation
of XRD peak broadening directly yields particle sizes from which
specific surface areas can be calculated. However, only crystalline
components are considered in this case. If a sample comprises of
both amorphous and crystalline components, one has to be very
careful in comparing the results obtained by gas adsorption and
XRD. Generally, a very simple check of the XRD data gives
a first indication whether large crystallites are present, which
somehow excludes high surface areas. The reflections of the
crystalline Al2O3 component, as shown in Fig. 22a, are quite
narrow indicating the presence of large crystallites. Electron
microscopy confirms the presence of rather large Al2O3 crystals
(Fig. 22b). One would not expect large specific surface areas for
that sample containing such large crystallites. Evaluation of the
crystal size by a modified version of the Scherrer equation yields
Fig. 22 (a)X-Ray diffraction pattern of Al2O3. The increased back-
ground, marked as grey area, indicates the presence of an amorphous
phase (sample provided by A. Martinez-Joaristi). (b) TEM image of the
Al2O3 sample shows a very broad particle size distribution and the
presence of very large crystals (TEM provided by A. Martinez-Joaristi).
sizes between 70 and 80 nm. Based on this crystal size, the specific
surface area can be estimated according to eqn (13):
6
A¼ (13)
d,d
with A being the specific surface area (m2 g1), d the particle
dimension (m), and d the density (g m3).
This simple equation is based on geometric relations between
the surface area, volume, and mass of a body and strictly holds
only for cubes (d ¼ length of the edge) and spheres (d ¼ diam-
eter). Using that equation, the specific surface area for the
crystalline Al2O3 phase is calculated to be about 22 m2 g1. From
N2 adsorption data, a specific surface area of 238 m2 g1 is
calculated. This surface area would correspond to a hypothetical
crystal size of 6 nm. How can this mismatch be explained? A
closer look on the diffraction pattern shows that the sample
contains a large fraction of an amorphous component repre-
sented by the hump between 20 and 50 2q. The amorphous
component also contributes to the specific surface area of the
sample as determined by gas adsorption. The high specific
surface area is obviously caused by the amorphous compound
rather than by the crystalline Al2O3 phase.

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As a recommendation, it might be useful to distinguish clearly

whether the surface area of the entire sample is of interest or
rather the surface area of the crystalline component. In the first
case, gas adsorption data can be used because they represent the
integral surface area of the entire sample, in the latter case it is
more reasonable to use data derived from XRD peak broadening
or TEM.

1.5 Determination of diffraction peak positions

The unit cell parameters of crystalline materials are determined
from the angular positions of the Bragg reflections. It is obvious
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that only a precise determination of the peak positions allows the

determination of exact unit cell parameters. The determination
of reflection positions is very sensitive towards misalignment of
Fig. 24 Si (111) X-ray reflection measured with (a) too low sample
both the instrument and the sample position. Fig. 23 shows the position, (b) correct position, and (c) at too high sample position.
effect of the sample height on the peak position for Bragg–
Brentano geometry.
All three components, i.e., X-ray source (S), sample surface, Table 2 summarizes the errors resulting from the deviation
and detector (D), have to lie on the focusing circle of the from the optimum sample position for a goniometer with radius
diffractometer. If that is the case, the focusing conditions are R ¼ 275 mm using the data as shown in Fig. 24. A position shift
perfectly fulfilled and a given Bragg peak will be detected at the of the sample of only a few hundred micrometres results in
correct 2q position (Fig. 23a). If the sample is positioned too low, significant peak shifts and, as a result, significant shifts of the
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either due to incomplete filling of the sample holder or due to
wrong positioning of the sample stage and/or sample holder, the
same Bragg reflection will be detected at too low 2q angle
(Fig. 23b). If the sample is positioned too high (Fig. 23c), the
Bragg reflection will be determined at too high 2q angle. The use
of incorrect reflection angles results in either too small or too
large lattice parameters. The magnitude of the position error in
radian can be expressed as eqn (14):38
cos q
D2q ¼ 2s
R ened peaks is difficult. Therefore, the lattice parameters
with s being the displacement of the sample (mm) and R the
radius of the goniometer circle (mm).
lattice parameters.
How can peak positions be determined precisely? First, the
alignment of the diffractometer should be checked. For correc-
tion of specimen displacement, an internal standard should be
used. There exist several reference materials, such as silicon or
LaB6 powders that are commercially available. Precise determi-
nation of reflection positions is mandatory for the interpretation
of changes of a given unit cell (swelling, shrinkage, incorporation
of guest atoms or molecules in a crystal structure). For nano-
(14) particles the exact determination of positions from the broad-
calculated from these peak positions are less precise and require
very careful evaluation.

