Vibrational Spectroscopy 77 (2015) 5–9

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Vibrational Spectroscopy
journal homepage: www.elsevier.com/locate/vibspec

Short communication

Raman scattering and optical properties of lithium nanoparticles

obtained by green synthesis
Ramón A.B. Álvarez a , M. Cortez-Valadez a, * , R. Britto-Hurtado a , L. Oscar Neira Bueno b ,
N.S. Flores-Lopez a , A.R. Hernández-Martínez c , R. Gámez-Corrales d, R. Vargas-Ortiz e ,
J.-G. Bocarando-Chacon f , H. Arizpe-Chavez a , M. Flores-Acosta a
a
Centro de Investigación en Física, Universidad de Sonora, Apdo. Postal 5-88, 83190 Hermosillo, Sonora, Mexico
b
Grupo de Espectroscopia y Laser, Universidad Popular del Cesar, C.P. 2503 Valledupar, Cesar, Colombia
c
Centro de Física Aplicada y Tecnología Avanzada (CFATA), Universidad Nacional Autónoma de México, Campus Juriquilla, Blvd. Juriquilla
3000 Juriquilla, Querétaro, Mexico
d
Departamento de Física, Universidad de Sonora, Apdo. Postal # 130, Hermosillo, Sonora 83000, Mexico
e
Universidad Autónoma de Sinaloa, Facultad de Ingeniería Mochis, Ciudad Universitaria, C.P. 81223, Los Mochis, Sinaloa, Mexico
f
Universidad Tecnológica de Querétaro, UTEQ. Avenida Pie de la Cuesta # 2501, C.P. 76148 Querétaro, Mexico

A R T I C L E I N F O A B S T R A C T

Article history: The first report on lithium nanoparticles synthesized experimentally is presented. The nanoparticles
Received 15 September 2014 were obtained using the extract of Opuntia ficus-indica through “green synthesis”. The optical, structural
Received in revised form 2 February 2015 and vibrational properties were studied through optical absorption, TEM microscopy and Raman
Accepted 2 February 2015
spectroscopy. The particles show a size of approximately 5 nm. The absorption bands were found at
Available online 3 February 2015
315 and 415 nm in the samples after the synthesis of the nanoparticles. One Raman band was detected at
around 280 cm
1. Several levels of approximation of the density functional theory and the Hartree–Fock
Keywords:
method on the structural and vibrational study of the lithium clusters (Lin,n = 2–18) are incorporated. A
Lithium nanoparticles
Radial breathing modes
radial breathing mode (RMB) type Raman mode was found for the case Lin (n > 3) in the predicted Raman
Raman in metal nanoparticles spectrum. This mode shows the highest relative intensity for each case, and a shift to lower wavenumbers
DFT approximations when the amount of atoms in the cluster increases.
Green synthesis ã 2015 Elsevier B.V. All rights reserved.

1. Introduction Other important advantages of metallic nanoparticles are their

application in catalysis, fuel cells, optical devices, biomedical use,
Lithium seems to be the appropriate and irreplaceable element among others [6–9]. Since these properties regularly depend on
for the improvement of electronic devices such as long-lasting the size and morphology of the nanoparticles, it is important to
rechargeable batteries. Currently, the development of the nano- find an effective and low-cost synthesis method. The “green”
metric material and nanostructured material sciences, has led to a synthesis with the plant Opuntia ficus-indica (Ofi) has succeeded
number of studies that have been focused on developing for synthesize and stabilize several types of crystalline and
interactions of lithium with nanometric materials containing: amorphous metallic nanoparticles [10–12]. In addition to this,
aluminium, titanium, iron, and cobalt [1–4]. This was done with the see-through property of this extract allows the detection of
the objective of improving their electrical and electrochemical changes in the colour-scheme spectrum, which is visible after the
properties, among others. Mainly by contributing to the efficiency synthesis of the nanoparticles. This facilitates the immediate
of the fast charging capacity as shown by Hwang et al., who used detection of colloidal nanoparticles in the sample. Consequently,
nanoparticles of nickel oxide [5]. Another results show that Silicon the absorption bands in UV–vis spectrum are detected allowing the
nano-spheres cathodes contribute to the durability of lithium study of the plasmonic properties of the nanoparticles. Raman
rechargeable batteries. spectroscopy is other technique widely used in the characteriza-
tion of nanoparticles. This technique facilitates the identification at
level of single molecule of materials in the samples [13]. Because of
* Corresponding author.
this, Raman spectroscopy is a characterization sensitive to the size
E-mail addresses: manuelcortez@live.com, jose.cortez@unison.mx [12] and morphology [14] of nanoparticles. The results of our group
(M. Cortez-Valadez). show evidence of RBM in small metallic nanoparticles [15].

