X-ray Absorption Spectroscopy Studies

on Materials Obtained by the Sol-Gel Route

Francesco d’Acapito

Contents
Introduction to X-ray Absorption Spectroscopy (XAS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
Data Collection and Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
Data Analysis Procedures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
Applications of XAS to Sol-Gel Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
Materials for Optics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
Materials for Catalysts and Sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
Electrodes for Batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
Perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22

Abstract
This chapter reports on the use of X-ray Absorption Spectroscopy in the charac-
terization of materials obtained by the Sol-Gel method. Firstly, an introduction to
the theoretical bases of the technique is given followed by a brief description of
the most relevant data collection schemes and data analysis. Successively, a
collection of recent relevant experiments is presented putting in evidence, case
by case, the peculiar information retrieved thanks to this technique. These studies
are classed following the kind of material or its use: materials for optics,

F. d’Acapito (*)
CNR-IOM-OGG c/o European Synchrotron Radiation Facility, LISA CRG, Grenoble, France
e-mail: dacapito@esrf.fr

# Springer International Publishing Switzerland 2016 1

L. Klein et al. (eds.), Handbook of Sol-Gel Science and Technology,
DOI 10.1007/978-3-319-19454-7_31-1
2 F. d’Acapito

nanoparticles, materials for catalysis and sensors, and materials for batteries.
Eventually, a brief overview is given on the future perspectives of the technique
in terms of new data collection methods and data analysis. A rich list of biblio-
graphic references completes this contribution.

Introduction to X-ray Absorption Spectroscopy (XAS)

Theory

X-ray Absorption spectroscopy (XAS) (Lee et al. 1981) is an experimental technique

that permits the quantitative determination of structural parameters around chosen
atomic species and to obtain a description of the electronic structure. In particular, it
derives this information from the small oscillations that appear in the absorption
coefficient as a function of energy just above the edge step from a deep core state
(1s or 2s, 2p). These oscillations appear only when the absorbing atom is regularly
surrounded by other atoms as shown in Fig. 1.
XAS permits the determination of the number of neighbors N and distance R from
the atom that absorbs the X-ray photon (hereafter defined as the absorber) with an
accuracy of about 10 % for N and 1 % for R. Moreover, it is chemical selective as the
absorption edges of elements are well spaced in energy from each other (for edge
energy values refer to data in Bearden and Burr (1967)). The presence of small
Absorption Coefficient µ (Arb. Units)

10800 11000 11200 11400 11600 11800 12000 12200 12400

Energy (ev)

Fig. 1 Example of a XAS spectrum: the Ge-K edge of crystalline Ge (Data collected at the GILDA
beamline, European Synchrotron Radiation Facility)
X-ray Absorption Spectroscopy Studies on Materials Obtained by the Sol-Gel. . . 3

oscillations above the absorption edge was reported much earlier but only in the
early 1970s (Sayers et al. 1971), and with the successive advent of synchrotron
radiation facilities (Kincaid and Eisenberger 1975), XAS theory has been fully
understood and developed (Rehr and Albers 2000), and the technique has been
used in a variety of fields like solid state physics, materials science, environmental
science, chemistry, structural biology, and archaeometry as can be seen in a series of
publications on this technique (Köningsberger 1988; Bunker 2010).
The physical origin of the μ oscillations above the edge is the modification, due to
the neighboring atoms, of the final state of the electron emitted by the atom that
absorbs the incoming X-ray photon (hereafter called “Central” or “Absorber” atom)
(Lee et al. 1981; Stern 1988). The X-ray absorption cross-section, Σ, of an atom
!
interacting with a photon described by a dipole transition operator D is given by
(Natoli and Benfatto 1986):

X D  ! ! E2

Σ ¼ 4π2 Eα  i p  D f  δðE  Ef þ E0 Þ (1)
f

where E is the photon energy, α the fine structure constant, EF is the photoelectron
  energy. hii and hfi are, respectively, the initial and
energy, and E0 is the threshold
!
final electron states, and p is the electron momentum operator. The initial state hii
is usually an atomic core state (K or L) so it is strongly localized around the central
atom site: This means that the space integrals in Eq. 1 are calculated in a restricted
region around the absorber. In the case of the isolated atom, h f | is an outgoing
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
spherical wave where k is the photoelectron wavevector k ¼ 2m ðEE 0Þ
ℏ . In this
case, hfi is a smooth and structureless function of E, and a similar behavior will be
found in the absorption cross section Σ0.
When a neighbor (Backscattering atom) is placed near to the central atom, a part
of the outcoming electron wave will be backscattered by the neighbor: hf i will be
the sum of the original outgoing wave plus a modified part hΔf i, coming from the
waves backscattered by the neighbors. The backscattered wave will have an
amplitude A(k, Rj) and a phase φ(k, Rj) which depend on the details of the
scattering potential. The interference between these two terms in the absorber
site gives rise to the oscillations observed in the experimental data.
The oscillatory part χ of the signal is defined considering Σ0 (containing hfi) and
Σ (containing hf þ Δf i) and taking χ ¼ ðΣΣ 0Þ
Σ0 . The explicit expression for χ in the
case of an “S” state excitation and considering only single scattering events is (Lee
et al. 1981):

X X Nj      2 2  
χ¼ χj ¼ 3S20 ^ j 2 (2)
A k, Rj sin 2kRj þ φ k, Rj þ 2δc ðkÞ ek σj e2Rj λ ^e  R
j j kR2j
4 F. d’Acapito

Here the sum is extended over the various coordination shells indexed by j, each
containing Nj identical atoms at a distance Rj from the central one. The backscat-
tering amplitude and phase, A and φ, are expressed in terms of the bond length Rj
!
(curved wave approximation). In Eq. 2, e is the field polarization unit vector and the
related term expresses the dependence of χ on the beam polarization. This depen-
   !
!
dence comes from the p  D operator and is of particular interest for single
crystal samples, where the absorption coefficient depends on the sample orientation.
This effect is different if {K, LI} or {LII, LIII} edges are considered. In the former case,
the relation between the amplitude N of a single bond making an angle δ
with the polarization vector is NK, LI ¼ 3  cos2 δ, whereas in the latter case, it is
NLII , LIII ¼ 0:7 þ 0:9  cos2 δ (Iwasawa 1997). Conversely, in the case of isotropic
 
! ! 2
samples (polycrystalline powders, amorphous, liquids,. . .), the e  R j term is
replaced by its angular average, 1/3.
In the χ(k) formula shown above, other terms are added to the simple scattering
approximation in order to account for two damping processes. One is the limited
lifetime of both the photoelectron and the core-hole. Indeed, the excited atom keeps
this state for a limited time, after which an electron from the upper state fills the hole
in the core state, destroying the extended X-ray absorption fine structure (EXAFS)
signal. This problem is particularly severe when working on edges of heavy ele-
ments at high (E > 40 keV) energies (Borowski et al. 1999) as the broadening due to
the core-hole limited lifetime can be several eV (Krause and Oliver 1979). Also,
when the emitted photoelectron undergoes momentum transfer or inelastic scattering
with other electrons, the EXAFS signal is cancelled. All this can be accounted for by
adding an imaginary part to the scattering potential (Chou et al. 1987) and is
contained in the exp(rj/λ) term. As λ is of the order of a few Å, EXAFS signals
coming from long paths are rapidly damped and this makes the technique sensitive
only to the local atomic structure around the absorber.
Simultaneously with the electron emission, other electrons can also be excited in
the central atom, both to bound states or continuum states (Lee and Beni 1977), as
shown by photoemission experiments. This reduction of the overall amplitude is
accounted for by the S02 term.
The physical process at the origin of the EXAFS signal is interference, so it
strongly depends on the spatial disorder of the back-scattering centers. The disorder
can be originated by thermal vibrations or by random positions of the neighbor
atoms in amorphous systems. Considering this, the χj function should be calculated
as the integral of χj(R), weighted by the Pair Distribution Function (PDF) relative to
the i-th shell (Benfatto et al. 1989). If we suppose a small disorder and a gaussian
pair distribution function with mean square displacement σ2j, the result of the
integral is the exp(k2σj2) term in Eq. 2 (Beni and Platzmann 1976). Note that
this term, although similar to the Debye-Waller factor in X-ray diffraction, has here a
different meaning. Whereas in the latter case, σ is related to the variation of the
atomic position with respect to the ideal lattice site, in EXAFS it means the relative
displacement of the neighbor relative to the absorber position. If thermal disorder
X-ray Absorption Spectroscopy Studies on Materials Obtained by the Sol-Gel. . . 5