2. X-Ray photoelectron spectroscopy (XPS)

X-Ray photoelectron spectroscopy (XPS) is a surface sensitive
spectroscopic method for the chemical characterization of the
first atomic layers of a solid surface. It provides information
about the chemical elements on or close to the surface, i.e., their
oxidation states and their chemical environments. XPS was
developed for probing the surfaces of structured samples, such as
thin films or layered materials. Nowadays, surface sensitive
Fig. 23 (a) Sample is positioned correctly, (b) sample position is too low, methods are also applied in the fields of heterogeneous catalysts
and (c) sample position is too high. and nanoscaled materials. The following examples might help to
avoid frequent mistakes in interpretation of XPS data.
Table 2 Influence of the sample height on peak position and lattice
parameter of silicon standard 2.1 Encapsulated particles: what is inside what is outside?
Too high Ideal position Too low It has been shown previously that small Au nanocrystals (15 nm)
 can be encapsulated in a shell consisting of nanocrystalline ZrO2
2q position ( ) for Cuka 28.551 28.458 28.216
D2q/ 0.093 0 0.242 (Fig. 25).39 The thickness of the wall of the ZrO2 shell was
d Value/A 3.1238 3.1337 3.1602 determined to be about 15 nm.
Sample shift/mm 220 0 600 The sample was analyzed by XPS with respect to the question
Lattice parameter/A  5.4106 5.4277 5.4736
DLattice parameter/A  0.017 0 0.0459 whether it would be possible to detect the nanoparticles inside the
hollow spheres by such a type of surface sensitive method. The

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Fig. 27 TEM image of nanoparticles of Fe2O3 encapsulated in the pores

Fig. 25 TEM image of Au nanoparticles encapsulated in ZrO2 hollow of synthetic CMK-5 carbon material (sample provided by J. Nitz and A.
spheres (sample provided by M. Paul). H. Lu).

Fe2O3, reflections originating from the sample holder are

present. The transmission of the X-ray beam in carbon materials
is very high for which reason the X-ray beam might penetrate
completely through the sample and finally hits the bottom of the
sample holder. If the sample holder consists of crystalline metal
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such as aluminium or steel, diffraction peaks of the sample

holder material are produced. If the reflections cause any prob-
lems during data evaluation, sample preparation on sample
holders made from cut single crystals or polymeric material is
recommended.
Since the walls of the carbon host are only several nanometres
thick, one might try detecting the embedded nanoparticles by
XPS. However, this is not possible as shown in Fig. 29. The main
Fe 2p signal at 711 eV is not visible, indicating a complete
Fig. 26 XPS scans of an as-made sample of Au in ZrO2 hollow spheres shielding of the photoelectrons by the carbon matrix. A possible
and of a crushed sample. The insets show the high resolution scans of the explanation might be the high electron conductivity of the
Au 4f energy range. carbon host which does not allow the photoelectrons to escape
from the sample. Another explanation might be that the carbon
walls are in fact too thick (more than 2–3 nm), so that photo-
as-made sample does not show any Au signals with significant electrons, generated in the Fe2O3 nanoparticle, cannot escape
intensities, whereas a second sample, for which the spheres have from the inner part of the sample to the surface.
been crushed prior to analysis, clearly shows the presence of Au
(Fig. 26). The figure shows the survey scans for both samples
with the main photopeaks belonging to C, O, and Zr. The high
resolution scans in the energy range characteristic for the main
Au 4f signal collected with high counting rates exhibit a clear Au
signal for the crushed sample in contrast to the very weak
intensities for the as-made sample. This experiment shows that
there is a high probability that nanoparticles encapsulated in
a matrix or shell cannot be detected by surface sensitive XPS. In
the case of the crushed spheres, the nanoparticles are no longer
buried inside the closed spheres but exposed to the surface and
thus detectable by XPS.
The second example highlights Fe2O3 nanoparticles encapsu-
lated in the pores of a synthetic carbon material (CMK-5)
(courtesy of An-Hui Lu). TEM investigations confirm that the
nanoparticles are almost completely incorporated in the pores of
the carbon host (Fig. 27). The quite monodisperse nanoparticles
are visible as dark spots inside the carbon matrix. The crystalline
character and the composition of the nanoparticles are verified Fig. 28 Powder diffraction data of the Fe2O3 nanoparticles in carbon.
by XRD analyses (Fig. 28). Beside the reflections belonging to The marked reflections are due to the sample holder.