http://dx.doi.org/10.1016/j.vibspec.2015.02.001
0924-2031/ ã 2015 Elsevier B.V. All rights reserved.
6 R.A.B. Álvarez et al. / Vibrational Spectroscopy 77 (2015) 5–9
[(Fig._1)TD$IG]
This report shows the synthesis of metallic nanoparticles of
lithium with Ofi extract. The experimental evidence of the
plasmonic properties of lithium nanoparticles is reported for the
first time. Low frequency Raman bands were detected after the
synthesis of lithium nanoparticles in the extract. A complementary
structural and vibrational study in small clusters of lithium was
undertaken by the density functional theory. This predictive study
showed the existence of vibrational modes in the Raman spectrum
of the structures under study. These RBM are located at low
wavenumbers matching with the experimental results of Raman
spectroscopy.

2. Materials and methods

The extract was taken from a young leaf of the Ofi plant. The
prickles were removed, in order to peel it and chop it finely. 25 g of
the chopped mixture was placed in 50 mL of deionized water, and
then placed under magnetic stirring for 30 min at 60  C. Another
solution 0.001 M of LiCl, acted as a precursor solution of the Li ion.
Afterwards, 25 mL of the precursor solution was mixed with 3 mL
of the plant extract, in order to reduce the Li+ ions in metallic
lithium. The solution was kept at 60  C for 1 h.
The Raman spectra in the colloidal samples was recorded with the
Micro Raman X0 plora equipment model BX41TF OLYMPUS HORIBA
Jobin IVON with a class 3B argon laser with 20–25 mW, at 532 nm. Fig. 1. TEM image of the lithium nanoparticles synthesized in the Ofi extract.

2.1. Theory and calculations nanoparticles with spherical morphology and 10 nm diameter,
show absorption bands in the ultraviolet spectrum around 310 nm
The density functional theory at the generalized gradient approximately [19]. A deconvolution of the absorption spectrum
approximation level B3LYP (Becke’s three-parameter exchange allows us to view the contribution of the optical properties of the
functional and the gradient corrected functional of Lee Yang and lithium nanoparticles and Ofi extract. A band located at 263 nm, is
Parr) combined with the basis set LANL2DZ (the effective core the absorption band of special features of the plant Ofi extract. The
potentials and associated double-zeta valence basis set) were used additional band located at 315 nm have a good agreement with the
for the structural and vibrational study of the lithium clusters; both band referred to above, for the theory of Mie [19] assigned to the
are included in the Gaussian package 09 [16]. Only the cases Lin surface plasmon in lithium colloidal nanoparticles located in
(2  n 18) were treated, due to computational cost. Additionally, 310 nm. Predictive calculations about the theory of Mie reported
we consider the lithium unit cell at several approximation levels previously by our group [11] show a shift towards higher
and basis sets. All the structures were optimized; subsequently the wavelengths when the particle size is increased. Because of this,
vibrational spectrum was obtained to guarantee a local minimum. the band focused on 375 nm could be caused by the surface
The Lin structures were optimized and obtained from the addition plasmon in nanoparticles or agglomerates with size greater than
or subtraction of one or more atoms in previously reported clusters 10 nm (Supplementary information).
(Lin
1, Lin+1, Lin
2, Lin+2, etc.). The stationary points on the Lin After the synthesis of the nanoparticles, the Raman band was
potential energy surface, in their lowest electronic states in each detected centred approximately at 280 cm
1 as shown in Fig. 3.
case, were initially located and analysed by vibrational spectros- Because the Ofi extract does not show Raman bands relevant to the
copy using DFT with the hybrid functional B3LYP in conjunction [(Fig._2)TD$IG]
with the LANL2DZ basis set. The stability of the optimized geometries
was confirmed by wavenumber calculations, which gave positive 1.2
values for all the obtained wavenumbers in the Lin clusters, 263
guarantee a local minimum in the potential energy surface.
Optical Absorbance/ Arb. Units

1.0

3. Results
0.8

Lithium nanoparticles were synthesized in the Ofi plant extract.

