FT-IR study of nanosurface phenomena

I. Markova Deneva
University of Chemical Technology and Metallurgy Sofia, 8 St. Kl. Ohridski blvd., 1756 Sofia, e-mail:
vania@uctm.edu
Abstract
IR study of metal nanoparticles in amorphous or crystalline state obtained via water solution of metal salts by
borohydride reduction with NaBH4, as well as of nanowires prepared using mesopore ceramic supports has been carried out.
FT-IR spectra in mid-infrared region of visible spectrum (4000-400 cm-1) of these nanoscaled materials have been
undertaken. IR spectroscopy possibilities have allowed to investigate the nanosurface phenomena and to prove the creation of
different chemical bonds such as B-O, B-H, Si-O, O-H in surface atom groups. FT-IR spectra have provided information
about the technological and hydrodynamic conditions such as a kind of the initial salt, a type of the reactor used (T, Y, A
methods), different ceramic supports used (SiO2, SiMCM and ALMCM), different variants of the support introducing
(surface wetting), as well as about the nanosclaled materials composition, their structure state and nucleation.
Key words: FT-IR spectroscopy, FT-IR spectra, nanoscaled materials, nanoparticles, nanowires, nanosurface phenomena,
chemical reduction, supports.
1. Introduction
IR spectroscopy is widely used in both research
and industry as a simple and reliable technique for
measurement and has been highly successful for
applications in both organic and inorganic chemistry. IR
spectroscopy has also been utilized in the field of
semiconductor microelectronics. Less data is available
for IR spectroscopic studies in the field of inorganic
chemistry, as well as in the field of nanoscaled materials.
Our team considers IR spectroscopy, especially
FT-IR spectroscopy as a sensitive method to investigate
nanoscaled materials surface atom state [1-3]. We have
used IR spectroscopy in mid - IR region of the visible
spectrum approximately 4000 400 cm-1 to study the
fundamental vibrations and vibrational nanostructures.
We have successfully investigated by FT-IR spectroscopy
different atom groups formed on the nanoscaled materials
surface on the basis of their natural vibrations at a fixed
frequencies.
The aim of this work is commonly to study by IR
spectroscopy with Fourier transformation the nanosurface
phenomena occurring on the interface of nanoparticles
and nanowirwes synthesized by chemical reduction via
aqueous solutions of metal salts with NaBH4 [4],
respectively to investigate on the basis of the FT- IR
spectra the surface structure of the nanoparticles and
nanowirwes.
2. Experimental details
The investigated metal nanoparticles have been
synthesized by a chemical reduction method via water
solutions of metal salts with different anion content with
NaBH4 at a room temperature and an atmospheric
pressure. Three types of reactors providing different
hydrodynamic conditions of solutions mixing (this one of
the metal salt and the other one of reducing agent) have
been used [5].
Amorphous Co nanoparticles have been
synthesized via water solutions of CoSO4.7H2O using a
reactor with an ideal mixing conditions (the so called Tmethod), while Co nanoparticles with crystalline
structure have been synthesized using an antigravity

reactor working in an ideal displacement regime ( the

so called A-method) [9].
Cu nanoparticles have been obtained via water
solutions of three kinds of copper salts (CuSO4.5H2O,
CuCl2.2H2O and CuCl2) using three kinds of reactors
working at different hydrodynamic conditions of mixing
of both water solutions (T and A-methods mentioned
above and the so called Y-method of a full mixing of the
solutions).
Ni nanoparticles have been prepared via water
solutions of Ni salts with a different anion content
(NiSO4.6H2O, NiCl2.6H2O) using T - reactor of an ideal
mixing of both solutions.
Ni nanowires have been obtained using different
ceramic supports (SiO2, SiMCM and AlMCM) with a
different chemical nature (element content) and a
different specific surface area [m2/g]. Two variants of the
support wetting procedure have been used: the so-called
A-variant (the support is introduced with Ni salt solution
to the reducing agent solution) and B-variant (the support
is introduced with the reducing agent solution to Ni salt
solution) [6]. The weight Ni/support ratio is determined
in the range of 10 to 1.
IR spectroscopy study has been carried out with
IR spectrophotometer EQUINOX (Bruker) with Fourier
transformation in 4000 to 400 cm-1 frequency region
using KBr matrix, respectively IR spectra of
nanoparticles and nanowires sintesized have been
undertaken. The samples for IR spectroscopy
investigations have been prepared mixing nanoscaled
materials amounting to 1 mg and KBr (Spectral purity)
amounting to 200 mg and pressed in a tablet form with a
diameter 13 mm under a press loading of 8 t/cm2.
3. Experimental results
3.1. IR study of Co nanoscaled materials (Co
nanoparticles)
Co nanoparicles structure has been investigated in
previous our works [3,5,6] by means of electron
microscopy (TEM, SEM) and X-ray diffraction (XRD).
IR spectroscopy used in this work as a method for
structure investigations has proved its advantages over

