This is the peer reviewed version of the following article: S.

Hinokuma, G. Wiker, T. Suganuma, A. Bansode,
D. Stoian, S. Caminero Huertas, S. Molina, A. Shafir, M. Rønning, W. van Beek, A. Urakawa, EurJIC
2018, which has been published in final form at https://onlinelibrary.wiley.com/doi/abs/10.1002/ejic.201800140
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Versatile IR spectroscopy combined with synchrotron XAS-XRD:
Chemical, electronic and structural insights during thermal
treatment of MOF materials
Satoshi Hinokuma,[a,b] Geir Wiker,[c] Takuya Suganuma,[d] Atul Bansode,[e] Dragos Stoian,[c] Silvia
Caminero Huertas,[e] Sonia Molina,[e] Alexandr Shafir,[e] Magnus Rønning,[f] Wouter van Beek,[c] and
Atsushi Urakawa*[e,g]
Abstract: Understanding the physicochemical origin of functional
materials generally requires multi-faceted information on their
material characteristics investigated by various analytical methods.
In this respect, simultaneous multi-probe approach to study
materials by complementary methods is of great value, particularly to
follow dynamically varying processes such as chemical and
structural transformation under reactive environment. Herein, we
report facile and versatile approaches to combine synchrotron X-ray
absorption spectroscopy and diffraction with IR spectroscopy in
transmission and diffuse-reflection sampling configurations to study
pellet samples under controlled environment. The high practicality of
the approach was enabled by the use of a modular IR spectrometer.
Rich information on chemical, electronic and structural changes of
Zr-BTC and Cu-BTC MOFs during a thermal treatment was gained
by the multi-probe approach. The advantages and practical
challenges of the combined approaches are discussed.

Introduction
Functionality of inorganic materials is widely investigated and
understood by spectroscopic and diffraction methods through
rich information on their physicochemical properties including
chemical interactions, long-range order and electronic/magnetic
structures. Remarkable progresses have been made in modern
detection techniques; however, convincing solutions to the
puzzles in chemistry and material sciences often require multifaceted information. In theory, holistic information to solve the

[a]

[b]
[c]
[d]
[e]

[f]
[g]

Department of Applied Chemistry and Biochemistry, Graduate
School of Science and Technology, Kumamoto University, 2-39-1
Kurokami, Chuo-ku, Kumamoto 860-8555, Japan
International Research Organization for Advanced Science and
Technology, Kumamoto University, Japan
The Swiss-Norwegian Beamlines (SNBL) at ESRF, BP 220, F38043 Grenoble, France
Toyota Motor Corporation, 1200, Mishuku, Susono, Shizuoka,
Japan
Institute of Chemical Research of Catalonia (ICIQ), The Barcelona
Institute of Science and Technology, Av. Països Catalans 16, 43007
Tarragona, Spain
*Emai: aurakawa@iciq.es
Department of Chemical Engineering, Norwegian University of
Science and Technology, 7491 Trondheim, Norway
JST, PRESTO, 4-1-8 Honcho Kawaguchi, Saitama 332-0012, Japan