0.6
The particles have a crystalline structure and quasi-spherical
morphology. The interplanar distance of one of the planes is 2.65 Å,
very close to the 2.69 distance reported by Barret [17] which 0.4
corresponds to one of the crystalline planes with higher intensity 315 375
(1 0 0) for metallic lithium. The size of the particle is around 5 nm in 0.2
some the crystalline planes, can be observed with a semi-
crystalline morphology, as shown in Fig. 1. 0.0
The absorption bands in the ultraviolet spectrum were detected
after the reduction of the lithium ion. After 24 h of synthesis -0.2
processing, optical properties of the samples with colloidal lithium 200 250 300 350 400 450 500 550
nanoparticles were studied in an aqueous solution. The optical
Wavelength (nm)
absorption spectrum is shown in Fig. 2. The predictive calculus of
the Mie theory [18,19], indicate that the lithium colloidal Fig. 2. Optical absorption spectrum of Ofi extract with lithium nanoparticles.
 R.A.B. Álvarez et al. / Vibrational Spectroscopy 77 (2015) 5–9 7
[(Fig._3)TD$IG]
500 inferior wavenumbers at 450 cm
1, we suppose that the Raman
band may be assigned to vibrational modes present in small
450 lithium particles. Raman spectroscopy may be sensitive to the
400
morphologic and structural changes of the nanoparticles; this is
Raman Intensity/Arb. Units

why this technique has become increasingly important in the

350 characterization of metallic and semiconductor nanostructures.
The most recent result of our group shows the presence of Raman
300 280
modes in the small metallic particles [10–12].
250 Additionally, small structures of Li through DFT level of
approximation B3LYP are obtained, in its minimum energy
200
(local–minimum). This structures are shown in Fig. 4 and the
150 geometric name is described in Table 1. The bond length for the Li2,
obtained by Minaev et al. [20] is 2.67 Å, calculated by the multi-
100
configuration self-consistent field method (MCSCF). We obtained a
50 similar result of bond length of 2.721 Å at the approximation level
B3LYP. This result matches as well with the result obtained from
0
the DFT at the PBE approximation level with the basis set 6–311 G
450 400 350 300 250 200
-1
(d, p) [21]. For Li4 and Li6–8, Blanc et al., obtained the same
Wavenumber (cm ) symmetry groups applying ab-initio configuration interaction (CI)
Fig. 3. Raman spectra of lithium nanoparticles synthesized in Ofi extract.
calculus [22]. For the clusters Li9–18 the structures match with the
ones obtained by Fournier et al. [23].
Wu predicts two possible structural configurations for Li4
experimentally obtained: cubic and rhombic [24]. The comparative
[(Fig._4)TD$IG]

Fig. 4. Small lithium clusters in its local minimum energy by DFT at the B3LYP approximation level: Lin (symmetry group).
8 R.A.B. Álvarez et al. / Vibrational Spectroscopy 77 (2015) 5–9
[(Fig._5)TD$IG]
Table 1
Suggested geometric name for Lin clusters. a
Lin Geometric type
400
Li2 Linear

Radial Breathing modes (cm )

-1
Li3 Triangular
Li4 Planar rhombus
Li5 Trigonal bipyramidal
Li6 Octahedral
Li7 Pentagonal bipyramid 300
Li8 Capped square antiprism
Li9 Centered square antiprismatic
Li10 Capped square antiprism
Li11 Regular pentagonal prism with atoms in center and base
Li12 Octahedral with pentagonal bipyramid 200
Li13 Icosahedron
Li14 Double centered square antiprim
Li15 Double centered square antiprim with one atom face capped
Li16 Dodecahedron truncated type
Li17 Capped icosahedron
Li18 Capped icosahedron with atom in the top face 100
0 2 4 6 8 10 12 14 16 18
cluster size (n)
results of the minimum energy by DFT in this work, about both
configurations, predict that the rhombic structure has lower b 3500
energy and therefore the existence of a Li4 cluster in this
configuration is more likely (D2h). 3000
For the cases under study Lin (n = 3–18) we obtained the Raman
spectrum at the B3LYP approximation level combined with the RBM intensity (Arb. Units) 2500
basis set LANL2DZ. A RBM frequency was found in the Raman
spectrum of each cluster. Blanc et al. [22] predict 6 vibrational
bands assigned to Li4 for the symmetry group (D2h) by ab-initio (CI) 2000