dominates, the values of σj can be calculated from the dynamic properties of the
lattice under study, as shown in Beni and Platzmann (1976) and Sevillano
et al. (1979). When the atomic oscillations become large, and this is the case, namely,
for lattices at temperatures near or above their Debye temperature or in case of
strongly disordered systems, the pair distribution functions also acquires a
nonsymmetric character with respect to the distribution maximum, i.e., they become
skewed at higher r values. This is due to the atomic interaction potential, which
generally exhibits a Lennard-Jones-like behavior. The asymmetry of the PDF leads
to unphysical results if data are treated in the gaussian approximation, typically a
contraction of the distances and a drop in the coordination numbers, as shown in
Eisenberger and Brown (1979). In this case, an analysis based on a more detailed
model for the PDF is needed, by taking into account higher cumulants of the
distribution (Tranquada and Ingalls 1983) or introducing ad hoc PDFs (Filipponi
et al. 1995; Filipponi and DiCicco 1995; Kuzmin 1997) for the construction of the χ
function.
So far we have considered the photoelectron interactions in the solid as a series of
single scattering events with the surrounding atoms. In a more general view, we
should take into account processes where the photoexcited electron is scattered by
several neighbors before returning to the central atom. While the scattering ampli-
tude dies with the path length, the number of possible paths increases and it comes
out that multiple scattering (MS) phenomena are not negligible in the interpretation
of an X-ray Absorption Spectrum (Lee and Beni 1977) and extend up to several tens
of eV above the edge (Benfatto et al. 1986). The calculation of the photoelectron final
state hf i, accounting for multiple scattering events, can be carried out in several
ways, like in the scattering approach, the band-structure approach, or the Green-
function approach (Natoli and Benfatto 1986), all leading exactly to the same result.
The X-ray cross section is expressed in matrix form by Natoli and Benfatto (1986):
" #
1 X h 1
i0, 0
σ ¼ σ0 ℑ ðI  TGÞ T 
ð2L0 þ 1Þ sin2 δ0l m lm, lm
" # (3)
1 X X 0, 0
σ0 ℑ 2 0
ℑ ½ðTGÞn Tlm, lm
ð2L0 þ 1Þ sin δl m n

Here, G is the so-called Propagator matrix and contains all the geometrical details
of the cluster surrounding the absorber, whereas T is the “Scattering matrix” and it
contains the details of the scattering potentials. L0 is the angular moment of the initial
state, and σat is the (structureless) atomic cross section. The (1 + GT)1 term can, in
some cases, be replaced by its series expansion, giving rise to the so-called multiple
scattering series approximation of σ (right side of Eq. 3). The terms with n = 2 in the
expansion correspond to single scattering events (photoelectron scattered by the
neighbor and back to the absorber), whereas terms with n = 3, n = 4, . . . correspond
to events where the photoelectron is scattered 2, 3, . . . times by other neighbors,
before reaching back the absorber. Examples of single and multiple scattering paths
are given in Fig. 4. The multiple scattering expansion is valid provided that the
6 F. d’Acapito

related series is convergent. As the G matrix elements depend on 1/k or, equivalently,
pffiffiffiffiffiffiffiffiffiffiffiffiffiffi
on 1= E  E0 (whereas the elements of the T matrix depend on the chemical nature
of the scatterer), the convergence criterium is usually satisfied for photoelectron
energies above a few tens of eV and depends on the system under investigation
(Natoli and Benfatto 1986).
The standard EXAFS formula shown in the first paragraph can be obtained from
the MS expansion, taking L0 = 0 and cutting the series at the n = 2 term. For the
higher terms, it can be demonstrated (Zabinsky et al. 1995) that, for any given path i,
they can be reduced to expressions similar to that shown in Eq. 2 with suitable
amplitudes Ain(k, Ri) and phases φin(k, Ri), where now Ri is half the total path
length. In the example of Fig. 4, the path in (c) is associated to a given χi and the path
in (d) to a different χj. By summing all these partial χi, the total signal can be
reproduced. Debye Waller factors related to Multiple Scattering paths have been
defined via a generalized formula as presented in Poiarkova and Rehr (1999). Using
a different approach (Filipponi and DiCicco 1995), the contribution to the total χ of a
given atomic arrangement, called γi, can also be parametrized similarly to Eq. 2.
When approaching the absorption edge, the photoelectron mean free path
becomes appreciably large (as well as its wavelength) and a larger number of
paths contribute to the total signal. There exists a limit beyond which the MS
expansion no longer converges, so it is not possible to calculate the cross section

Fig. 2 Partition of a typical XAS spectrum in the EXAFS and XANES regions, here for the
spectrum of hematite (Fe2O3) at the Fe-K edge. In the EXAFS region (roughly above 50 eV from
the edge), only Single Scattering (SS) or a mixture of Single and a limited number of Multiple
Scattering paths contribute to the spectrum. In the XANES region, all the possible paths contribute
to the spectrum and the Full Multiple Scattering (FMS) approach is needed to reproduce the
spectrum
X-ray Absorption Spectroscopy Studies on Materials Obtained by the Sol-Gel. . . 7

in this way. The 1/(1  GT) matrix has to be calculated explicitly and this is the
so-called Full Multiple Scattering method (Tyson et al. 1992). This region is called
XANES (X-ray Absorption Near Edge Structure) and it contains in principle three-
dimensional information on the absorber site (Fig. 2).
Apart from the complex spectrum simulations, XANES can be easily used for the
determination of the valence state and local symmetry of the element under inves-
tigation prior to comparison with known compounds. The valence state is derived
from the energy position of the edge (Cramer et al. 1976), the more oxidized states
corresponding to higher edge energy values. The local symmetry can be derived
from the intensity of the small peak appearing before the edge (that in the case of K
edges of the 3d metals are due to partially forbidden 1s-3d transitions) with tetrahe-
dral environments exhibiting more intense peaks (Galoisy et al. 2001).

Data Collection and Analysis

The absorption coefficient, μ, of a sample as a function of the energy is defined as:


Φ 1 ð EÞ
μðEÞ ¼ ln (4)
Φ 0 ð EÞ

Fig. 3 Experimental setup Sample

for the direct (a) and indirect
a Ic 1 Ic 0
(b) measurement modes of the
X-ray absorption coefficient
of a sample

Transmission Mode

b
X-ray or Electron Detector

Ic 0

Sample
Fluorescence (or Electron detection) Mode
8 F. d’Acapito

where Φ0 and Φ1 are the photon fluxes before and after the sample, respectively
(Fig. 3a). The fluxes are normally measured by an ionization chamber, usually filled
with low-pressure gas. There are different methods to measure the absorption
coefficient, depending on the nature of the sample being investigated. As a thumb-
rule, when the atomic species of interest contributes significantly to the total
absorption of the sample, it is convenient measuring the intensity transmitted after
the sample (transmission mode). This is commonly the case of systems with a high
number of absorbing centers, like bulk, heavy (high atomic number Z) elements. The
measure of the transmitted intensity is carried out by a second ionization chamber
(Lee et al. 1981).
In some cases, e.g., samples with a low concentration of absorbers, it is better to
measure indirectly μexp, looking at the processes usually coupled to the X-ray
absorption. Indeed, the photoionization process creates a hole in the core state that
is suddenly filled by another electron. This occurs through a couple of competitive
processes: a radiative one, where an electron “falls” from a higher energy state to the
ionized one emitting a photon (fluorescence). Alternatively, hole filling can be
accompanied by the emission of fast electrons to balance the energy (Auger pro-
cesses). The higher the Z of the involved atom, the more probable is the fluorescence
process, with equal probability occurring at roughly Z = 30. It must be noted that the
emission of the photon occurs at a well-determined energy, depending on the atom
and on the level involved. It is thus easy to separate the desired signal from the
background.
Exploiting the first effect described above is called the fluorescence collection
mode (Jaklevich et al. 1977) (Fig. 3b). In this case, an energy-selective detector
(namely, solid state detectors such Li:Si, Si Drift, High Purity Ge, . . .) is used to
separate the fluorescence from the background (coherent and incoherent scattering),
or fluorescence from other elements. This method is particularly well adapted for the
analysis of diluted samples but leads to spectrum distortions when applied to
concentrated samples. In this case either data-correction routines have to be applied
(Troger et al. 1992) or data have to be collected at grazing exit angle (Pfalzer
et al. 1999). Recently, a novel detection scheme for fluorescence XAS on concen-
trated samples has been proposed (Achkar et al. 2011) where the absorption signal of
an atom A is collected by recording the modulations of the fluorescence yield of a
lighter atom B while scanning the energy through the A absorption edge.
A method that gained considerable popularity in the latest years is the High
Energy Resolution Fluorescence Detection (HERFD). Indeed, as shown in
H€am€al€ainen et al. (1991), collecting the fluorescence yield from a sample with an
energy resolution lower than the core-hole linewidth produces XANES spectra no
longer broadened by the initial state, so permitting to evidence structures in the
spectrum barely visible with the conventional data collection. This technique is
called High Energy Resolution Fluorescence Detection (HERFD) and results to be
particularly effective in the analysis of the L edges of 5d metals where the typical
broadening of the states is of the order of 5–10 eV. The detector is usually a multiple
crystal analyzer with a limited solid angle acceptance, so this technique can be
carried out only on very intense sources. A description of a complete spectrometer
X-ray Absorption Spectroscopy Studies on Materials Obtained by the Sol-Gel. . . 9