puzzles can be obtained separately by various detection
methods on a sample under an identical environment, but it is
always of great challenge to ensure the comparability of the
results. This is especially true when materials are studied under
a specific set of conditions where chemical and structural
transformation takes place, such as a reaction environment
common in catalytic reactions. Obviously, measurements
performed simultaneously by different techniques (i.e. multiprobe) are the most ideal solution to make sure that the
inorganic material state is absolutely identical. Hence, numerous
researchers have reported such approaches, each providing
distinct advantages depending on the analytical techniques
chosen and the cell design [1].
The use of synchrotron X-ray has shown its unique advantages
in performing in situ and operando spectroscopic and diffraction
studies and its use became a standard in the modern chemical
and material science [2]. This is facilitated by better accessibility
to synchrotron radiation facilities seen over the past few
decades. For instance, it is increasingly possible to combine Xray absorption spectroscopy (XAS) and X-ray diffraction (XRD)
with
Raman
spectroscopy simultaneously or
quasisimultaneously [3]. On the other hand, simultaneous
measurements of X-ray spectroscopy with infrared (IR)
spectroscopy has been limited, although IR spectroscopy is the
most versatile analytical method used under in situ conditions to
study chemical structures and interactions of gas, liquid, solid
and their interfaces [4]. This scarcity mainly originates from the
restrictive requirement of optical components as well as from the
geometrical inconvenience of the combined measurements, e.g.
the placement of an IR spectrometer that would enable
simultaneous IR and X-ray spectroscopies. In this respect,
Raman spectroscopy has evident advantages because Raman
excitation laser and signals can be conveniently transmitted
through optical fiber and hence only requires placing a portable
probe near the sample. Despite the difficulties to perform
simultaneous IR and X-ray spectroscopies, Newton et al.
pioneered such combination with diffuse reflectance Fourier
transform IR spectroscopy (DRIFTS) to study powder samples
and extensively applied the combined approaches in operando
studies of catalytic materials [5].
Herein, we report proof-of-principle experiments of the combined
XAS-XRD with, for the first time to the best of our knowledge,
transmission IR spectroscopy as well as DRIFTS using a pelletshaped material using a cell suited for combined XAS-XRD [6]

adapted to allow IR detection. Particularly, we show the use of a
modular IR spectrometer, enabling these combinations in a
facile and versatile fashion, manifesting ample opportunities for
far-ranging combination of IR spectroscopy with other detection
methods. To verify the power of the combined approach and
good signal quality, chemical, geometrical and electronic
structural changes of benzene-1,3,5-tricarboxylate (BTC)-based
Zr and Cu metal-organic framework (MOF) materials were
studied during the thermal treatment process.

Transmission IR spectroscopy combined with XAS-XRD
Simultaneous measurements of transmission IR and XAS-XRD
were made possible by fixing a heatable sample holder (Figure
1B) in the cell at about 45° to the X-ray and with respect to the
surface of the pellet (Figure 1A). Nearly orthogonal to the X-ray,
IR light was passed through the sample. In practice the angle
was slightly tilted to increase the sampling area by the IR light by
quickly and conveniently adjusting the position of the IR
spectrometer and detector (Figure 1C). Such an orthogonal
configuration of the light paths and alignment capability are very
difficult, if at all possible, with conventional box-shaped
spectrometers. The freely-movable interferometer with the IR
source and the mid-IR (thermoelectrically cooled MCT) detector
of the mobile IR spectrometer system (Arcoptix S. A., OEM
model) allowed flexible positioning and sensitive signal detection.
The study of pellet sample is by itself challenging in terms of
achieving the best quality signals in the multi-probe
measurement due to the necessity to optimize the sample
amount/thickness. The situation is further complicated when an
ultra-thin self-supporting wafer is required in IR spectroscopy.
Here we evaluated an option of using a pellet made by a twostep process, by first preparing a 13 mm diameter pellet of NaCl
(50 mg) at high pressure and then placing softly a small amount
of the sample (3 mg of Zr-BTC, vide infra) at low pressure. This
method allows for optimisation of the material amount for use in
transmission IR and XAS. The requisite for the base supporting
pellet is that it should be transparent to both IR and X-ray at the
energy of the measurement. Hence, the typical material for IR
pellet, KBr, cannot be used conveniently in this case, since Br is
a comparably heavy chemical element, thus absorbing most
incident X-ray. At the K-edge of Zr (ca. 18 keV), NaCl is highly
transparent and can be conveniently used and thus this material
was chosen.

Figure 1. (A) Schematic drawing of the cell (top view) and IR light and X-ray
optical paths to perform the simultaneous IR-XAS-XRD measurements. (B)
Pellet sample holder. The holes are to insert heating cartridges. (C) The IRXAS-XRD system in action where the cell was purged with He at 100 mL min-1
during the thermal treatment.