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Fig. 29 XPS spectrum of Fe2O3 nanoparticles encapsulated in carbo-
naceous CMK-5. The intersection shows the narrow scan for the main
Fe2p3/2 energy region.
As the examples illustrate, care must be taken if XPS is used
for the analysis of encapsulated or matrix-embedded particles.
The escape depth of electrons is not very deep and therefore the
embedded nanoparticles become invisible for this method.
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2.2 Sputtering of nanosized compounds with argon cations
Sputtering with argon ions is a very common method for
cleaning surfaces of solid samples from contamination or from
surface oxygen layers. While this treatment is very suitable for
solid structured materials, such as coated wafers, it cannot really
be recommended for nanosized materials. The two examples
presented below show that sputtering does not only remove
surface contamination but that it also might change the chemical
nature of elements. Scan (a) in Fig. 30 displays the energy region
Fig. 30 XPS spectra of CoAl2O4 sample (a) before and (b) after
sputtering with Ar ions.
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of the Co 2p photopeak of bulk CoAl2O4. The two Co 2p signals
at 780.6 eV and 796.5 eV represent the spin–orbit couple typical
for Co in the oxidation state +2.40 The spin–orbit interaction
(also called spin–orbit coupling) is an interaction between the
spin and the angular momentum of an electron after photo-
polarization. For unpaired electrons, there are two possible
energetic states depending on whether spin and orbital angular
momentum are parallel or anti-parallel. This causes shifts in the
energy levels of electrons which become detectable as splitting of
spectral lines. After sputtering the sample for several minutes, an
additional signal appears at 777.8 eV, belonging to metallic
cobalt.40 Since the presence of metallic cobalt in the original
spinel sample can be excluded, the metallic species is likely to be
generated during sputtering. This effect is known as preferential
sputtering.41 Ion bombardment can lead to a depletion of the
element with the higher sputter yield corresponding mostly to the
elements with low mass. Transition metal oxides are known to
release oxygen during sputtering, which then is associated with
the reduction of the metals.42,43
The example shown in Fig. 31 demonstrates that cobalt is not
the only element that gets reduced by ion bombardment. MoO2 is
also sensitive to preferential sputtering. Spectrum (a) shows the
Mo 3p photopeaks (Mo 3p3/2 and Mo 3p1/2) of commercial
MoO2 before ion bombardment. The binding energy of 397 eV
for the Mo 3p3/2 indicates Mo2+ as the oxidation state. After
sputtering for 5 min (spectrum b) the main signal at about 397 eV
became less intensive and a second signal at about 393.4 eV has
appeared. After 10 min sputtering time, the signal at 397 eV has
disappeared completely and only the signal at 393.4 eV,
belonging to metallic Mo, is remaining.
The examples demonstrate that surface cleaning by ion
bombardment of a sample containing transition metal ions
creates substantial problems for reasonable discussions about the
oxidation states of specific elements. There is a high probability
that the oxidation state of several transition metals is modified by
Fig. 31 XPS spectra of MoO2 (a) before sputtering, (b) after 5 min
sputtering, and (c) after 10 min sputtering.
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Fig. 32 (a) Structured sample consisting of a metal substrate (Co0) and
cobalt oxide (CoO) layer and (b) spherical nanoparticles with an inner
part consisting of metallic cobalt coated by CoO.
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Fig. 33 Sketch of structured macroscopic samples and nanosized
samples and the illustration of exposed surfaces: (a) before sputtering, (b)
after short sputtering, and (c) after extended sputtering.
the sputtering procedure itself. That makes any assessment of
oxidation states of the pristine materials quite difficult. Another
question one might raise is whether it makes sense at all to
sputter nanosized particles with the purpose to remove surface
oxide layers. Fig. 32 illustrates two entirely different sample