can be found in Glatzel et al. (2005) and Rovezzi and Glatzel (2014). The drawback
is that using crystal analyzers greatly reduces the effective collection solid angle for
the fluorescence so the total efficiency (flux on the detector) results to be greatly
reduced with respect to the conventional method with a considerable increase of the
minimum concentration limits.
Alternatively to fluorescence, the total electron yield from the sample due to
cascades initiated by the Auger processes can be detected (Citrin et al. 1978). The
signal is measured with a channeltron detector or simply by measuring the photo-
ionization current from the sample. This method has the peculiarity of probing a few
thousand Å under the sample surface (due to the limited electron escape depth) and
can be useful in studying macroscopically layered structures, e.g., ion-implanted
materials.
The other way to study surfaces is based on the x-ray total reflection: When the
x-ray beam impinges with a sufficiently small angle on the sample, the x-ray
penetration is limited to a few Å (Parratt 1954). In this case, the signal can be
collected both from the fluorescence yield from the sample or from the reflected
beam, using detectors described above such as photodiodes or scintillation detectors
(Heald et al. 1988). In this setup, the ultra-high vacuum environment is not needed
and it can be exploited to investigate liquid surfaces buried interfaces or gas-solid
interfaces. An example of a typical experimental apparatus for total reflection
EXAFS can be found in d’Acapito et al. (2003 and references therein) and consists
of an accurate sample positioning stage with detectors for the impinging and
reflected beam as well as for the fluorescence from the sample. The main limitation
of this procedure is the need of sufficiently long (a few cm) and smooth (microscope-
slide grade) samples. This method, enhancing the signal from the surface thin film
with respect to the substrate, is particularly indicated in the study of thin layers like
those obtained by sol-gel (d’Acapito et al. 2008).
By exploiting the luminescent properties of the samples, it is possible to derive
interesting results using the X-ray excited optical luminescence (XEOL) technique.
XEOL is a particular data collection technique (Rogalev and Goulon 2002; Sham
and Rosenberg 2007) which derives the absorption coefficient μ from the optical
luminescence that follows the absorption of an X-ray photon in particular materials.
The electrons emitted in each absorption event produce a shower of lower energy
electrons (that extends far from the X-ray absorbing atom) in the conduction band
that excites the luminescent centers contained in the material with consequent
emission of a low energy photon. The intensity of this signal is proportional to the
absorption coefficient and will contain the XAS signal related to the environment of
the absorbing atoms. The site selectivity between luminescent and nonluminescent
zones under investigation can be achieved provided that the two families are
sufficiently spatially separated (10 nm (Rogalev and Goulon 2002) for soft
X-rays, an order of magnitude more for hard X-rays). In practical terms, the data
collection is realized by collecting the optical emission from the sample with a lens
focusing on an optic fiber leading to the entrance slit of a wavelength dispersive
optical monochromator. Different portions of the emission spectrum can be thus
used for the data collection permitting the selection of the luminescent sites.
10 F. d’Acapito

a 1.8 b
1.6
Absorption Coeff. (Arb. Units)

3
1.4
2
1.2
1
1

k2 * x(k)
0
0.8
-1
0.6
0.4 -2

0.2 -3

0 -4
10500 11000 11500 12000 12500 13000 13500 0 5 10 15 20
-
Energy (eV) k [Å 1]
c 4 d 200

3.5 150
Magnitude of the F T [Å ]
-3

3 100
2.5 q2 * x(q) 50

2 0

1.5 -50

1 -100

0.5 -150
0 -200
0 1 2 3 4 5 6 7 8 0 5 10 15 20

R [Å] q [Å -1]

Fig. 4 Example of EXAFS data treatment relative to crystalline Ge. (a) raw absorption spectrum,
(b) extracted EXAFS spectrum χ(k), (c) Fourier Transform, (d) Back Fourier Transform

Data Analysis Procedures

It can be seen in Eq. 2 that each particular coordination shell contributes to the total
signal with a sine oscillation in k space with frequency 2R (plus a term ϕ(k, Rj)
weakly depending on k). Here we provide a description of the standard data analysis
procedure (Lee et al. 1981): the raw absorption spectrum (Fig. 4a) the oscillating part
χ is isolated by subtraction of a structureless atomic background (Fig. 4b). When the
χ signal is Fourier transformed (FT), peaks appear in the spectrum each
corresponding to a different coordination shell (Fig. 4c). By windowing the FT in
a way to leave only one peak and by applying to this function a back Fourier
transform, the contribution from only one coordination shell is obtained (Fig. 4d).
The basic principle of EXAFS data analysis is to reproduce the filtered experi-
mental data (Fig. 4d) with a model based on the expression shown in Eq. 2. In that
expression, two kinds of variables are present:

• Parameters linked to the photoelectron interaction with the medium, like the
backscattered amplitude A(k, Rj), phase φ(k, Rj), photoelectron mean free path
λ, and S02.
• Parameters linked to the local atomic structure, like the number of neighbors Nj,
the bond length Rj, and the Debye-Waller factor σj.
X-ray Absorption Spectroscopy Studies on Materials Obtained by the Sol-Gel. . . 11

The former parameters can be calculated from ab initio methods. Several codes,
like FEFF (Zabinsky et al. 1995; Ankudinov et al. 1998), GNXAS (Filipponi et al.
1995), and EXCURVE (Binsted) are available for this purpose. These functions can
be used in a multiparameter fitting procedure with variable atomic structure param-
eters, to reproduce the experimental data. Different strategies of data fitting are used,
the fit being done on Fourier-filtered EXAFS data (Lee et al. 1981) or directly on the
FT (Zabinsky et al. 1995; Newille 2005). In both cases, the analysis can be done on a
part of the spectrum (namely, the first shell) or on the whole. Other codes fit directly
the absorption coefficient, making no use of Fourier Transform (Filipponi and
DiCicco 1995), but in this case, a model accurately describing the entire structure
needs to be considered. In general, bond lengths are determined with relatively high
accuracy (0.02 Å, or better) whereas amplitude parameters (N and σ) are deter-
mined within 10 %.
A different approach is made on the XANES region. Here, since the calculation of
the absorption coefficient is quite time consuming, the spectrum is reproduced at a
qualitative level starting from a supposed three-dimensional model of the structure.
Different codes based on a real space approach, like CONTINUUM (Tyson
et al. 1992), FDMNES (Joly 2001), FEFF9 (Rehr et al. 2009) permit a modeling
of the XANES part starting form a given structure and using the FMS approach.
Other codes based on band structure methods (WIEN2K (Blaha et al. 1990),
SPRKKR (Ebert 1998), XSPECTRA (Gougoussis et al. 2009)) are also available.
Quite recently a new code called MXAN has been presented (Benfatto et al. 2001),
permitting the structural refinement using the XANES part of the spectrum, with
interesting results in biological applications (Della Longa et al. 2001).