Multi-Material Micro Manufacture

S. Dimov and W. Menz (Eds.)
2008 Cardiff University, Cardiff, UK. Published by Whittles Publishing Ltd. All rights reserved.

the other investigation structural methods in regards to

the surface structure and surface phenomena. IR spectra
reveal differences as regards a nanoscaled materials
structure state.
Fig. 1 presents FT-IR spectrum of heat treated at
200degC amorphous Co nanoparticles. This is a typical
infrared spectrum of materials in amorphous state (clear
absorption bands are missing). Fig. 2 presents FT-IR
spectrum of Co nanoparticles with the same chemical
composition, but in a crystalline state also treated at 200
degC. The observed infrared absorptions at characteristic
frequencies can be related to the formation of chemical
BO3 and BO4 groups. The atoms in these groups vibrate
in different ways: symmetrical stretching 1 (BO4) at
1030 cm-1 and antisymmetric stretching 3 (BO3) at 1310
cm-1, as well as scissoring (deformation vibrations) 4
(BO4) at 520cm1.
0.8

Fig. 1. FT-IR spectrum of amorphous

nanoparticles at
200degC

0.7

Transmittance,a.u.

0.6
0.5
0.4

Nanoparticles with different composition have

been prepared via water solutions of metal salts with
different anion contents (SO2-4, Cl-) using reactors
working at different hydrodynamic conditions of mixing
for both solutions: T-method ensuring ideal mixing
conditions, Y-method of full mixing conditions and Amethod of ideal displacement conditions.
3.2.1. Co nanoparticles
Figs. 4-5 present FT-IR spectra of Co
nanoparticles obtained via water solution of CoSO4.7H2O
(A-method) heat treated at different temperature.
With increasing temperature from 200 to 850
degC the absorption band grows in intensity and shifts to
lower frequencies. The quantity of BO4 groups increases
relatively at the expense of a spending of BO3 groups
from the boroxol ring with three non-bridging oxygen. At
lower temperatures (200 degC) the bands are broad (Fig.
2), while at higher temperatures (550-850 degC) they are
intensive and sharp (Figs. 3, 4, 5).

Fig. 4. FT-IR
spectrum of
Co nanoparicles
at 550degC

0.3
0.2
0.1
0.0
4000

3500

3000

2500

2000

1500

1000

500

Wavenumber,cm-1
0.8

Fig. 2. FT-IR spectrum of crystalline

nanoparticles
at 200degC

0.7

Transmittance, a.u.

0.6
0.5
0.4

Fig. 5. FT-IR
spectrum of
Co nanoparticles
at 850degC

0.3
0.2
0.1
4000

3500

3000

2500

2000

1500

1000

500

Wavenumber, cm-1

0.8

Fig. 3. FT-IR spectrum of crystalline

nanoparticles
at 750degC

Transmittance, a.u.

0.6

0.4

0.2

0.0

4000

3500

3000

2500

2000

1500

1000

500

Wavenumber, cm-1

In Fig. 3 is shown FT-IR spectrum of crystalline

nanoparticles treated at 750 degC. FT-IR spectra of the
crystalline nanoparticles treated over 550 degC are
characterized by intensive sharp bands observed in 1500
1100 cm-1 region. These absorption bands are very
sensitive to B-O-B bond angle and to B-O bond length in
BO3 groups.
The different shape of nanoscaled materials FTIR spectra demonstrates the state of these nanomaterials
(amorphous or crystalline). The absorption in this mid IR rg applies to B-O bonds in BO3 and BO4 groups.
Our IR investigations demonstrate IR spectroscopy as a
useful method when it comes to study nanoscaled
interface.
3.2. IR investigations of nanoparticles with
different composition