types. Sample (a) shows a macroscopic Co metal substrate with
a thin CoO surface layer, sample (b) a cobalt nanoparticle coated
with the same surface layer. The sketch in Fig. 33 illustrates what
happens during ion bombardment of these samples.
Without sputtering in both cases only the Co oxide surface
coating will be detected (Fig. 33a). At the begin of ion sputtering,
the spectrum does not change for the macroscopic sample
whereas for the nanomaterial, depending on thickness of the
surface layer and sputtering time, both Co2+ and Co0 are detected
(Fig. 33b). After a certain time of sputtering, the surface layer of
the macroscopic sample will be removed completely and the Co
support is exposed (Fig. 33c). For the nanosized sample, the
situation has not changed, still both, Co2+ and Co0, are detected
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simultaneously. For nanosized materials, even after extended
sputtering, one always will detect a mixture of oxidation states.
These differences have to be taken into account for the inter-
pretation of XPS results from ion-sputtered samples.
Sputtering of nanosized materials is a difficult issue which
should only be applied if it can be excluded that the chemical
elements are reduced by the ion bombardment. It should also be
considered that for coated systems always a mixture of the
oxidation state of the inner and out species will be measured.
2.3 Different results for XRD and XPS analyses
Whenever results from different analytical methods are
compared, it should be taken into account to what the different
methods are sensitive. Interpretation of powder diffraction and
XPS data from the same sample might lead to completely
different conclusions about the composition of the sample. The
semiconductor material TiSi2 is considered as a photocatalyst for
water splitting.44 For characterization of the bulk material, the
sample was investigated with X-ray powder diffraction. From
the powder pattern, a mixture of crystalline phases with TiSi2 as
a main compound along with Ti, TiSi, and Si by-phases has been
identified (Fig. 34).
Additionally to the XRD analysis, X-ray photoelectron spec-
troscopy was performed (Fig. 35). The spectra for the two main
elements Ti and Si show that on the surface both elements are
present in the oxidation state +4. This is due to the oxidation of
the surface layers of TiSi2. The contribution of the zerovalent
elements to the surface composition is relatively low. In contrast
to the XPS data, the powder diffraction measurements did not
show any indication for oxidic phases in the sample. This is due
Fig. 34 X-Ray powder diffraction pattern of bulk TiSi2.
Fig. 35 High resolution scans (a) of the Ti 2p binding energy range and
(b) of the Si 2p energy range.
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Fig. 36 Proposed model for the structure of the TiSi2–TiO2 composite.
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to the fact that the oxide layer is rather thin and its total volume
is thus too small for detection with conventional XRD. The
contribution of TiSi2 to the diffracting volume is much higher
than that of the oxidic surface phases. In addition, the oxidic
phases may be non-crystalline. In that case, they would be not
detectable directly by XRD even if present in larger amounts.
However, the combination of both bulk sensitive (XRD) and
surface sensitive (XPS) methods is very powerful and allows
establishing the model as shown in Fig. 36.
Another very valuable combination for the characterization
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of nanosized compounds is the combination of XRD with
solid state nuclear magnetic resonance spectroscopy (NMR).
While XRD investigates structural long-range order, NMR
spectroscopy analyses short-range order phenomena. This
allows closer inspection of nanosized compounds which are
either too small for XRD or for which the structures are not
well-ordered.
3. Gas adsorption
Physical gas adsorption is one of the most important techniques
to characterize nanosized porous materials in terms of specific
surface area, pore size distribution, and pore volume.
3.1 Specific surface area
The specific surface area of a (porous) material is determined