Results and Discussion
IR spectroscopy combined with XAS/XRD on a same sample
has been scarcely reported due to geometrical constraints as
well as the compatibility of optical materials and sample
concentration or thickness, in particular to perform IR
spectroscopy with XAS (XRD has less restrictions in practice).
Herein we evaluated two different IR sampling configurations,
namely transmission IR spectroscopy and DRIFTS in
combination with XAS-XRD, to study pellet samples under
controlled environment (sample temperature and atmosphere).
The possibility of two IR sampling configurations broadens the
scope of materials which can be studied by the combined
method. Below, the sections are separated by the
measurements using the respective IR sampling configuration.

Figure 2. (A) Geometrical structure of BTC. (B) Zirconium oxide secondary
building unit (SBU) where six octahedrally disposed zirconium atoms are held
together. Hydrogen atoms are not shown for the sake of clarity. The figure
shows how six BTCs and formates coordinate to Zr (the structure as reported
by Yaghi and coworkers as MOF-808 [7]. Note that the Zr-BTC of this study
contains acetates instead of formates. (C) The MOF-808 formed made by the
SBU and BTC.

Figure 2 shows the constituting molecular units and the structure
of the Zr-MOF material studied by the multi-probe approach. The
linker of the MOF material is benzene-1,3,5-tricarboxylate (BTC,
Figure 2A), connecting the zirconium oxide secondary building
unit (SBU) where six octahedrally disposed zirconium atoms are
held together by bridging carboxylates. The structure is known
as MOF-808 [7] and is related to the more popular Zr-based
MOF structures, such as the classical terephthalate-based UiO66. For MOF-808, six BTC linkers are connected to each SBU
(Figure 2B), with acetates providing the rest of the stabilization
for the Zr6 SBU (formates were used in the original work in [7]),
resulting in the structure shown in Figure 2C. Hereafter we call
the material, simply Zr-BTC. Prior to the thermal treatment, the
sample was pretreated by the procedure, so-called, activation. It
consists of evacuation for 5 h at room temperature and then for
15 h at 100 °C following a ramp of 1 °C min-1. The sample was
then exposed to air; thus the initial state of the sample mainly
contains a large amount of H2O in the porous structure (ca. 10
wt% according to TGA analysis). This type of MOF materials are
known to show unique characteristics for water adsorption and
absorption [7].

the thermal treatment (Figure 3B) as the temperature increased.
During the treatment, mainly water desorption took place as
evident form the drastic decrease of the broad band at ca. 3300
cm-1 characteristic of hydrogen-bonded, adsorbed H2O. Among
the six bands, the band at 1657 cm-1 disappeared during the
thermal treatment, while the changes of the other bands as shift
or decrease was less pronounced. According to the DFT
calculation (Figure 3C) this band can be assigned to the
asymmetric C-O stretching vibration of acetate ligand on the Zr
SBU. This indicates that the stability of the acetate ligand is
higher than adsorbed water, but they can be gradually removed
at 150 °C. Another prominent band of the acetate is the
combined C-C stretching and symmetric C-O stretching mode
experimentally observed at ca. 1387 cm-1. Both bands
underwent changes slightly with broadening or shift when water
was removed from the structure and then remarkably at ca.
150 °C (point 2, in Figure 3B), resulting in the band
disappearance. The small band of C-H bending vibration of
acetate, theoretically predicted to be at ca. 1460 cm-1, seems
emerging at ca. 1480 cm-1 when H2O was removed from the
MOF structure and then the band disappears as the prominent
1.5

10

B

1.2

RT

8

FT magnitude / Å–4

Normalized absorption / a.u.

A
0.9

0.6
150 °C

0.3

6
150 °C

4

2

RT
0.5

0.0
18000

18000

18010

0

18020
18040
Energy / eV
RT

0

1

2
Distance / Å

3

4

C

150 °C

3

1

Figure 3. (A) Ex situ transmission IR spectrum of Zr-BTC in air after the
activation treatment. The bar of 0.2 refers to Absorbance units. (B) In situ
transmission IR spectrum during the thermal treatment where Zr-BTC was
heated from RT to 150 °C at 0.5 °C/min and then kept for 4 h. The background
was taken using the last spectrum of this experiment (i.e. at the end of the
thermal treatment). (C) Calculated IR spectra of BTC and acetate anions at
B3PW91/6-311++G(2d,2p) and the band assignments from the normal mode
analysis.