Applications of XAS to Sol-Gel Materials

A variety of examples on the use of XAS on materials obtained by sol-gel route will
be presented here, with particular attention to materials for optical applications,
catalysis, nanoparticles, and batteries.

Materials for Optics

A considerable work has been carried out on Rare-Earth doped phosphors for
applications in white Light Emitting Diodes. Indeed, these devices emit light in
the blue or near ultraviolet (UV) portion of the spectrum and need a conversion agent
to obtain white emission. Sol-Gel revealed to be a powerful technique for the
realization of phosphors via treatments using low temperatures. Potdevin
et al. (2010a, b) have studied the effect of Acetylacetone (acacH) as a chemical
modifier in the synthesis of Tb-doped Y3Al5O12 (Yttrium Aluminum Garnet, YAG)
phosphor in powder form. Indeed, sol-gel procedures revealed to be interesting with
respect to the preparation via solid-state reaction involving high temperatures
(T 1500 C) as this process can lead to byproducts spoiling the luminescent
12 F. d’Acapito

properties. In the procedure of production of YAG, it was found that using acacH
instead of hydrolyzing the solution with water (Potdevin et al. 2010a), it was
possible to obtain better materials using lower temperatures for treating the xerogels.
A XAS investigation at the Y-K edge carried out on xerogels obtained with or
without acacH revealed that in the former case the realization of a crystalline order
around Y started already at 600 C whereas 800 C were necessary in the case of the
materials obtained with the standard hydrolysis method (Fig. 5).
The same behavior was evidenced in the environment of Tb dopants, confirming
that the crystalline order was realized at lower temperatures in the matrix obtained
with acacH and that dopants are incorporated in crystalline nuclei since the early
stages of the process.
Nakajima et al. (2013) have studied the incorporation of Ca-α-SiAlON phosphor
doped with Eu (again for applications in white LEDs) in TiO2-SiO2 matrices
obtained by sol-gel. Analyzing the XANES spectra, the authors have found that Ti
was 5-coordinated for low Ti content (10 mol%) and turned predominantly
6-coordinated for high content (30 mol %). Eu contained in the phosphor was
affected by the incorporation in the sol-gel matrix as the ratio Eu2+/Eu3+ was altered
with a reducing effect (higher Eu2+ content) following the incorporation.
Ye et al. (2013) have demonstrated the possibility of doping Mg2TiO4 with Mn
via a sol-gel method with the aim of obtaining a red phosphor to be used in the
wavelength conversion in white LEDs. In this case, X-ray Diffraction (XRD)
revealed the formation of the Mg2TiO4 phase after annealing the xerogel at
1300 C. The chemical state and location of Mn dopants was elucidated by XAS
at the Mn-K edge. By comparison with model compounds, the valence state of Mn
was defined at Mn4+ and the detailed analysis of the XAS data (3 coordination shells)
permitted to recognize MnTi as the incorporation site of this metal as required for the
formation of the phosphor.
Light conversion is needed not only in LED technology but also in solar cells.
Indeed, the mismatch between the gap of Si and the solar spectrum leads to a limited
efficiency of this kind of cells. To overcome this problem, particular coatings for
solar cells have been proposed, called Quantum Cutting materials, capable to convert
energy from the UV-visible (VIS) region into Near Infra-Red (NIR) where Si cells
have a high efficiency. Sol-gel is an interesting method to produce these materials for
the capability of covering large areas and the limited cost of the process. Terra
et al. (2013) have investigated the formation of Tb3+-Yb3+ doped ZrO2 nanocrystals
obtained by sol-gel. The two rare-earth ions have different roles: Tb3+ is the
sensitizer that absorbs light in the VIS range and then transfers the excitation to
Yb3+ (activator) which emits in the NIR. During the production of the material, it is
of paramount importance that the dopants enter the matrix in the Zr-substitutional
site and keeping the 3+ valence state. Materials were obtained with the one-step
sol-gel method and contained different amounts of Yb (0–20 mol%) and fixed
(1 mol%) amount of Tb. XRD showed that Yb favors the formation of cubic zirconia
for content values above about 5 mol%. XAS at the Tb-L3 edge elucidated the
valence state of Tb in the xerogel and calcined materials. In the former case, Tb is 3+
for any value of Yb content, presumably due to the fact that Tb nitrate was used as
X-ray Absorption Spectroscopy Studies on Materials Obtained by the Sol-Gel. . . 13

F(R) /arb.units

1100 °C
800 °C
700 °C
600 °C
400 °C
200 °C
xerogel
0 2 4 6 8
R/Å
−1
k/A

F(R) /arb.units

1100 °C
800 °C
700 °C
600 °C
400 °C
200 °C
xerogel
0 2 4 6 8

R/Å

Fig. 5 Comparison between the Fourier Transforms of XAS data at the Y-K edge in xerogels
obtained with standard hydrolysis method (left) or with acetylacetone (right) (Figure Reproduced
from Ref. (Potdevin et al. 2010a) with permission from The Royal Society of Chemistry). The peaks
appearing around 3A are due to the second coordination (cationic) shell and indicate the formation
of a crystalline nucleus. In the right panel (relative to samples prepared with acacH the second shell
peak start to appear already at 600 C whereas the same peaks appear at 800 C in the case (left
panel) of samples prepared with the standard hydrolysis method

precursor. Upon calcination, formation of Tb4+ was observed for low-Yb containing
materials, whereas Tb resulted to keep the 3+ state for Yb at 20 mol%. The inhibition
of the unwanted oxidation of Tb was explained by the effect of oxygen vacancies
generated by Yb (aliovalent with respect to Zr) and permitted to define the optimum
conditions for obtaining an effective QC material. Similar effects linked to the
14 F. d’Acapito

valence state of rare earths have been also reported in Carvalho et al. (2016) where
the valence state of Pr in Gd-doped ZrO2 obtained by a standard sol-gel procedure
was controlled via the Gd content as revealed by XAS at the Pr-L3 edge. The authors
have shown that with Gd at 10 mol % the structure of ZrO2 is cubic and that Pr is
exclusively in the Pr3+ state.
Codoping can be used also to improve the behavior of photocatalysts as shown in
the case of TiO2 by Majeed et al. (2015). TiO2 is known to be an excellent
photocatalyst but it suffers from the fact that its gap is 3.15 eV so it can use only
about 3–5 % of the solar spectrum. Doping TiO2 with metals can contribute to an
improvement of its properties as in the case of Mo doping. TiO2 was prepared via
sol-gel with the addition of molybdic acid as Mo precursor. Mo was added at
different concentration values from 1 % to 10 % and the obtained samples were
analyzed by XAS at the Mo-K edge. The XAS data revealed that Mo is present in
two phases: substitutional phase in TiO2 and a separated MoO3 phase. Mo is totally
substitutional for the samples at 1 % and the amount of this phase decays with Mo
content, being only 7 % in the highly doped sample. Tests of efficiency were carried
out measuring the photodegradation of Methylene-Blue pigment in presence of the
catalyst under visible irradiation. The result was that the better performing sample
was that containing 5 % Mo out of which 30 % is in substitutional phase, demon-
strating that the interplay of all three components (TiO2, Mo: TiO2, and MoO3)
contribute to the improvement of the efficiency of the catalyst.
Studying luminescent materials permits the exploitation of nonconventional XAS
techniques like X-ray Excited Optical Luminescence (XEOL). This technique has
been used to characterize Ge nanoparticles (NP) (Little et al. 2014) in free-standing
form (comparing in this case oxygen-terminated particles with hydrogen-terminated
particles) and Ge nanoparticles embedded in silica produced by the sol-gel route.
The spectra at the Ge-K edge were collected in transmission mode (sensitive to all
the Ge species) and XEOL mode (sensitive to Ge species in luminescent regions) for
comparison. In the case of Ge nanoparticles surrounded by O species (O-terminated
free standing NPs or NPs embedded in silica), both spectra revealed a predominance
of Ge-O bonds meaning that the luminescence comes from the oxidized zones. In the
case of free NPs terminated with hydrogen, the XEOL spectrum exhibited a higher
disorder and a comparison with Molecular Dynamics simulations permitted to
establish that the luminescent regions were the most disordered one at the boundaries
of the particle.
XEOL detection was also used to characterize Rare-Earth doped nanospheres for
medical applications (Fortes et al. 2014). Hollow and bulk silica particles coated
with Er2O3 and Yb2O3 were characterized by XAS in fluorescence and optically
excited mode. The comparison between the spectra obtained in the two ways showed
no differences meaning that all the rare-earth species were present in luminescent
portions of the samples.
Further uses of XAS for the characterization of materials for optical applications
produced by sol-gel can be found in the case of Er-doped Silica-Hafnia waveguides
for optical amplifiers (d’Acapito et al. 2008; Afify et al. 2007), glass ceramics (Van
et al. 2015), and scintillator for detectors (Liu et al. 2015b).
X-ray Absorption Spectroscopy Studies on Materials Obtained by the Sol-Gel. . . 15

