NANOCHEMISTRY & APPLICATIONS

CHAPTER 1-7:

Dr. Nguyen Van Dung

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

Email: [email protected]

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

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X-RAY

✓ X-rays were first observed by Röntgen in 1895.

✓ Röntgen himself took pictures of the bones of the hand, and X-rays were
quickly used in medicine.
✓ In 1912, von Laue et al. demonstrated the wave nature of X-rays through
X-ray diffraction on copper sulfate crystals and also demonstrated that in
the crystal, the atoms are arranged in a spatial lattice.

Wilhelm Conrad Rontgen (1845-1923)

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

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X-RAY

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

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X-RAY

Band Wavelength Interaction

Gamma < 1 pm Nucleus
X-ray 1 nm - 1 pm Inner electrons
UV 400 nm - 1 nm Outer electrons
VIS 750 nm - 400 nm Outer electrons
Near IR 2.5 m - 750 nm Molecular vibrations
IR 25 m - 2.5 m Molecular vibrations
Microwave 1 mm - 25 m Molecular rotation
Radio > 1 mm Nuclear spins

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

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X-RAY

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

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X-RAY

X-rays are produced by the movement of electrons in the inner layer.

The conversion efficiency into X-rays

is very low (only about 0.8%); most
of the energy generated by impact
is converted into heat.
Dr. Nguyen Van Dung, Faculty of Chemical Engineering, HCMUT
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DIFFRACTION

Diffraction is a phenomenon observed when waves propagate through a

small gap or the edge of an obstacle (most clearly with obstacles whose
size is equivalent to the wavelength), in which the wave is deflected and
spreads in all directions from the obstacle position and self-interferes with
other waves spreading from the obstacle.

Diffraction is observed with all types of waves, such as sound, water

waves, electromagnetic waves (such as X-ray or radio waves), or particles
that exhibit wave properties through wave-particle duality.
Dr. Nguyen Van Dung, Faculty of Chemical Engineering, HCMUT
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BRAGG'S LAW

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BRAGG'S LAW

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

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BRAGG'S LAW

2θ deviation
Beam 1

Beam 2  

 d

▪ Path difference between beams 1 & 2 = 2d.sin

▪ Diffraction conditions: n = 2d.sin
Dr. Nguyen Van Dung, Faculty of Chemical Engineering, HCMUT
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BRAGG'S LAW

Based on the Bragg formula 2dsin = n, the following

methods can be used:

Keep the incident angle, change wavelength

+ Laue method

Keep wavelength, change incident angle

+ Rotating-crystal diffraction
+ Debye-Schrerrer method (Powder method)

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

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LAUE METHOD

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LAUE METHOD

Crystal

X-ray beam

Laue diffraction image of Si in the [0 0 1] direction

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

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ROTATING-CRYSTAL DIFFRACTION

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

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POWDER METHOD

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

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POWDER METHOD

Diffracted beam
Diffracted beam

Incident beam

Incident beam
Single crystal

Polycrystal

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

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X-RAY DIFFRACTOMETER

Detector

Monochrome
filter

Crystal
Monochrome
filter
X-ray beam

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

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XRD INSTRUMENT

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

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XRD INSTRUMENT

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XRD OF SiC
a.u.

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

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XRD OF AMORPHOUS MATERIALS

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

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INFORMATION FROM XRD RESULTS

Position of diffraction peaks (2)

+ Gives information about the elements of translational
symmetry, which means determining the shape and size of the
unit cell
+ Determine the names of minerals, materials, compounds,
and phases (compare with standard XRD)

Intensity of diffraction peaks

+ Calculate the electron density inside the lattice cell, which
means determining the position of the atoms in the lattice cell

Peak shape and width

+ Provide information about defects in the crystal
Dr. Nguyen Van Dung, Faculty of Chemical Engineering, HCMUT
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INTENSITIES OF X-RAY DIFFRACTION

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

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INTENSITIES OF X-RAY DIFFRACTION

The diffraction intensity is

significantly affected by
the arrangement of
atoms within the unit cell.

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

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INTENSITIES OF X-RAY DIFFRACTION

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

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STANDARD XRD PATTERNS

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STANDARD XRD PATTERNS

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

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STANDARD XRD PATTERNS

35-0734 Wavelength = 1.54056 Å

SrTiO3 2 Int hkl
Strontium Titanium Oxide 22.873 12 100
Tausonite, syn 32.424 100 110
Rad.: CuKa1 : 1.5405 Filter: Ni Beta 39.984 30 111
Ref: Swanson, H., Fuyat, Natl. Bur. Stand. (U.S.), Circ. 539, 3, 44, (1954). 46.483 50 200
52.357 3 210
System: Cubic S.G.: Pm m (221) 57.794 40 211
a: 3.9050 Å b: c: 67.803 25 220
a: b: g: 72.543 1 300
77.175 15 310
Pattern taken at 25 ˚C. Sample from Nat. Lead Co. 81.721 5 311
Spectrographic analysis: <0.01% Al, Ba, Ca, Si; <0.001% Cu, Mg. 86.204 8 222
Perovskite SuperGroup, 1C Group. PSC: cP5. To replace 5-634 95.127 16 321
and 40-1500.
Mwt: 183.52. Volume [CD]: 59.55

