NANOCHEMISTRY & APPLICATIONS

CHAPTER 1-5: ANALYTICAL METHODS FOR

CHARACTERIZATION OF NANOMATERIALS

Dr. Nguyen Van Dung

Faculty of Chemical Engineering, Ho Chi Minh City University of Technology (HCMUT)

Email: nvdung@hcmut.edu.vn

Dr. Nguyen Van Dung, Faculty of Chemical Engineering, HCMUT

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SEM

The JEOL JSM-7500F is an ultra high resolution field emission

scanning electron microscope (FE-SEM)

Dr. Nguyen Van Dung, Faculty of Chemical Engineering, HCMUT

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SEM

SEM IMAGES
(a) (b) (c) (d)

(e) (g) (f) (h)

Fig. A1, p.82 and B6, p. 90 & 91: SEM images at 30,000 of magnification
of (a) h-BN1-550, (b) Au/BN1-300; (c) Au/BN1-450; (d) Au/BN1-600 and
(e) h-BN2-550, (f) Au/BN2-300; (g) Au/BN2-450; (h) Au/BN2-600
Dr. Nguyen Van Dung, Faculty of Chemical Engineering, HCMUT
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SEM

(a)

(e)

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TEM

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TEM
HRTEM images of nano rod OMS-2

The gold nanoparticles in the image are

about 15-20 nanometers

cotton CNCs
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TEM

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Atomic force microscopy (AFM)

The atomic force microscope (AFM) system has evolved into a useful tool for direct
measurements of intermolecular forces with atomic-resolution characterization that can be
employed in a broad spectrum of applications such as electronics, semi-conductors,
materials and manufacturing, polymers, biology and biomaterials. AFM provides additional
capabilities and advantages relative to other microscopic methods (e.g. scanning electron
microscopy (SEM) and transmission electron microscopy (TEM)) in studies of metallic
surfaces and micro-structures by providing reliable measurements at the nanometer scale .
AFM can also be used for nanoindentation to provide in situ imaging ability without moving
the sample, switching tips, relocating the area for scanning, or using an entirely different
instrument to image the indentation . Force modulation microscopy (FMM) which is an
extension of AFM imaging, is used extensively for the characterization of mechanical
properties and in applications such as imaging composition changes in a composite material,
analyzing polymer homogeneity, and detecting contaminants in manufacturing processes.
Assembly of nanoparticles and linking them to electrical leads, such as random deposition of
clusters between electrodes, binding by wet chemistry, and electrostatic trapping, all serve as
other important applications of the AFM technique.

Jalili, N. and K. Laxminarayana (2004). "A review of atomic force microscopy imaging systems:
application to molecular metrology and biological sciences." Mechatronics 14(8): 907-945.
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Atomic force microscopy (AFM)

To determine
the shape, size
and/or size
distribution of
nanoparticles,
surface
roughness,...
and chemical
information of
samples

Fig. 1. Schematic of basic AFM operation (left), real micro-cantilever and components (right)

Dr. Nguyen Van Dung, Faculty of Chemical Engineering, HCMUT

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Atomic force microscopy (AFM)

Dr. Nguyen Van Dung, Faculty of Chemical Engineering, HCMUT

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Atomic force microscopy (AFM)

Figure 1: Topography images of TiO2 nanoparticles on Silicon; frame size: 1m. The deposition of
nanoparticles was accomplished by using a dilution of (a) 1:10, (b) 1:40 and (c) 1:50 from a 0.04%
aqueous TiO2-suspension. The height of the nanoparticles is in the range of 9-11 nm.

Fig. 2. A 3µm x3 µm image of nanoparticles displayed as a three dimensional projection. These

nanoparticles range in size from 4nm to 12nm in diameter.
[1] Rao, A., et al. (2007). Journal of Physics: Conference Series 61: 971-976
[2] https://www.afmworkshop.com/applications/atomic-force-microscopes-for-nanoparticles-characterization

Dr. Nguyen Van Dung, Faculty of Chemical Engineering, HCMUT

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Atomic force microscopy (AFM)

Atomic force microscopy images silver nanoparticles on glass; scanned area 1 μm × 1 μm: (A)
2-D topography; (B) 3-D topography; (C) profile of the cross-section along the arrow in panel A.