Nanoparticles

The sol-gel process permits to produce nanocrystalline materials with a good control
of composition and size that reveals to be invaluable for a large variety of systems.
Metal oxide nanoparticles, namely, find applications in several fields like gas
sensors, catalysts, electrodes for batteries and transparent electrodes.
Caetano et al. (2014) have studied in detail the structural evolution from the gel to
the densified material of SnO2 nanoparticles using time-resolved XAS at the Sn-K
edge. The synthesis was based on Tin Chloride (SnCl4 • 5H2O) dissolved in ethanol
that was subsequently hydrolyzed with water. Quick-XAS data were collected at a
frequency of 2 Hz during hydrolyzation and XAS, and Raman spectra were collected
at the same time in a specially conceived cell. The first 30 min of the process have
been described as a progressive loss of chlorine ligands for Sn substituted by oxygen
ligands. The XAS data as a function of time could be reproduced as a linear
combination of different complexes in solution [SnClx(H2O)6x]4x (with x = 3, 4
and 5) and the spectrum of SnO2 nanoparticles. With the support of Raman data, it
was possible to describe the evolution of the various complexes involving Sn as
shown in Fig. 6.
Time-resolved XAS was also used in the description of the growth of TiO2
nanoparticles in sol-gel as reported in Stotzel et al. (2010). In an ad hoc conceived
reaction, cell Titanium tetraisopropoxide was solved in isopropanol and successively

Fig. 6 Evolution of different species [SnClx(H2O)6x]4x and SnO2 in solution during

hydrolyzation and annealing. Results from XAS and Raman data collected in situ at the same
time (Reprinted with permission from Ref. (Caetano et al. 2014). Copyright 2014 American
Chemical Society)
16 F. d’Acapito

a water-isopropanol solution was added to carry out the hydrolysis of the solution. At
the same time, XAS spectra were collected with a duration time of 5 s (10 successive
spectra were averaged to improve the signal to noise ratio) up a total process time of
1500–2000s. The analysis of the XAS data was carried out by linear combination of
the spectra at different times with model compounds. The formation of TiO2 particles
involves different steps: polynuclear titanium species are created and, after a few
minutes, oligomers of the type Ti11O13 and Ti12O16. The consumption of the precursor
is particularly evident as it exhibits a particularly strong pre-edge resonance at about
4970 eV that is considerably damped in the oligomers and TiO2 species due to the
different site symmetry in the two cases. In an intermediate phase, the oligomers start
to form titania nanoparticles and, at the end, they are totally converted in TiO2.
The doping of SnO2 nanoparticles with Sb, obtained by sol-gel processing, has been
studied by V. Geraldo et al. (2010). In this case, gels at different Sb content (3–16 %)
were prepared from SbF3 and (SnCl4 • 5H2O) precursors. The obtained xerogels were
treated at 200 C or 500 C to study the evolution of the valence state and incorporation
site of Sb. It was evidenced that after treating at 200 C, Sb is pentavalent if present at
low concentration (
4 %) and a trivalent fraction is present for higher Sb content. After
firing at 500 C, Sb is predominantly pentavalent. Sb5+ species enter the SnO2 matrix in
a substitutional site. Conversely Sb3+ species, more abundant at high concentration
values, remain grafted at the surface of SnO2 particles.
The formation of Cooxide nanoparticles in porous silica has been studied by Liu
et al. (2015a). In this case, Cobalt doped silica at different Co/Si molar ratio (5 %,
10 %, 25 %) was obtained by sol-gel using Tetraethoxysilane (TEOS) for silicon and
[Co(NO3) • 6 H2O] as precursor for Cobalt. The sols were first dried at 60 C and
then ground in fine powder and calcined at 630 C. The materials were successively
tested with a hydrothermal treatment (HT) consisting in annealing the samples at
550 C for 40 h in an atmosphere containing water vapor at 75 mol%. XAS
measurements at the Co-K edge were carried out to reveal the chemical status of
the metal prior or after the HT. All samples revealed to be stable under HT; no
remarkable differences were present in the XAS spectra with respect to the non-HT
ones. In samples containing 5 % Co, Cobalt was found tetracoordinated to oxygen
with a faint signal from a Co second shell. On the other samples with higher Co
content, a well-defined second shell signal was visible that was attributed to the
formation of Co3O4 nanoparticles.
Again on the topic of metallic nanoparticles, Takao et al. (2012) have demon-
strated the production of metallic Pd and PdO particles in hollow silica
nanoparticles. This method possesses the advantage of producing metallic clusters
with an extremely reduced number of atoms (4–60) that is difficult to be obtained in
other ways. The hollow nanoparticles were produced starting from a spherical
template of Pd12L24 where L is a suitable ligand (triethoxysil group). The silica is
deposited on the surface of this template by using tetramethoxysilane with the
standard procedure. Successive calcination at 400 C in air eliminated the ligands
leaving small clusters with 12 Pd atoms inside the hollows of the spheres. XAS at the
Pd-K edge showed that the clusters are made of PdO and that further treatment with
H2 leads to the formation of metallic Pd.
X-ray Absorption Spectroscopy Studies on Materials Obtained by the Sol-Gel. . . 17

Further studies on nanoparticles obtained by sol-gel and characterized by XAS

have been carried out for the production of magnetic semiconductors (Bilecka et al.
2011; Kumar et al. 2014; Hu et al. 2011; Liu et al. 2010) and catalysts (Santos
et al. 2012; Prieto et al. 2010; Mathew et al. 2011).

Materials for Catalysts and Sensors

Metallic nanoparticles (MNP) embedded in a porous material are largely used in

heterogeneous catalysis but these systems easily undergo deactivation by sintering.
A way to limit this problem is to host them in a suitable host to maintain their
dispersion. Among others, silica Aerogels have been proposed but their use remains
limited due to their high production costs. Recently, Kristiansen et al. (2011, 2012)
have succeeded in incorporating Cu in silica aerogels produced by Ambient Pressure
Drying, a method that greatly simplifies the production of this kind of material. In the
first paper (Kristiansen et al. 2011), the group has demonstrated the dispersion of Cu
species in the aerogel by looking to the XAS spectra collected at the Cu-K edge and
verified that no Cu-Cu bonds were present. In a subsequent study (Kristiansen
et al. 2012), the group has used XAS to study the formation of Cu nanoparticles in
presence of a reductive atmosphere (5 % H2 in He) and at high temperature. The
XAS spectra presented metal-metal bonds with a reduction of the first shell coordi-
nation number due to the reduced size of the particles (estimated to contain about
80 atoms). Data were collected at increasing temperature values and differences in
the spectra were evidenced suggesting a change in shape and local symmetry of the
clusters. In order to interpret the XAS experimental data, XAS spectra were simu-
lated based on the results of atomistic simulations (in the framework of the DFT
theory) of clusters of different shape. The results of the study are collected in Fig. 7.
At about 300 C, Cu forms nanoclusters that, from the number of Cu first
neighbors observed (8) and comparison with DFT theoretical data, are identified
as clusters with Td symmetry (fcc structure) containing about 80 atoms. The size of
these particles (about 1.4 nm) is well matched with that of the typical pores (<2 nm)
in the aerogel. Rising the temperature at 450 C, a lower coordination number is
reported that is in agreement, by comparison with XAS theoretical spectra generated
from the structural simulations, with the formation of flat clusters with C2h symmetry
(face centered cubic, fcc, structure) or D2h symmetry (body centered cubic, bcc,
structure). The successive exposure to oxidizing agents leads to the redispersion of
Cu ions in the aerogel with total loss of Cu-Cu bonds. This demonstrates that silica
aerogels can host metallic ions that can be reversibly converted in metallic
nanoparticles under reducing/oxidizing conditions. The presence of metallic parti-
cles in the pores guarantees against the sintering process making this material
particularly interesting for applications in catalysis.
Ordered mesoporous silica is of extreme interest for catalysis as it exhibits
ordered pore structure, tunable pore size, and high specific areas. Carta
et al. (2014) have reported on the successful production of mesostructured silica
(SBA-16 type) doped with Co and Fe and followed its behavior upon various thermal
18 F. d’Acapito