The sample was heated from room temperature (RT) to 150 °C
at 0.5 °C min-1 under He flow and then kept at the temperature.
Chemical, geometrical and electronic information of Zr-BTC was
gained by the combined IR-XAS-XRD. Figure 3 summarizes the
IR view on the material during the thermal treatment. Figure 3A
shows the ex situ IR spectrum of the Zr-BTC before the thermal
treatment, showing six relatively-broad bands in the
characteristic frequency region. It is interesting to note that all
six bands underwent intensity change and/or band shift during

2

3

3.5

4
5
2q / degree

4

4.5

6

5

7

8

acetate band at 1657 cm-1 disappears. This implies that the
polarity environment changes near the methyl group of acetate
during the water removal. On the other hand, the bands due to
BTC at 1450, 1571 and 1622 cm-1 underwent minor changes in
absorbance (apparently the changes seems considerable but
this is due to the nature of difference spectrum). Generally all
bands showed red-shifts upon H2O removal, due to the higher
interactions between BTC and Zr-SBU upon thermal treatment.

Figure 4. XAS and XRD results during the thermal treatment. (A) Zr K-edge
normalized XANES spectra, (B) Fourier transforms (FT) of k3-weighted EXAFS
of Zr-BTC, and (C) XRD patterns of the Zr-BTC/NaCl pellet measured at three
time points (1: blue, 2: red, 3: green) during the thermal process as indicated
in Figure 3B.

Figure 4 summarises the electronic and structural views by XAS
and XRD on Zr-BTC under the thermal treatment. The Zr K-edge

X-ray absorption near-edge spectra (XANES, Figure 4A) show
the absorption energy and the intensity become lower upon the
treatment, implying the formation of a metal center with a
reduced coordination number, although the extent of the shift is
not drastic. On the other hand, the structural information gained
by extended X-ray absorption fine structure (EXAFS) shows a
great change in the local environment near Zr (Figure 4B). FT
magnitudes of the two prominent peaks at 1.8 and 3.3 Å
decreased, accompanying an increase of the peaks at 1.6 and
2.8 Å. A detailed analysis shows that the two peaks are
assigned to Zr-O and Zr-Zr distances, respectively. Similar
XANES and/or FT-EXAFS profiles of a related Zr-MOF material
have been disclosed [8]. Lillerud et al. studied by XANES and
EXAFS the effect of progressive dehydration of a Zr-MOF during
a heating treatment from RT to 300 °C, and similar behavior and
coordination change related to Zr were clarified. In fact, in a
seminal 2010 report, Lillerud, Lamberti and co-workers were
able to establish for the prototypical UiO-66 MOF a change in
the nature of the Zr6 SBU unit in going from the “as-synthesized”
materials to the dehydrated form [8b]. Specifically, a
combination of XRD, XAS and IR measurements showed a
reduction in the immediate Zr coordination sphere from 8
(refined for EXAFS with two independent Zr-O distances) to a
smaller value due to the loss of two molecules of water,
presumably from the initially present µ3-OH ligands. The change
meant that the cluster symmetry was reduced from tetrahedral
(Td) to D3d. Recently; a related solution-state study was also
reported for the discreet Zr6 SBU prepared as its acetate form
[8g]. It should be mentioned, however, that despite their
similarities, there exists an important structural difference
between the Zr6 units present in the UiO family of MOFs and in
the Zr MOFs based on 3-fold symmetric linkers, such as BTC
used in this study. Indeed, the metallic node in the Zr-BTC
system is expected to only contain 6 edges bridged by the
linker-bound carboxylates, with the remaining 6 edges occupied
by mono-carboxylates. This may lead to a thermal behaviour
different from that observed for the more highly connected UiO66. Even so, the observed spectral changes of Zr-BTC by XAS
are reasonable and the removal of acetate ligand was firmly
proven in this work by the complementary information of IR.
From XRD (Figure 4C), there are slight peak shifts observed and
some reflection intensities are altered mainly due to the electron
density changes in the pore, although generally the change was
rather minor (ca. 0.2% unit cell volume reduction according to
the Rietveld refinement). All these results indicate that the
framework (MOF) structure was retained after the thermal
treatment, but the structure and chemical environment of the Zr6
SBU did undergo a change. According to the IR results (Figure
3), the acetate ligands were removed, following the water
removal from the pore, and this should have a direct impact on
the structure of the SBU. XAS results (Figures 4A and 4B)
indicate that upon the acetate removal the Zr in the cluster unit
is more electronically saturated most likely due to the loss of
coordinating oxygen of acetate, and this induces the
readjustment of the coordination environment of Zr by
shortening the atomic distance among Zr atoms. These changes
are reminiscent to those due to the loss water from the Zr6