located at: 100, 165, 172, 224, 296 and 349 cm
1. We obtained
6 vibrational bands located in: 97.9, 168.7, 175.1, 226.6, 311.7 and 1500
the last one with higher relative intensity located in 353 cm
1.
Assigned to an RBM frequency in this cluster. Other theoretical 1000
results quantitatively predict the vibrational bands of the clusters
Li11, Li13 and Li18 by DFT at the LSD approximation level. This leads
500
to the following results in the vibrational modes with higher
intensity: for Li11 at 290 and 320 cm
1, for Li13 at 250 and 260 cm
1
and for Li13 at 220 and 225 cm
1 [25]. These vibrational bands, as 0
0 2 4 6 8 10 12 14 16 18 20
we suppose, can be assigned to RBM frequency. As well as at our
calculations, the bands with higher intensity generally correspond Cluster size(n)
to RBM frequency. In this study, RBM for Li11, Li13 and Li18 is located Fig. 5. DFT vibrational calculations at the B3LYP approximation level (a) radial
at 277.5, 242, and 220 cm
1, respectively. Generally, the approxi- breathing modes (RBM) in small clusters of Li and (b) RBM Raman intensity in small
mation level LDA underestimates the bond length, generating an clusters of Li.
increase in the vibrational modes to higher wavenumbers with
respect to the approximation level, B3LYP.
These modes show a dependency in the number of atoms as calculations are not considered in this work. Likewise, if we link
shown in Fig. 5a. This generally reflects a decrease to lower this vibrational behaviour to the metallic nanoparticles synthe-
wavenumbers when the cluster is made up of a higher number of sized in the Ofi extract, we can observe that the mode type tends to
atoms. The intensity of the Raman RBM obtained from calculations decrease to a particular particle size. In general terms, we can say
of DFT is shown in the following Fig. 5b. There has been a that this type of mode can be found in lithium nanoparticles and
significant decay in the intensity of the modes for clusters with size possibly lithium nanoparticles with lower size than 10 nm.
above (Lin, n > 15). We assume that for larger clusters the intensity Complementing the theoretical calculations and considering
of the RBM will show probably a decay in congruence with the the structure of the unit cell type for bulk lithium (Fig. 6), the cubic
non-detection of Raman bands in metal bulk. Due to the structure was optimized by Hartree–Fock (HF) method and the
calculation time and availability in our equipment these approximation levels B3LYP, B3PW91 (Becke’s, Burke and Ernzer-
hof functional) and LSDA (local spin density approximation) with
the basis set LANL2DZ, SDD (Stuttgart/Dresden) and cc-pVTZ
Table 2
Radial breathing modes found in the lithium unit cell (FCC type) by HF and DFT
(Dunning correlation-consistent, polarized valence, triple-zeta
approximations, combined with basis set LANL2DZ, SDD and cc-pVTZ. basis). Subsequently, obtaining the Raman spectrum of that
structure in each theory level. An RBM was detected in this
Approximation LANL2DZ SDD cc-pVTZ
structure for the levels of theory previously mentioned, located
Radial breathing mode (cm
1) around 213 cm
1 for the approximation level B3LYP.
B3LYP 217.2 213.07 215.06 Table 2 shows the vibrational results obtained by HF and the
B3PW91 211.57 209.34 210,70 different approximation levels of DFT. Generally, due to the
PBE 216.61 209.43 215.04 considered theories, we suppose that the RBM frequency is located
LSDA 226.36 221.71 224.61
HF 194.79 193.07 193.38
between 193–220 cm
1. Even though we know that the vibrational
mode technically depends on the length bond. As we know, HF
 R.A.B. Álvarez et al. / Vibrational Spectroscopy 77 (2015) 5–9 9
[(Fig._6)TD$IG]
Acknowledgements

The computational resources for this investigation was

facilitated by UNISON/Acarus. This research was supported by
Conacyt Proyect # 1420001.

Appendix A. Supplementary data

Supplementary data associated with this article can be found, in

the online version, at http://dx.doi.org/10.1016/j.
vibspec.2015.02.001.

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