Fig. 7 Formation and Morphological evolution of Cu clusters in a silica aerogel when treated with
reducing atmosphere (H2, upper panel) or oxidizing atmosphere (O2, NO, lower panel) (Reprinted
with permission from Ref. (Kristiansen et al. 2012). Copyright 2012. American Chemical Society)

treatments. The samples were produced via a template-gelation method and contained
5 M % of Co, Fe, or both with respect to Si. The gels were calcined in air at 500 C and
successively reduced in H2 atmosphere at 800 C. XAS spectra at the Co-K and Fe-K
edges were collected to follow the evolution of the chemical state of the metals with
XAS during the calcination and reduction processes. After calcination, Co is present
as a layered silicate Co3Si2O5(OH)4 in the samples containing only this metal, whereas
it is in oxide phase in the case of mixed doping. Fe on the contrary, is always in the
oxide phase. Upon reduction, Co forms fcc clusters with no trace of oxidation whereas
Fe forms BCC cluster with a sizeable fraction of oxide.
Porous layers of SnO2 are used for applications as gas sensing materials, and the
doping with Pt or Au is reported to improve the properties. In order to understand the
role of Pt in a Pt:SnO2 sensor, H€ubner et al. (2011) have investigated this system with
XAS at the Pt-L3 edge and under exposure to gases like CO or H2. In order to
circumvent experimental problems posed by the underlying Au electrode, the data
collection has been carried out in the so-called High Energy Resolution Fluorescence
Detection (HERFD) (H€am€al€ainen et al. 1991). This particular data collection mode
uses a detector with high energy resolution (crystal analyzer with ΔE  1 eV) to
carefully select only the emission of the desired element and get rid of unwanted
additional emissions. In this case, HERFD permitted the collection of the Pt emission
without being overwhelmed by the Au emission form the electrode. The XAS
spectrum revealed an exceptionally high white line (the sharp resonance on the
edge) six times more intense than the atomic level, revealing a highly oxidized
Pt. On the contrary, the intensity of the white line did not changed significantly
upon exposure to the gases meaning that the role of Pt in the improvement of the
behavior of the sensor is not a direct interaction with the gas but rather provides free
carriers to the bulk SnO2. The same group (H€ ubner et al. 2012) found similar results
on Au-doped SnO2 collecting HERFD XAS data at the Au-L3 edge.
X-ray Absorption Spectroscopy Studies on Materials Obtained by the Sol-Gel. . . 19

Fig. 8 Fourier Transforms of the XAS spectra of samples treated at different temperatures: left:
high Zr content samples, right: low Zr content (Figure reproduced from Ref. (Meneghetti
et al. 2010) with permission from The Royal Society of Chemistry)

Meneghetti et al. (2010) have studied the crystallization properties of composite

materials consisting in ZrO2 embedded in silica and obtained by a sol-gel procedure.
Samples containing a high (1:1.3 with respect to Si) or low (1:40 with respect to Si)
Zr amount were prepared and their crystallization behavior were compared at
different annealing temperatures. In this case, XAS reveals to be extremely useful
as it permits to monitor the state of Zr also in the amorphous phases that are invisible
to XRD or Transmission Electron Microscopy (TEM).
The analysis of the XAS data (see Fig. 8, left) reveled that in the case of Zr at high
concentration, the environment of Zr consists in O first neighbors and Zr second
neighbors. These are just nuclei as no crystalline phase is evidenced by XRD or TEM
and the Zr-Zr distance is typical of that found in the monoclinic phase. Upon heating,
crystalline ZrO2 is formed between 700 C and 900 C and the Zr-Zr distance is
typical of the tetragonal phase as then confirmed by XRD. On the other hand, Zr added
in low amount (see Fig. 8, right) does not form any crystalline phase even after
treatment at 1000 C. This comes from the fact that Zr is well dissolved in the matrix
and the concentration is too low for the efficient diffusion process that make the nuclei
grow.
20 F. d’Acapito

Electrodes for Batteries

Pivko et al. (2012) have carried out an in situ XAS study on the reversible uptake of
alkali A (Li or Na) in A3V2(PO4)3 materials for battery electrodes. The need of
comparing the two alkali elements comes from the search of alternative technologies
for Li-ion batteries due to the shortage of world resources of Li. The aim of the
experiment was to demonstrate that Na can be reversibly inserted in the material. For
this purpose, a XAS experiment at the V-K edge was carried out with in situ
treatment and collecting XAS spectra at times during charging/discharging of the
electrode.
Data has shown full reversibility of the process in both cases, i.e., V is oxidized
upon alkali load (with consequent shift of the absorption edge at higher energy
values) and reduced upon alkali release (inverse behavior of the edge position), as
shown in Fig. 9. Intermediate XANES data could be reproduced as linear combina-
tion of the extremes (i.e., full oxidized and full reduced) and this has permitted to
follow with the charging/discharging time, the amount of V4+ with respect to the
total V. The analysis of the EXAFS data yielded results that confirmed the XANES
findings: upon oxidation, the V-O bond length slightly contracted as expected for an
increasing fraction of the V4+ ion. The same material was studied by Li et al. (2015)
with the addition of Mg to form Na3V2xMgx(PO4)3. The magnesium was found
not to alter the overall structure and that it was hosted in the matrix as a substitution
for V.
Bezza et al. (2015) have investigated the redox behavior of LiFe0.4Mn0.6PO4
electrodes for Li-ion batteries. The materials were prepared by sol-gel using acetates
as the precursors of the metal species and citric acid as chelating agent. After drying
and calcination, the material was mixed with sucrose and annealed again for
realizing the carbon coating of the particles. XANES data at the Fe and Mn-K
edges were collected during full charge/discharge cycles for a total duration of
about 20 h. The position of the metal edges was monitored with time and it could
be evidenced a metal oxidation (Fe2+ ! Fe3+, Mn2+ ! Mn3+) in the charge cycle
and vice versa in the discharge cycle. Fe appeared to change its valence state since
the beginning of the process whereas Mn changed state only in the vicinity of the
highest (4.0 V) potentials. The Fe oxidation/reduction is reported to be complete
whereas this process is only partial for Mn.
A more complex analysis method for XAS data permitting to determine the
temporal (i.e., with the potential) evolution of different phases in a process was
presented by Conti et al. (2010). Here a chemometric approach through the Fixed
Size Window Evolving Factor Analysis (FSWEFA) was used to study the transfor-
mation of Cu in a Cu-doped (5 mol % with respect to V) V2O5 cathode upon
lithiation. The method permitted to follow the evolution of the different chemical
phases involving Cu during the cell cycling.
Further works involving XAS characterization of battery materials obtained by
sol-gel are reported as a new method to prevent Mn loss during cycles in LiMn2O4
materials for cathodes (Lu et al. 2014), sol-gel preparation used to control and
optimize the texture in LiCoO2 cathodes (Gao et al. 2015), use of new materials
X-ray Absorption Spectroscopy Studies on Materials Obtained by the Sol-Gel. . . 21

Fig. 9 Left: evolution of the XANES of V during Na discharge in Na3V2(PO4)3 (V oxidation).

Center: evolution of the XANES of V during Na load in Na3V2(PO4)3 (V reduction). Right: time
evolution of the ratio V4+/total V as a function of time compared with the voltage profile (black) as a
function of time (Reprinted from Ref. (Pivko et al. 2012) Copyright (2012), with permission from
Elsevier)

like oxyphosphates obtained by sol-gel (Ni0.5TiOPO4) of Li4Ti5O12 (Kuo and Lin

2014) as new electrodes.