structural building units of UiO-66, although now the acetate
ligands may also be engaged in this thermal loss of bridging
ligand loss [8b]. Such detailed insights are uniquely gained by
the multi-probe approach, especially by the addition of the IR
spectroscopy which can provide chemically highly relevant
information. The results indicate that upon sufficiently long
thermal treatment at 150 °C in inert atmosphere, an
electronically richer (less coordinatively saturated) Zr center is
formed, thus possibly offering sites for catalytic reaction.

Figure 5. (A) The SBU of Cu-BTC where two copper atoms are held together.
The figure shows how four BTCs coordinate to Cu and two water molecules
are disposed (only oxygen atoms are shown) [9]. (B) Cu-BTC structure (known
as HKUST-1) formed by the SBU and BTC. Hydrogen atoms are not shown for
the sake of clarity.

DRIFTS combined with XAS-XRD
While transmission IR spectroscopy is ideal from quantitative
and less-temperature-dependency points of views, in some
cases measurement of pellet sample in combination with XASXRD is not possible. For example, when a Cu-MOF is studied, it
is not possible to use the same approach as shown above with a
NaCl supporting pellet due to the low Cu K-edge absorption
energy (ca. 9 keV). For this reason, we evaluated another IR
sampling configuration, DRIFTS, so that sample concentration
for IR is not limited any longer and one can increase it to an
optimum level for XAS-XRD. Here we performed a similar study
by a combined DRIFTS-XAS-XRD using a self-supporting wafer
of Cu-BTC MOF (known as HKUST-1, Figure 5).
Figure 6 shows the schematic configuration of the cell affording
DRIFTS. To enable both IR and X-ray spectroscopies from the
same window, a hole was made on a NaCl window which was
then sealed with a Kapton material. Using such a window and
placing the sample holder close to the window, there was
enough space for IR light to travel through the NaCl part of the
window and also for X-ray to travel through the hole, reaching
the sample and up to respective detector. Such configuration

was again possible due to the modular nature of the IR
spectrometer used in this study.

Figure 7. (left) DRIFT spectra of Cu-BTC in the OH stretching region during
the thermal treatment (ramp at 1 °C min-1) and (right) the area of the broad
band shown on the left and the signal of water (m/e=18) recorded by mass
spectrometry during the treatment.