Dr. Nguyen Van Dung, Faculty of Chemical Engineering, HCMUT

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FTIR

FTIR (Fourier-transform infrared spectroscopy) and DRIFTS (diffusion

reflectance infrared fourier transmission spectroscopy)

DRIFTS principle

https://en.wikipedia.org/wiki/Fourier-transform_infrared_spectroscopy

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FT-IR

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FTIR

3-(aminopropyl)triethoxysilane

FT-IR spectra of SBA-15, SBA-NH2 and AuNPs/SBA-NH2, 3-

(aminopropyl)triethoxysilane used for surface modification of SBA-15
Neeli, C. K. P., et al. RSC Advances 4.27 (2014): 14128-14135.

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FTIR

FTIR spectra of MCN

before and after calcine

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Raman spectroscopy

Raman spectroscopy has historically played an important role in the structural

characterization of graphitic materials, in particular providing aluable
information about defects, stacking of the graphene layers and the finite sizes
of the crystallites parallel and perpendicular to the hexagonal axis.

[1] Pimenta, M. A., et al. (2007). "Studying
disorder in graphite-based systems by Raman
spectroscopy." Physical Chemistry Chemical
Physics 9(11): 1276-1290
Fig. 3 Raman spectrum of a nanographite sample,
showing the main Raman features, the D, G, D' and
G' bands taken with a laser excitation energy
(wavelength) of 2.41 eV (515 nm)

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Raman spectroscopy

the D-band (1350 cm-1); G-band

(1580 cm-1) and G'-band (2700 cm-1)

Fig. 1. Raman spectra from several sp2 nanocarbon and

bulk carbon materials. From top to bottom: crystalline
mono-layer graphene, HOPG, an SWNT bundle sample, Fig. 2. Raman shift of amorphous carbon
damaged graphene, single-wall carbon nanohorns (SWNH).
Note that some authors call the G’ by 2D and the G” by 2D’

[1] https://www.researchgate.net/figure/Gaussian-fit-of-D-and-G-bands-of-amorphous- carbon_fig5_316549008

[2] Hofmann, M., et al. (2011). Advances in Physics 60(3): 413-550

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Raman spectroscopy

Red shift
Raman shift spectra of OMS-2R and its derivatives

Dr. Nguyen Van Dung, Faculty of Chemical Engineering, HCMUT

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UV-Vis

UV-Vis DRS
0.8
523
0.7
Surface plasmon resonance
dAu
0.6
(nm)
505 Au/BN1-300 C
o

Absorbance
0.5

0.4 498 4.0  0.5

Au/BN2 o
300 C
0.3 3.4  0.5
o
450 C
0.2 518 2.5  0.2
0.1 Ref. sample: BaSO4
o
600 C

RT in N2 3.9  0.7
Au/BN2
0.0
200 400 600 800
Wavelength (nm)
Fig. 1: in situ UV Vis DRS of (a) h-BN and Au/BN Au/BN at various calcinations in air; (b) The spectra
measured from (1a) after cool in N2 to RT; Ref. sample is BaSO4 in N2.