Perspectives

Novel techniques for data collection and analysis have been proposed recently and
will play a major role in the forthcoming activity in XAS with sure advantages also
for sol-gel materials.
From the experimental point of view, the so-called photon-in–photon-out tech-
niques based on the energy analysis of the X-ray emission from the sample are
attracting a growing interest. HERFD was already mentioned in the previous
22 F. d’Acapito

sections; a further technique based on the collection of the sample emission with a
high energy resolution detector is the X-Ray Emission Spectroscopy (XES) or
Resonant Inelastic X-ray Scattering (RIXS) (for a recent review, see (Rovezzi and
Glatzel 2014) and the many references therein). This procedure is based on the
analysis of the shape and position of the emission lines from which it is possible to
retrieve information on the upper-lying electronic states that are more affected by the
chemical environment. In particular, by analyzing emission lines coming from
Valence-to-Core (VTC) transitions, it is possible to determine the nature of ligands
even if they are neighbors in the periodic table, whereas by analyzing transitions
coming from Core-to-Core states, the spin state of the element can be derived. As
this technique requires the use of high-energy resolving crystal detectors, the same
limitations discussed in section “Data Collection and Analysis” apply.
From the data analysis point of view, it must be stressed that recent developments
in computational material science have provided in the recent years new tools for
structural simulations. Advanced codes based on the Density Functional Theory
(DFT) (like ABINIT (Gonze et al. 2009), QUANTUM-ESPRESSO (Giannozzi
et al. 2009), VASP (Kresse and Furthmller 1996), WIEN2K (Blaha et al. 1990))
have appeared that permit an interpretation of the XAS data in close relation with the
theory (d’acapito 2011). In the case of disordered systems or high temperatures, it
was shown to be possible to calculate XAS spectra from Molecular Dynamics
calculations (Palmer et al. 1996; McCarthy et al. 1997) and now these methods
have become widespread due to the improved speed of modern computers. By
averaging a suitable number of structural frames (around 100–200 units, following
(d’Angelo et al. 2008), it is possible to generate ab initio EXAFS spectra in good
agreement with the experiment as verified for ions in aqueous solutions (d’Angelo
et al. 2008; Cauet et al. 2010) and for metallic clusters at high temperatures (Vila
et al. 2007; Vila et al. 2008) so providing an effective method for the comparison
between theory and experiment and to identify the correct structure for the material
under study.

References
Achkar AJ, Regier TZ, Wadati H, Kim Y-J, Zhang H, Hawthorn DG. Phys Rev B. 2011;83:081106(R).
Afify ND, Dalba G, Armellini C, Ferrari M, Rocca F, Kuzmin A. Phys Rev B. 2007;76:024114.
Ankudinov AL, Ravel B, Rehr JJ, Conradson SD. Phys Rev B. 1998;58:7565.
Bearden JA, Burr AF. Rev Mod Phys. 1967;39:125.
Benfatto M, Natoli CR, Bianconi A, Garcia J, Marcelli A, Fanfoni M, Davoli I. Phys Rev B.
1986;34:5774.
Benfatto M, Natoli CR, Filipponi A. Phys Rev B. 1989;40:9626.
Benfatto M, Della Longa S, Natoli CR. J Synchrotron Radiat. 2001;10:51.
Beni G, Platzmann PM. Phys Rev B. 1976;14:1514.
Bezza I, Kaus M, Heinzmann R, Yavuz M, Knapp M, Mangold S, Doyle S, Grey CP, Ehrenberg H,
Indris S, Saadoune I. J Phys Chem C. 2015;119(17):9016–24.
Bilecka I, Luo L, Djerdj I, Rossell MD, Jagodic M, Jaglicic Z, Masubuchi Y, Kikkawa S,
Niederberger M. J Phys Chem C. 2011;115(5):1484–95.
Binsted N. http://srs.dl.ac.uk/XRS/Computing/Programs/excurv97/intro.html
X-ray Absorption Spectroscopy Studies on Materials Obtained by the Sol-Gel. . . 23

Blaha P, Schwarz K, Sorantin P, Trickey SB. Comp Phys Commun. 1990;59(2):399–415.

Borowski M, Bowron DT, De Panfilis S. J Synchrotron Radiat. 1999;6:179–81.
Bunker G. Introduction to XAFS: a practical guide to X-ray absorption fine structure spectroscopy.
Cambridge, UK: Cambridge University Press; 2010.
Caetano BL, Florian M, Santilli CV, Pulcinelli SH, Magnani M, Briois V. Chem Mater.
2014;26:6777.
Carta D, Casula MF, Bullita S, Falqui A, Casu A, Carbonaro CM, Corrias A. Microporous
Mesoporous Mater. 2014;194:157–66.
Carvalho JM, Lastusaari M, Rodriguesa LCV, Holsa J, Felinto MCFC, Brito HF. J Lumin.
2016;170:627.
Cauet E, Bogatko S, Weare JH, Fulton JL, Schenter GK, Bylaska EJ. J Chem Phys. 2010;132
(19):194502.
Chou SH, Rehr JJ, Stern ED, Davidson ER. Phys Rev B. 1987;35:2604.
Citrin PH, Eisenberger P, Hewitt RC. Phys Rev Lett. 1978;41:309.
Conti P, Zamponi S, Giorgetti M, Berrettoni M, Smyrl WH. Anal Chem. 2010;82(9):3629–35.
Cramer SP, Eccles TK, Kutzler FW, Hodgson KO, Mortenson LE. J Am Chem Soc. 1976;98:1287.
d’Acapito F. Semicond Sci Technol. 2011;26:064004.
d’Acapito F, Davoli I, Ghigna P, Mobilio S. J Synchrotron Radiat. 2003;10:260.
d’Acapito F, Marques A, Santos LF, Almeida RM. J Non-Cryst Solids. 2008;254:4940.
D’Angelo P, Migliorati V, Mancini G, Barone V, Chillemi G. J Chem Phys. 2008;128(8):084502.
Della Longa S, Arcovito A, Girasole M, Hazemann JL, Benfatto M. Phys Rev Lett.
2001;87:155501.
Ebert H. Lect Notes Phys. 1998;535:191.
Eisenberger P, Brown GS. Solid State Commun. 1979;29:481.
Filipponi A, DiCicco A. Phys Rev B. 1995;52:15135–49.
Filipponi A, DiCicco A, Natoli CR. Phys Rev B. 1995;52:15122–34.
Fortes LM, Goncalves MC, Pereira JC, d’Acapito F. J Non-Cryst Solids. 2014;402:244.
Galoisy L, Calas G, Arrio MA. Chem Geol. 2001;174:307.
Gao S, Wei W, Ma M, Qi J, Yang J, Zhang J, Guo L. RSC Adv. 2015;5:51483.
Geraldo V, Briois V, Scalvi LVA, Santilli CV. J Phys Chem. 2010;114:19206.
Giannozzi P, Baroni S, Bonini N, Calandra M, Car R, Cavazzoni C, Ceresoli D, Chiarotti GL,
Cococcioni M, Dabo I, Dal Corso A, de Gironcoli S, Fabris S, Fratesi G, Gebauer R,
Gerstmann U, Gougoussis C, Kokalj A, Lazzeri M, Martin-Samos L, Marzari N, Mauri F,
Mazzarello R, Paolini S, Pasquarello A, Paulatto L, Sbraccia C, Scandolo S, Sclauzero G,
Seitsonen AP, Smogunov A, Umari P, Wentzcovitch RM. J Phys Condens Matter.
2009;21:395502.
Glatzel P, de Groot FMF, Manoilova O, Grandjean D, Weckhuysen BM, Bergmann U, Barrea R.
Phys Rev B. 2005;72(1):014117.
Gonze X, Amadon B, Anglade P-M, Beuken J-M, Bottin F, Boulanger P, Bruneval F, Caliste D,
Caracas R, Ct M, Deutsch T, Genovese L, Ghosez P, Giantomassi M, Goedecker S, Hamann
DR, Hermet P, Jollet F, Jomard G, Leroux S, Mancini M, Mazevet S, Oliveira MJT, Onida G,
Pouillon Y, Rangel T, Rignanese G-M, Sangalli D, Shaltaf R, Torrent M, Verstraete MJ,
Zerah G, Zwanziger JW. Comp Phys Commun. 2009;180:2582.
Gougoussis C, Calandra M, Seitsonen AP, Mauri F. Phys Rev B. 2009;80:075102.
H€am€al€ainen K, Siddons DP, Hastings JB, Berman LE. Phys Rev Lett. 1991;67(20):2850.
Heald SM, Tranquada JM, Chen H. Phys Rev B. 1988;38:1016–26.
Hu F, Liu Q, Sun Z, Yao T, Pan Z, Li Y, He J, He B, Xie Z, Yan W, Wei S. J Appl Phys.
2011;109:103705.
H€ubner M, Koziej D, Bauer M, Barsan N, Kvashnina K, Rossell MD, Weimar U, Grunwaldt
JD. Angew Chem Int Ed. 2011;50(12):2841–4.
H€ubner M, Koziej D, Grunwaldt JD, Weimar U, Barsan N. Phys Chem Chem Phys. 2012;14
(38):13249–54.
Iwasawa Y. Catal Surv Jpn. 1997;1:3.
24 F. d’Acapito