Figure 8A presents Cu K-edge normalized XANES spectra of
Cu-BTC during the thermal treatment. The spectra showed a
minor pre-edge peak assigned to a charge-transfer excitation
[10] and the absorption decreased with a slight shift to lower
energies upon increasing temperature. According to a previous
report [11], these observations imply that the Cu in Cu-BTC
becomes electronically more saturated during the treatment by
the removal of the water in the SBU. This behavior is apparently
less pronounced compared to the case of Zr-BTC (Figure 4A).
On the other hand, the FT of k3-weighted EXAFS of Cu-BTC
basically did not undergo major changes, although a small
decrease of the peak at 1.6 Å attributed to Cu-O distance was
observed. Also, from XRD (Figure 8C) there are slight peak
shifts observed and reflection intensities are altered, but
generally the Cu-BTC structure was retained and the volume
change was also minor (ca. 0.3% decrease). Considering all
results, it can be concluded that water at the SBU can be
removed by the thermal treatment at 150 °C and this causes
partial reduction of Cu; however, its extent and effects on the
SBU structure are minor compared to the case of Zr-BTC where
the removal of the ligand induces more drastic changes in the
electronic density of the metal center, large changes in the
coordination environment near Zr atoms and consequently the
transformation of the SBU structure.
1.5

B

1.2

RT

8

FT magnitude / Å–4

It should be mentioned that the in this work a common pelleting
method was used, resulting the Cu-BTC pellet with a smooth
surface. This is not ideal for DRIFTS where scattered diffusereflection by a rough surface should be maximized. As a
consequence, the IR signal originating from the sample was very
low. Nevertheless, the signature of adsorbed water in the
material could be detected and the evolution during the thermal
treatment is summarized in Figure 7. Evidently, water gradually
desorbed from Cu-BTC upon heating, first with a decrease of
water from the pore as recognized by the disappearance of the
broad band at 3300-3600 cm-1, followed by the desorption of
strongly-bound water at higher temperature as indicated by the
isolated O-H vibrations at ca. 3650 cm-1.

Normalized absorption / a. u.

Figure 6. (A) Schematic drawing of the cell (top view) and IR light and X-ray
optical paths to perform the simultaneous DRIFTS-XAS-XRD measurements.
(B) The DRIFTS-XAS-XRD system in action.

10

A
0.9

0.6
150°C

0.3

150 °C

6

4

2
0.5
8980

0.0
8970

RT
8990

0

8990
9010
Energy / eV

C

0

1

2
Distance / Å

3

4

150 °C
RT

4.2

1

2

3

4
5
2q / degree

5.2 5.3

6

6.3

7

8

Figure 8. XAS and XRD results during the thermal treatment. (A) Cu K-edge
normalized XANES spectra, (B) Fourier transforms (FT) of k3-weighted EXAFS
of Cu-BTC, and (C) XRD patterns of the Cu-BTC pellet measured during the
thermal process as indicated in Figure 7.

Conclusions
Simultaneous multi-probe measurements by combining
synchrotron XAS and XRD with IR spectroscopy in transmission
and diffuse-reflection sampling configuration, facilitated by the
modular IR spectrometer system, were successfully performed
to study physicochemical processes of the MOF materials under
thermal treatment. The two examples presented in this work
demonstrate a wide range of possibilities to combine IR
spectroscopy based on the modular spectrometer with X-ray
spectroscopy and other methods thanks to the high positioning
flexibility and miniature character of the IR spectrometer, which
are of particular importance at synchrotron radiation facilities.
Studying materials in a pellet form is often advantageous in
terms of signal quality at the expense of difficulty in sample
preparation and handling. This work presented a versatile
approach to support a small amount of sample on supporting
pellet which is largely transparent to both IR light and X-ray.
With such an approach, one can achieve high quality signals by
IR-XAS-XRD in transmission configuration. When thicker
samples are required for signal quality and optical component
reasons, one can perform measurements in the diffuse-reflection
sampling configuration for IR spectroscopy. The signal quality
was deteriorated due to the smooth surface of the pellet used
and further optimisation of sample form (e.g. surface roughing
by drop casting) is required but the proof-of-principle of the
multi-probe approach was firmly shown. For this work the same
cell was used for both the transmission IR and DRIFTS
measurements. The experimental geometry can be further
optimised by allowing larger incident angles for even more
techniques. The generally used activation protocol of MOFs by
the thermal treatment was shown to induce even chemical
transformation near Zr atoms by the release of ligands
accompanying a partial electronic structure change of Zr. Such
insights are of particular importance in understanding the
functionality of materials and envisioning their potential
applications.