from physical gas adsorption on the external and internal
surface. The amount of adsorbed gas is dependent on the
Fig. 37 Different types of physisorption isotherms as observed for
different adsorbents: type I: microporous, type II: non-porous or mac-
roporous, type III: non-porous or macroporous with weak interaction,
type VI: mesoporous, type V: mesoporous with weak interaction, and
type VI: layer-by-layer adsorption.
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relative vapor pressure (p/p0). The relation between relative
vapor pressure, p/p0, with p0 being the saturation pressure,
and the amount of adsorbed gas at a certain constant
temperature is called an adsorption isotherm. The classifica-
tion of isotherms into six types, as shown in Fig. 37, was
proposed by the IUPAC.45
The different types of physisorption isotherms are indicative
for different adsorbent materials (Fig. 37):
Type I isotherm: microporous adsorbents: isotherm is gov-
erned by adsorption in micropores at low relative pressure.
Type II isotherm: non-porous or macroporous adsorbents:
formation of multilayers of adsobate on surfaces of adsor-
bent, knee at point B indicates completion of monolayer
coverage.
Type III isotherm: non-porous or macroporous adsorbents:
weak adsorbent–adsorbate interactions; monolayer coverage
cannot be identified (non-wetting adsorbate).
Type IV isotherm: mesoporous adsorbents: initial mono-
layer–multilayer coverage on external and mesopore surface is
followed by capillary condensation in mesopores; different types
of hysteresis loops are observed depending on the shape of
pores.
Type V isotherm: mesoporous adsorbents: weak adsorbent–
adsorbate interactions; uncommon isotherm, e.g., observed for
water adsorption on activated carbon.
Type VI isotherm: highly uniform surface: layer-by-layer
adsorption on a highly uniform surface; uncommon isotherm.
The specific surface area of a given material can be assessed if
the number of molecules in a monolayer of the adsorbate and the
occupied space by one molecule are known. Usually, the volume
related to point B is supposed to be that of the monolayer. Quite
often, the exact determination of that point is rather difficult,
e.g., if the knee is not well defined. Therefore, models have been
developed to assess the monolayer capacity of a given adsorbent.
While the Langmuir model of adsorption is based on the
assumption that only a monolayer of gas is adsorbed on
the surface of a solid, multilayer adsorption is considered by the
method developed by Brunauer, Emmett, and Teller (BET
method).46 The BET theory, based on a simplified model of
monolayer–multilayer adsorption and representing an extension
of the Langmuir model, is used as a kind of universal method for
the determination of specific surface areas. However, the BET
method is a relatively limited method for determining surface
areas of nanosized materials because it is based on several
assumptions:
1. Homogeneous flat surface consisting of equivalent adsorp-
tion sites.
2. Only the uppermost molecules of a multilayered adsorbate
are in dynamic equilibrium with the vapor.
3. Heats of adsorption for all layers except the first are equal to
the heat of condensation.
4. A molecule covered by another molecule cannot evaporate.
5. At saturation (p/p0 ¼ 1) the number of layers becomes
infinite.
6. No lateral interaction between adsorbed molecules.
7. Equilibrium is achieved when the rate of condensation is
equal to the rate of evaporation.
Based on these assumptions, the BET can be expressed by
eqn (15):
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p 1 ðc  1Þ p
¼ þ  (15)
nads ðp0  pÞ cnm cnm p0
with p and p0 as equilibrium and saturation pressures of the
adsorptive at the adsorption temperature, nads amount of gas
adsorbed by unit mass of adsorbent, c is an empirical constant
related to the heat of adsorption and indicating the magnitude of
adsorbent–adsorbate interaction energy,47 and nm the monolayer
capacity.
The BET equation requires a linear relationship between
p/nads(p0  p) and p/p0 as shown in the BET plot (Fig. 38).
Linearity is typically observed only in the range of the relative
pressure (p/p0) between 0.05 and 0.3. At higher p/p0 values
capillary condensation occurs and the BET equation is no longer