The synthesis conditions of ideal displacement for

both solutions with a mechanic mixer stirring, as well as
the anion content of the initial salts used (SO2-4)
determine the formation of isotropic
by shape
nanoscaled materials.
IR spectra undertaken show the temperature
influence to form crystalline nanoparticles resulting from
solid phase recrystallization processes, as well as the
influence of the method and the reactor used.
3.2.2. Cu nanoparticles
In Figs. 6- 8 have been shown IR spectra of Cu
nanoparticles obtained from CuSO4.5H2O salt but at
different hydrodynamic conditions, respectively A, T and
Y methods. In FT-IR spectra of Cu nanoparticles
obtained from the sulfate slats nevertheless the reactors
used it can be seen clearly expressed bands of absorption
in 1500 - 1300 cm-1 frequency region and not clearly
expressed absorption bands in 1000 - 850 cm-1 frequency
region. They are assigned to vibrations characteristic for
B-O bonds in BO3 and BO4 groups forming different
structures: antisymmetric stretching 3(BO3) mode at
1450 cm-1 and 1345 cm-1, symmetric stretching 1(BH3)
mode at 1115 cm-1, 1(BO4) mode and 1(BO3) mode in

1000 cm-1 - 850 cm-1 region and deformation 4(BO3),

4(BO4) and 4(BO2) modes in 600 - 430 cm-1 region.
Fig.6.FT-IR
spectrum of Cu
nanoparticles,
T-method,
CuSO4.5H2O

method as regards to establish the atom groups created on

the nanoparticles surface.FT-IR spectra prove the
chemical bonds created in surface atom groups.
3.2.3. Ni nanoparticles
Ni nanoparticles obtained via water solutions of
Ni salts with different anion content (SO2-4 , Cl-) using a
reactor working at ideal nixing conditions (T-method)
also have been investigated by IR spectroscopy and their
FT-IR spectra have been shown in figs. 9 and 10.

2437

Fig. 9. FT-IR
spectrum of
Ni nanoparticles,
NiSO4.6H2O

0,25

0,20

Transmittance [%]

Fig. 7. FT-IR
spectrum of Cu
nanoparticles,
Y- method,
CuSO4.5H2O

0,15

0,10

0,05

0,00
400 0

350 0

300 0

250 0

200 0

1500

1000

500

-1

Wavenumber [cm ]

2147

Fig. 10. FT-IR

spectrum of
Ni nanoparticles,
NCl2.6H2O

0,10

Transmittance [%]

Fig.8.FT-IR
spectrum of Cu
nanoparticles,
A- method,
CuSO4.5H2O,

0,12

0,08
0,06
0,04
0,02
0,00
4000

3500

3000

2500

2000

1500

1000

500

-1

Wavenumber [cm ]

In Fig. 6 presenting FT-IR spectrum of Cu

nanoparticles the band at 1115 cm-1 which is missed in all
other FT-IR spectra can be related to the presence of B-H
bonds in BH3 groups. This band is due to stretching
vibrations of B-H bonds in the BH3 group.
The characteristic bands at around 3420 cm-1 and
at 1620 cm-1 referring to H-O-H vibration can also be
detected in figs. 6-8. An intensive sharp band (at 1620
cm-1) and a slight broad band (at 3420 cm-1) are
characteristic for symmetric stretching vibrations 1(OH)
of O-H bonds in OH groups and the adsorpted H2O
molecules on the nanoparticles surface.
The stretching vibrations at frequencies higher
1000 cm-1 characterize short and strong B-O chemical
bonds in BO3 group, while the stretching vibrations at
frequencies lower 1000 cm-1 are typical for weak and
longer B-O chemical bonds in BO4 group. The shift of
the bands to the higher frequencies is due to an increase
of the quantity of BO3 groups in the system probably
because of a formation of tetraborate units (a structure
unit with less BO4 groups than triborate unit). The shift of
the absorption bands to the lower frequencies is due to an
arise of BO4 groups in the system with diborate and
triborate units which changes the boron coordination
from 3(in BO3 groups) to 4(in BO4 groups). IR study of
Cu nanoparticles using different initial Cu salts,
respectively different reactors working at different
hydrodynamic conditions prove IR spectroscopy as a
suitable investigation method for the nanoparticles
surface phenomena occurring, as well as a sensitive