IR-XAS-XRD multi-probe experiments were performed at the SwissNorwegian Beamlines (SNBL, BM31) of the European Synchrotron
Radiation Facility (ESRF), France. For XAS-XRD combined with
transmission IR, Zr-BTC (3 mg) supported on a NaCl pellet (50 mg,
>99%, Sigma) was shaped into a disk of 13 mm diameter with ca. 0.2
mm thickness and it was put into the sample holder (Figure 1B). For
XAS-XRD combined with DRIFTS, Cu-BTC (16 mg) was also pelletized
into the self-supporting disk of 13 mm diameter with ca. 0.1 mm
thickness prior to mounting on the sample holder.
XAS spectra were recorded in transmission mode at the Zr and Cu Kedge using a double crystal Si(111) monochromator. Zr and Cu foils were
used for energy calibration. One XAFS spectrum was acquired in 5 min.
The XAFS data were processed using the IFEFFIT software package
(Athena and Artemis). EXAFS oscillations were extracted by fitting a
cubic spline function through the post-edge region. The k3-weighted
EXAFS oscillation in the 3.0-12.0 Å–1 region was Fourier transformed.
XRD patterns were recorded on a large MAR345 image plate detector
with the incident X-ray at the wavelength of 0.51105089 Å. The detector
calibration was performed with the LaB6 standard. One XRD pattern was
acquired for 10 min. Transmission IR and/or DRIFTS measurements
were performed using the modular FT-IR spectrometer (Arcoptix, OEM
model) and each spectrum was recorded for 60 s. The effluent gas
concentrations were recorded by a mass spectrometer (OmniStar,
Pfeiffer Vacuum).
The theoretical IR spectra of BTC and acetate was calculated with the
B3PW91 functional and 6-311++G(2d,2p) basis set using Gaussian 09
[13].

Acknowledgements
We thank the Generalitat de Catalunya for financial support
through the CERCA Programme and recognition (2014 SGR
893) and MINECO (CTQ2016-75499-R (AEI/FEDER-UE)) for
financial support and support through Severo Ochoa Excellence
Accreditation 2014–2018 (SEV-2013-0319). This work was
supported by JST PRESTO (JPMJPR16S3), Japan.
Keywords: IR spectroscopy • XAS• XRD • MOF
[1]

Experimental Section
Materials
Zr-BTC (Zr6O4(OH)4X6(BTC)2, X: acetate, BTC: benzene-1,3,5tricarboxylate) was synthesised according to the previous report [12].
ZrOCl2·8H2O was dissolved in a mixture of acetic acid and water in a
round bottom flask and to the resultant solution was added benzene1,3,5-tricarboxylic acid; mixture was then allowed to stir for a few minutes.
The flask was equipped with a reflux condenser and the reaction was
kept stirring at 130 º C for 24 hours. The resulting precipitate was
separated by centrifugation and washed with water, DMF and acetone.
To remove the solvents from the pores (i.e., activation), the material was
evacuated for 5 h at room temperature and then for 15 h at 100 °C after a
ramp of 1 °C min-1. Cu-BTC (C18H6Cu3O12, Basolite® C300, SigmaAldrich) was purchased and used as received.

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Entry for the Table of Contents

FULL PAPER
Simultaneous multi-probe
characterisation of MOF materials
under thermal treatment by combining
synchrotron XAS and XRD with
transmission IR and DRIFTS was
demonstrated using a unique modular
IR spectrometer, extending the
horizon of multi-faceted
characterisation of functional
materials.

Multi-probe characterisation
Satoshi Hinokuma, Geir Wiker, Takuya
Suganuma, Atul Bansode, Dragos
Stoian, Silvia Caminero Huertas, Sonia
Molina, Alexandr Shafir, Magnus
Rønning, Wouter van Beek and Atsushi
Urakawa*
Page No. – Page No.
Versatile IR spectroscopy combined
with synchrotron XAS-XRD: Chemical,
electronic and structural insights
during thermal treatment of MOF
materials