Published on 13 January 2011 on http://pubs.rsc.org | doi:10.1039/C0NR00561D
valid.
The specific surface area, SBET, is calculated from the mono-
layer capacity nm by eqn (16):
nm
SBET ¼ NA s (16)
M
with M being the molecular weight of the adsorbate, NA the
Avogadro constant, and s the surface area covered by one
molecule. nm and c can be obtained from the slope and intercept
of the linear BET plot.
The BET algorithm can be used for the calculation of specific
Downloaded on 13 April 2011
surface areas of nanoscopic materials but the surface of a particle
with a size of only a few nanometres is not flat but strongly
curved and the individual adsorption sites are not necessarily
uniform but energies of adsorption may vary significantly from
site to site. Also for nanoporous materials specific problems arise
as indicated in the next chapters.
3.2 Determination of specific surface area of microporous
materials
As kind of take-home message, it can be noted that the BET
method is applicable for the determination of specific surface
areas of non-porous solids as well as of mesoporous and mac-
roporous materials. The application of the BET equation to
microporous solids, however, fails since the BET model does not
correctly describe adsorption in micropores. Adsorption in
micropores is governed by strong adsorbent–adsorbate
Fig. 38 BET plot and relation between c and nm to slope and intercept of
y-axis.
This journal is ª The Royal Society of Chemistry 2011
View Online
interaction due to overlapping adsorption potentials of opposing
pore walls at very small distances to each other, resulting in
complete filling of the micropore at very low relative pressures (at
plateau of type I isotherm). Furthermore, multilayer adsorption,
which is the basic assumption for the BET model, is not possible
in the narrow micropores. Applying the BET algorithm on type I
isotherms would consider all molecules adsorbed in the volume
of the micropores to be located in a monolayer. Therefore,
monolayer capacity and thus specific surface area in most cases
result in unrealistically high values. Instead of using the BET
method for the determination of the specific surface area of
microporous materials, more elaborated methods based on the
non-local density functional theory (DFT) should be rather
used.48–50 Modeling of the interaction between a given adsorbate
with an adsorptive at a certain temperature allows calculation of
density profiles of adsorbate films on the surfaces of adsorbates.
Thus, model isotherms can be calculated for hypothetic materials
with a given pore size. Matching a measured isotherm with a set
of such model isotherms allows assessment of pore size distri-
butions, pore volumes, and pore wall surface areas.51,52 Micro-
pore volumes are as well accessible by application of empirical
methods such as the t-plot or as-plot methods.53
3.3 Determination of pore size distribution of mesoporous
materials
The adsorption behavior of mesoporous materials is determined
by both, adsorbent–adsorbate interactions and interactions
between the adsorbent molecules. This leads to pore condensa-
tion in addition to multilayer adsorption. For pore condensation,
a gas condenses in a pore to a liquid-like phase at pressures below
the saturation pressure p0 of the bulk liquid. Adsorption in
mesoporous materials is represented by type IV and V adsorp-
tion isotherms. In the region of low p/p0 values, the type IV
isotherm is similar to isotherms of non-porous materials (type
II). Monolayer adsorption and initial steps of multilayer
formation are similar on an external surface of a particle and on
the walls of mesopores. At higher p/p0, a deviation of the type IV
isotherm from the type II isotherm is visible which is caused by
capillary condensation in the mesopores. Capillary condensation
occurs in mesopores when multilayer adsorption in such pores
proceeds to a point at which adsorbed layers from opposing walls
meet each other and form a concave meniscus. Adsorption on
concave adsorbate films is strongly enhanced and thus rapid
filling of the mesopores is observed which is characterized by
a distinct step in the isotherm. The relation between the change in
vapor pressure and the curvature of a meniscus with radius r is
described by the Kelvin eqn (17):
 