Jaklevich J, Kirby JA, Klein MP, Robertson AS, Brown GS, Eisenberger P. Solid State Commun.
1977;23:679.
Joly Y. Phys Rev B. 2001;63:125120.
Kincaid BM, Eisenberger P. Phys Rev Lett. 1975;34:1361.
Köningsberger DC. In: Königsberger DC, Prins R, editors. X-ray absorption. New York: Wiley;
1988.
Krause MO, Oliver JH. J Phys Chem Ref Data. 1979;8:329.
Kresse G, Furthmller J. Phys Rev B. 1996;54:11169.
Kristiansen T, Mathisen K, Einarsrud MA, Bjørgen M, Nicholson DG. J Phys Chem C. 2011;115
(39):19260–8.
Kristiansen T, Støvneng JA, Einarsrud MA, Nicholson DG, Mathisen K. J Phys Chem C. 2012;116
(38):20368–79.
Kumar S, Basu S, Rana B, Barman A, Chatterjee S, Jha SN, Bhattacharyya D, Sahoo NK, Ghosh
AK. J Mater Chem C. 2014;2(3):481–95.
Kuo YC, Lin JY. Electrochim Acta. 2014;142:43–50.
Kuzmin A. J Phys IV. 1997;7:C2–213.
Lee PA, Beni G. Phys Rev B. 1977;15:2862.
Lee PA, Citrin PH, Eisemberger P, Kincaid BM. Rev Mod Phys. 1981;53:769.
Li H, Yu X, Bai Y, Wu F, Wu C, Liu LY, Yang XQ. J Mater Chem A. 2015;3(18):9578–86.
Little W, Karatutluy A, Bolmatov D, Trachemko K, Sapelkin AV, Cibin G, Taylor R, Mosselmans F,
Dent AJ, Mountjoy G. Sci Rep. 2014;4:7372.
Liu H, Yang J, Hua Z, Zhang Y, Yang L, Xiao L, Xie Z. Appl Surf Sci. 2010;256(13):4162–5.
Liu L, Wang DK, Kappen P, Martens DL, Smartab S, Diniz da Costa JC. Phys Chem Chem Phys.
2015a;17:19500.
Liu X, Wu F, Chen S, Gua M, Chen H, Liu B, Huang S, Zhang J. J Lumin. 2015b;161:422.
Lu J, Zhan C, Wu T, Wen J, Lei Y, Kropf AJ, Huiming Wu, Miller DJ, Elam JW, Sun Y, Qiu X, Qiu X.
Nat Commun. 2014;5:5693.
Majeed J, Nayak C, Jha SN, Bhattacharyya K, Bhattacharyya D, Tripathi AK. RSC Adv. 2015;5
(110):90932–40.
Mathew T, Suzuki K, Ikuta Y, Nagai Y, Takahashi N, Shinjoh H. Angew Chem. 2011;123
(32):7519–22.
McCarthy MI, Schenter GK, Chacon-Taylor MR, Rehr JJ, Brown GE. Phys Rev B. 1997;56
(15):9925–36.
Meneghetti F, Wendel E, Mascotto S, Smarsly BM, Tondello E, Bertagnolli H, Gross S. Cryst Eng
Comm. 2010;12(5):1639–49.
Nakajima S, Segawa H, Yanagida S, Yasumori A, Hirosaki N. J Ceram Soc Jpn. 2013;121:361.
Natoli CR, Benfatto M. J Phys Coll. 1986;C8:11.
Newille M. Phys Scr. 2005;T115:159.
Palmer BJ, Pfund DM, Fulton JL. J Phys Chem. 1996;100(32):13393–8.
Parratt LG. Phys Rev. 1954;95:359.
Pfalzer P, Urbach JP, Klemm M, Horn S, denBoer ML, Frenkel AI, Kirkland JP. Phys
Rev B. 1999;60:9335.
Pivko M, Arcon I, Bele M, Dominko R, Gaberscek M. J Power Sources. 2012;216:145–51.
Poiarkova AV, Rehr JJ. Phys Rev B. 1999;59(2):948–57.
Potdevin A, Chadeyron G, Briois V, Leroux F, Santilli CV, Dubois M, Boyer D, Mahiou R. Dalton
Trans. 2010a;39:8706.
Potdevin A, Chadeyron G, Briois V, Leroux F, Mahiou R. Dalton Trans. 2010b;39:8718.
Prieto PJS, Ferreira AP, Haddad PS, Zanchet D, Bueno JMC. J Catal. 2010;276(2):351–9.
Rehr JJ, Albers RC. Rev Mod Phys. 2000;72:621–54.
Rehr JJ, Kas JJ, Prange MP, Sorini AP, Takimoto Y, Vila F. C R Phys. 2009;10(6):548–59.
Rogalev A, Goulon J, in Chemical Applications of Synchrotron Radiation: X-ray applications Vol. 2
Chapter 15: Soft X-ray Excited Optical Luminescence Spectroscopies. Advanced Series in
Physical Chemistry (World Scientific Publishing Co. Singapore, 2002)
X-ray Absorption Spectroscopy Studies on Materials Obtained by the Sol-Gel. . . 25

Rovezzi M, Glatzel P. Semicond Sci Technol. 2014;29(2):023002.

Santos RDS, Faria GA, Giles C, Leite CA, Barbosa HDS, Arruda MA, Longo C. ACS Appl Mater
Interfaces. 2012;4(10):5555–61.
Sayers DE, Stern EA, Lytle FW. Phys Rev Lett. 1971;27:1204–7.
Sevillano E, Meuth H, Rehr JJ. Phys Rev B. 1979;20:4908.
Sham TK, Rosenberg RA. Chem Phys Chem. 2007;8:2557.
Shi T, Zhu S, Sun Z, Wei S, Liu W. Appl Phys Lett. 2007;90:102108.
Stern EA. In: Königsberger DC, Prins R, editors. X-ray absorption. New York: Wiley; 1988.
Stotzel J, Lutzenkirchen-Hecht D, Frahm R, Santilli CV, Pulcinelli SH, Kaminski R, Fonda E,
Villain F, Briois V. J Phys Chem C. 2010;114:6228.
Takao K, Suzuki K, Ichijo T, Sato S, Asakura H, Teramura K, Kato K, Ohba T, Morita T,
Fujita M. Angew Chem. 2012;51:5893–6.
Terra IAA, Borrero-González LJ, Carvalho JM, Terrile MC, Felinto MCFC, Brito HF, Nunes LAO.
J Appl Phys. 2013;113:073105.
Tranquada JM, Ingalls RI. Phys Rev B. 1983;28:3520.
Troger L, Arvanitis D, Baberschke K, Michaelis H, Grimm U, Zschech E. Phys Rev B.
1992;46:3283.
Tyson T, Hodgson KO, Natoli CR, Benfatto M. Phys Rev B. 1992;46:5997.
Van TTT, Turrell S, Capoen B, Vinh LQ, Cristini-Robbe O, Bouazaoui M, d’Acapito F, Ferrari M,
Ristic D, Lukowiak A, Almeida R, Santos L, Kinowski C. Sci Adv Mater. 2015;7:301.
Vila FD, Rehr JJ, Rossner HH, Krappe HJ. Phys Rev B. 2007;76(1):014301.
Vila F, Rehr JJ, Kas J, Nuzzo RG, Frenkel AI. Phys Rev B. 2008;78(12):121404.
Ye T, Li S, Wu X, Xu M, Wei X, Wang K, Bao H, Wang J, Chen J. J Mater Chem C. 2013;1:4327.
Zabinsky SI, Rehr JJ, Ankudinov A, Albers RC, Eller MJ. Phys Rev. 1995;B52:2995–3009.