In the case of NiSO4.6H2O salt FT-IR spectrum in

Fig. 9 has shown that on the nanoparticles surface have
been not formed BO4 atom groups characterizing by
weak B-O chemical bonds. But at 1450 cm-1 and 1270
cm-1 stretching vibrations of shot B-O bonds in BO3 atom
groups have been observed, as well as B-H2 bonds have
been created vibrating at 970 cm-1. In the case of
NiCl2.6H2O salt (Fig. 10) the creation of B-H2 bonds on
the nanoparticles surface vibrating at 970 cm-1 has been
observed too, as well as BO4 groups have been formed.
In both cases the bands at 1630 cm-1 due to
vibrations of O-H bonds in OH groups and the bands at
3430 cm-1 referred to H-O-H bonds vibrations in
adsorbed H2O molecules can also be detected.
On FT-IR spectra in figs. 9 and 10 it can be seen
the differences in surface groups formation due to
different initial salts used for nanoparticles synthesis.
3.2.4. Ni nanowirers
Figs. 11-12 show FT-IR spectra of nanowires
obtained via water solutions of NiSO4.6H2O using SiO2
support and A-variant of a wetting procedure, while Fig.
13 presents FT-IR spectrum of nanowires obtained at the
same conditions but using NiCl2.6H2O salt. Generally, on
FT-IR spectra the following absorption bands have been
observed: at 1430 cm-1 (BO3 groups), at 800-810 cm-1
(BO4 groups), at 650-670 cm-1 (B3O6 groups), at 11051110 cm-1 (Si-O bonds) and at 470-480 cm-1 (Si-O
bands).

2174

Transmiottance [%]

0,5

0,4

0,3

0,2

0,1

Fig. 11.FT-IR
spectrum
of Ni nanowires,
NiSO4.6H2O,
A-variant,
SiO2 support

0,0
4000

3500

3000

2500

2000

1500

1000

500

-1

Wavenum ber [cm ]

2254
0,8
0,7

Transmittance [%]

0,6
0,5
0,4
0,3
0,2
0,1

Fig. 12. FT-IR

spectrum
of Ni nanowires,
NiSO4.6H2O,
B-variant,
SiO2 support

0,0
4000

3500

3000

2500

2 000

1500

10 00

500

-1

Wavenumber [cm ]

2135
0,9
0,8

Transmittence [%]

0,7
0,6
0,5
0,4

Fig. 13. FT-IR

spectrum of
Ni nanowires,
NiCl2.6H2O,
A-variant,
SiO2 support

0,3
0,2
0,1
4000

3500

3000

2500

2000

1500

1000

500

-1

Wavenumber [cm ]

IR spectroscopy method has established the

difference between FT-IR spectra due to the different
away of the introduction and the surface
wetting of the supports.
FT-IR spectroscopy analysis gives an account
to initial salt used for the nanostructures synthesis
(using NiSO4.H2O salt BO3 groups predominate over
BO4 groups, while using NiCl2.6H2O salt BO4 groups
predominate), as well as gives an account to the
support used.
In
Figs. 14 and 15 are shown SEM
micrograph of nanoscaled materials investigated in this
work by IR spectroscopy [6].

Fig. 14. SEM micrograph

of nanoparticles,
NiCl2.6H2O [6]

Fig. 15. SEM micrograph

of nanowires,
NiSO4.6H2O [6]

Conclusion
IR study in mid - IR spectrum of 4000 400
cm-1 of the nanoscaled materials surface has
demonstrated IR spectroscopy as a sensitive method for
investigation of nanosurface phenomena on the
nanostructured materials interface. FT-IR spectra

undertaken have provided information about the

technological and hydrodynamic conditions of the
reduction process as regards the initial salt (Ni, Cu, Co
sulfates or chlorides), the type of the reactor used (T, Y,
A methods), the ceramic support used (SiO2, SiMCM
and ALMCM), the different variants of a support
introduction and surface wetting.
FT-IR investigations have shown the creation
of different bonds and the formation of different groups
on the nanomaterials surface. The characterization using
FT-IR has been focused on vibrational groups of attached
hydrogen, oxygen, boron, respectively on processes
occurred on the interface such as atoms reduction and
oxidation and molecules adsorption. FT-IR spectra mode
is different due to the stretching and deformation
vibrations of chemical bonds such as B-O, B-H, Si-O,
and O-H in4000 cm-1 to 400 cm-1 frequency region
forming different surface atoms groups.
Using FT-IR for studying surface phenomena,
respectively surface attached atoms and their bonds and
attached molecules has demonstrated IR spectroscopy as
an investigation structural methods for nanoscaled
materials in regards to surface phenomena and surface
atom groups formation.
Acknowledgement
The author gratefully acknowledges the financial
support from the National Science Fund at the Ministry
of Education and Science-Bulgaria on a Project NT-503, as well as expresses its appreciation to the Scientific
Center of UCTM - Sofia under a Contract No 814.
The author is thankful to prof. DSci. I. Dragieva
and a scientific researcher Dipl. Eng.K. Alexabdrova both
from the IEES - BAS, Sofia for the samples given to be
studied in this work and for their scientific help.
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