2gVm p0
rK ¼  ln (17)
RT p
with rK being the Kelvin radius (radius of curvature of hemi-
spherical meniscus), g the surface tension, and Vm the molar
volume of adsorbate in liquid.
In the case of complete wetting, a multilayer film has adsorbed
on the pore walls. The thickness t of a multilayer film has to be
considered for the calculation of the pore radius rp of cylindrical
pores (Fig. 39) by eqn (18):
Nanoscale, 2011, 3, 792–810 | 807
 View Online
Published on 13 January 2011 on http://pubs.rsc.org | doi:10.1039/C0NR00561D

Fig. 39 Formation of a multilayer film of the thickness t in cylindrical

pores with the pore radius, rp, and the Kelvin radius, rK.
rp ¼ rK + t
Fig. 40 Nitrogen sorption isotherms (77 K) for different SBA-15
materials with mesopores that are coated with carbon (experimental data
provided by An-Hui Lu, the isotherms of CCS40 and CCS30 have been
shifted by 60 and 90 cc g1).
(18)

isotherms exhibit a drop in the desorption branch close to p/p0 ¼

The Kelvin equation describes the interaction of a meniscus of 0.42 (dotted line).
Problems arise if the desorption branch is used for the evalu-
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liquid-like adsorbate with an adsorptive in the gas phase at

equilibrium and thus applies correctly only for the desorption ation of pore sizes of these materials with the BJH method, as
shown in Fig. 41. For all samples, pore diameters of about 35 A 
process since the capillary filling upon adsorption is no equilib-
rium process. The Kelvin equation based on cylindrical pores is
used for the evaluation of the pore size distribution of mesopores
by the Barrett–Joyner–Halenda (BJH) method.54 The pores
are filled by capillary condensation assuming a hemispherical
liquid–vapor meniscus and a defined surface tension. The BJH
algorithm is based on a stepwise emptying of the pores after the
stepwise reduction of p/p0. Because the Kelvin equation is
a purely thermodynamic construct and does not take explicit
account of the structure at the molecular level, it becomes
inaccurate for small mesopores (below about 50 A 4,5) and fails
to describe adsorption in micropores (defined as having pore
 55
widths <20 A).
A very comprehensive and helpful review on ‘‘.misinterpre-
tation and wrong assignment of adsorption data.’’ is given by
Groen.56 The focus of the review is on the correct determination
of pore size distributions. Pore size determination of materials
with small mesopores and materials with both meso- and
micropores can be influenced by a tensile strength effect or fluid-
to-crystalline like phase transitions. The tensile strength effect
causes a characteristic step-down in the hysteresis loop which is
related to the instability of the meniscus of the liquid–gas inter-
face rather than to properties of the pore structure of the mate-
rial. Ignoring this effect, the evaluation of the desorption branch
can result in an artificial narrow peak in a BJH pore size distri-
bution at about 3.5–3.8 nm due to a step at p/p0 z 0.42. Only the
careful evaluation of both, adsorption and desorption, branches
can prove whether this effect is real or not for materials with
uniform cylindrical pores. If only the evaluation of the desorp-
tion branch results in a narrow pore size distribution (i.e., only
the desorption branch shows a sharp step), then different factors Fig. 41 (a) Calculated pore sizes of three different SBA-15 materials if
have to be taken into account. Fig. 40 shows the nitrogen the desorption branch is used for the evaluation and (b) calculated pore
adsorption isotherms of three different mesoporous SBA-15 sizes if the adsorption branch is being used. The color code corresponds
samples, the pores of which are coated with carbon. The to the color code in Fig. 40.