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UV-Vis

Nano Ag

λmax = 418 nm

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XPS
X-ray Photoelectron Spectroscopy (XPS) also known as Electron Spectroscopy for
Chemical Analysis (ESCA) is the most widely used to analyze the chemical composition
of surfaces.
In 1981, Dr. Siegbahn was awarded the Nobel Prize in Physics for the development of
the XPS technique.
• Monoenergetic X-Ray beam (MgK or AlK):
– Irradiate the sample surface, hitting the core electrons (e-) of the atoms.
– The X-Rays penetrate the sample to the depth on the order of a micrometer.
– Ussually, e- signal is obtained only from a depth of around 10 to 100 A0 on the
surface.
• Ultrahigh vacuum environment used to eliminate excessive surface contamination.
• Cylindrical Mirror Analyzer (CMA) measures the kinetic energy (KE) of emitted e-
• The spectrum poltted by the computer from the analyser signals.
• Binding energy can be determinded from the peak positions & the elements in the
samples.
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XPS

Dr. Nguyen Van Dung, Faculty of Chemical Engineering, HCMUT

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XPS

BE is core electrons for element. The BE is determined by the attraction of the electrons to
the nucleus. If an electron with energy X is pulled away from the nucleus, the attraction
between the electron and the nucleus decreases and the BE decreases. Eventually, there
will be a point when the electron will be free of the nucleus.

The X-Ray & the Atom

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XPS

XPS of GO graphene

XPS study of the catalysts: Au 4f region

Johra, F. T., et al. (2014). Journal of Industrial and Engineering Chemistry, 20(5), 2883-2887
Smolentseva, E., et al. ChemCatChem 7, no. 6 (2015): 1011-1017.

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XPS

XPS spectra of cobalt ferrite nanoparticles: (a, b) annealed at 500 °C, and (c,d) annealed at 1100 °C.
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Cyclic voltammetry

Typical cyclic voltammogram where ipc and ipa show the peak
cathodic and anodic current respectively for a reversible reaction

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Cyclic voltammetry

Cyclic voltammetry analysis to calculate Pt active surface area

SCE: 0298 = 0.2444

Oxidation V

Reduction

Fig. 10th cycle isolated from the curve with oxydo-reduction specificities for platinum

https://www.bio-logic.net/wp-content/uploads/20101105-application-note-11.pdf

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N2 adsorption

IUPAC classification of adsorption isotherms.

IUPAC : International Union of Pure and Applied Chemistry

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N2 adsorption

Figure 4. Nitrogen adsorption-desorption Figure 2: Adsorption and desorption isotherms of N2

isotherms for non-porous MA-SiO2 and measured at 77 K on nonporous and nanoporous
mesoporous MA-SiO2 nanoparticles [1] (treated at 800 oC with KOH) carbon materials [2]

[1] Shin, W. K., Cho, J., Kannan, A. G., Lee, Y. S., & Kim, D. W. (2016), Scientific reports, 6, 26332
[2] Xu, Huaxing, et al. Journal of Nanomaterials 2014 (2014): 229.

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N2 adsorption

Figure 4: N2 adsorption/desorption isotherms of SBA-15

unwashed (2A), after washing with 5 mL (2B) and 30
mL (2C) quantities of solvent. The isotherms are offset
by 350 (2A) and 50 (2B) cm3/g.
Thielemann, J. P., Girgsdies, F., Schlögl, R., & Hess, C. (2011). Beilstein journal of nanotechnology, 2(1), 110-
118.

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N2 adsorption

Figure 11: Effect of narrowed pores in the SBA-15 structure on the

isotherm shape.

Thielemann, J. P., Girgsdies, F., Schlögl, R., & Hess, C. (2011). Beilstein journal of nanotechnology, 2(1), 110-118.

Dr. Nguyen Van Dung, Faculty of Chemical Engineering, HCMUT

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N2 adsorption

Dv (d)
[cm3/g/nm] Distribution of pore size of MCNs
0.18
0.16
0.14
0.12
0.10 Mẫu MCN-0,5
0.08 Mẫu MCN-1,0
0.06
Mẫu MCN-2,0
0.04
0.02
0.00
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

Pore Diameter [nm]

Sample SBET (m2/g) Vt (cm3/g) dmax (nm) dpore (nm)

MCN-0.5 413 0.25 3.2 3.2

MCN-1.0 297 0.24 3.9 3.6

MCN-2.0 321 0.26 3.7 1.2

Dr. Nguyen Van Dung, Faculty of Chemical Engineering, HCMUT