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are calculated from the desorption branch (Fig. 41a). If the
adsorption branches are used instead, significantly different pore
diameters are calculated for the different samples (Fig. 41b).
What are the reasons for those differences? In Fig. 40 one can
discern two different types of hysteresis loops, one that closes at
relative pressures above 0.42 (CCS30) and two that close more or
less exactly at that pressure (CCS40 and CCS60). For the sample
CCS30 for which the hysteresis loop closes above the relative
pressure of 0.42, the desorption step indeed reflects a pore width,
namely that of narrow pore entrances that extend to wider inner
pores (ink bottle effect). On the contrary, the adsorption branch
of the hysteresis reflects adsorption on these wider inner pores
and data evaluation of that branch results in a pore width for
Published on 13 January 2011 on http://pubs.rsc.org | doi:10.1039/C0NR00561D
that part of the pore system.
For the other two samples, the hysteresis loops close at
a relative pressure of 0.42. One should mention here, that the
visible lines simply connect neighboring data points and do not
necessarily reflect the true shape of the isotherms in regions with
abrupt changes of slopes. In these cases it is difficult to discern
between the tensile strength and ink bottle effect. The adsorption
branches increase quite steadily whereas the desorption branches
drop instantly at the mentioned pressure. For these samples one
cannot conclude with certainty that a narrow pore neck exists
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from nitrogen adsorption isotherms. If more information is
needed on such materials, sorption measurements with argon as
adsorbent can be helpful. For argon the tensile strength effect is
observed at lower relative pressures, especially if measurements
are performed at 77 K instead of 87 K.57
Another effect that can be effective in changing the shape
hysteresis loops is cavitation. It occurs during desorption from
pores that are blocked at their entrances by very narrow
windows.58–60 In such cases, an empty bubble is formed within the
pore fluid while the pore necks are still filled with adsorbate. The
critical pore diameter for adsorption in infinitely long cylindrical
channels in silica materials below which cavitation is likely to be
encountered is about 5 nm for nitrogen adsorption at 77 K and
argon adsorption at 87 K, and about 4 nm argon adsorption at
77 K.61,62 These critical pore diameters have been estimated from
model calculation on the basis of the non-local density functional
theory (NLDFT).
This theory also allows computing of interactions of molecules
in gas phase with solid surfaces. Thus, model isotherms for
materials with given pore shapes and surface properties can be
calculated. Complete sets of model isotherms can then be
matched to measured isotherms.63–65 As the result, pore size
distributions are obtained which are considered to be much
preciser than those obtained from the BJH theory. The latter is
known to underestimate pore sizes, especially for smaller meso-
pores.
Modern program packages for sorption data evaluation make
use of that NLDFT approach. Calculating pore widths from the
desorption branches of the isotherms as shown in Fig. 40 with
the Autosorb 1.52 software package of Quantachrome, using the
kernel for nitrogen adsorption on carbons at 77 K applying the
 for
equilibrium model, results in pore widths of about 51 A
CCS30, 49 A  for CCS40, and 47 A  for CCS60. These numbers
are significantly larger than those calculated by the BJH model
and confirm that BJH underestimates pore sizes. However, also
the NLDFT method has its limitations. Pore blocking effects, as
This journal is ª The Royal Society of Chemistry 2011
View Online
discussed above, are not considered in the models for long
cylindrical channels and thus, the same limitations as for BJH are
encountered. The desorption branch reflects the neck size and the
adsorption branch the real pore width. Unfortunately, NLDFT
kernels for the evaluation of adsorption branches are less
abundant than those for desorption branches which are not
reflected in equilibrium models. Thus, proper evaluation of the
above shown data by the NLDFT method is difficult since model
isotherms that reflect the adsorption branch are not available for
carbon materials.
This shows another difficulty of the NLDFT method. It is
applicable only to a given material with given pore shapes. This
causes significant problems when materials for which no model
isotherms exist are under investigation (polymers, metals,
biomaterials, etc.). The materials of which the isotherms are
shown in Fig. 40 consist of mesoporous silica (SBA-15) the pores
of which are coated with amorphous carbon. Here a NLDFT
kernel for carbon might be applied with certain validity.
However, that could be very different for functionalized silica or
carbon materials as well as for composite materials. In such cases
no NLDFT model is valid and the results are rather meaningless.
In such cases, one often reverts to the classical BJH method. The
drawbacks of that method are known and the method can be
used reproducibly in all laboratories worldwide.
Thus, using the NLDFT method is highly recommended if
appropriate model isotherms are available with respect to
adsorbent, adsorbate, and pore geometry.66 If this is not the case,
NLDFT is as wrong as any other method and one should then
revert to classical methods as long as no better alternatives exist.
4. Summary
Nanoparticles and nanoscopically ordered materials are fasci-
nating and therefore under investigation in numerous laborato-
ries worldwide. Their characterization, often appearing
straightforward at first glance, bears several pitfalls. Standard
data evaluation that would be completely correct for bulk
materials easily results in a false picture of a given material.
However, if one is aware of such pitfalls, awkward mistakes can
be avoided and the data will withstand critical examination. As
a general conclusion one should say that using complementary
characterization methods provides most accurate pictures.
Therefore, using combinations of methods that allow a compre-
hensive assessment of the properties of a given material is rec-
ommended rather than focussing on one specific method.
Acknowledgements
The author is grateful to Dr Wolfgang Schmidt (MPI) for many
helpful discussions, to Prof. An-Hui Lu (School of Chemical
Engineering, Dalian University of Technology) and Prof. Chun
Hua Yan (State Key Lab. of Rare Earth Materials Chemistry &
Applications, Peking University) for providing samples. Mr
Bernd Spliethoff (MPI M€ ulheim) and Mr Axel Dreier (MPI
M€ulheim) are gratefully acknowledged for TEM measurements.
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