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

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XRD OF TiO2

Measured XRD pattern of TiO2 mixture and its phases analysis

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

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XRD OF KAOLIN

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

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XRD OF QUARTZ

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

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CALCULATION FOR CUBIC STRUCTURE

n = 2d hkl sin  Cu Ka ( = 1.54 Å) on d110 = 2.22 Å

d hkl
=2 sin  n sin  Lattice plane
n 1 0.34 20.7º Level 1 (110)

 = 2d nh nk nl sin 
Level 2 (110)
2 0.69 43.9º
Or (220)

 = 2d hkl sin  d 220 =

a
d 220 1
8 =
a a d110 2
d hkl = d110 =
h +k +l
2 2 2
2
Dr. Nguyen Van Dung, Faculty of Chemical Engineering, HCMUT
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CALCULATION FOR CUBIC STRUCTURE

λ = 2dhkl sin θhkl

1/d = 2 sin θ/ λ
1/d2 = 4 sin2 θ/ λ2
• d values can be calculated from Miller indices (hkl)
1/d2 = (h2 + k2 + l2)/a2
• Combining these equations, we have the expression:
sin2 θ /(h2 + k2 + l2) = λ2 /4a2
• Thus, we must find the values h,k,l so that the ratio
sin2 θ/(h2 + k2 + l2) is constant.

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

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SELECTION RULE

Structure Diffraction Non-diffraction

SC All No

BCC (h2+k2+l2) = Even (h2+k2+l2) = Odd

h, k, l are either all All h, k, l are not all odd

FCC
odd or all even or all even

Calculate h2 + k2 + l2 for each cubic structure

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

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SELECTION RULE
Prohibited number SC FCC BCC hkl
1 100
2 2 110
3 3 111
4 4 4 200
5 210
6 6 211
7
8 8 8 220
9 221-300
10 10 310
11 11 311
12 12 12 222
13 320
14 14 321
15 -
16 16 16 400
Dr. Nguyen Van Dung, Faculty of Chemical Engineering, HCMUT
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XRD OF NaCl

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

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XRD OF NaCl

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

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EXAMPLE

A material has a cubic structure with the following diffraction angles ():

9.30 13.26 16.32 19.01 21.27 23.41 25.44

The most intense diffraction peaks include the fourth peak (I/Io = 1), the
first peak (I/Io = 0.9), and the seventh peak (I/Io = 0.55).

Give Cu = 1.541Å,

a) Determine the cubic structure of this material

b) Calculate the lattice parameters of the material

c) Based on the standard data table, determine the material name

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

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EXAMPLE

 9.3 13.26 16.32 19.01 21.27 23.41 25.44

sin 0.162 0.229 0.281 0.326 0.363 0.397 0.430
sin2 0.026 0.053 0.079 0.106 0.132 0.158 0.185
dhkl 4.768 3.359 2.742 2.365 2.124 1.939 1.794
d2 22.732 11.284 7.518 5.595 4.511 3.761 3.217
TH1: SC 1 2 3 4 5 6 8
a2 22.73 22.568 22.555 22.381 22.556 22.565 25.738 const
TH2: BCC 2 4 6 8 10 12 14
a2 45.46 45.137 45.111 44.762 45.113 45.131 45.042 =const
TH1: FCC 3 4 8 11 12 16 19
a2 68.20 45.137 60.147 61.548 54.135 60.174 61.128 const
Vậy vật liệu này có cấu trúc bcc (lập phương tâm thể). Từ đó tính
được luôn thông số mạng a của vật liệu là a = 45.108 = 6.716Å
Dr. Nguyen Van Dung, Faculty of Chemical Engineering, HCMUT
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EXAMPLE

1 2 3 4 5 6 7
 9.3 13.26 16.32 19.01 21.27 23.41 25.44
sin 0.162 0.229 0.281 0.326 0.363 0.397 0.430
sin2 0.026 0.053 0.079 0.106 0.132 0.158 0.185
dhkl 4.768 3.359 2.742 2.365 2.124 1.939 1.794

d values in the fourth (2.365; I/Io=1); first (4,768; I/Io=0.9) and

seventh (1,794; I/Io=0.55)
Check the standard data table for the value d = 2.365 and the
corresponding intensity ratios, obtaining:

2.365 (1) 4.77 (0.9) 1.794 (0.55) Brucite Mg(OH)2

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

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

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SCHERRER EQUATION

t (kích thước tinh thể) is the mean size of the ordered (crystalline) domains,
which may be smaller or equal to the grain size, which may be smaller or equal
to the particle size.
Dr. Nguyen Van Dung, Faculty of Chemical Engineering, HCMUT
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MICROPOROUS MATERIALS (ZSM-5 ZEOLITES)

https://pubs.rsc.org/en/content/articlelanding/2018/RA/C7RA11763A

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

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MICROPOROUS MATERIALS (MOF-5 Zn4O(BDC)3)

https://pubs.acs.org/doi/10.1021/acsomega.8b02332
Dr. Nguyen Van Dung, Faculty of Chemical Engineering, HCMUT
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MICROPOROUS MATERIALS (OMS-2)

https://link.springer.com/article/10.1007/s10562-019-02828-1
https://pubs.acs.org/doi/10.1021/jp0300593

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

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MESOPOROUS MATERIALS (MCM-41)

https://www.mdpi.com/2073-4344/9/7/606/htm
https://www.mdpi.com/1996-1944/11/5/779

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

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MESOPOROUS MATERIALS (FDU-16)

SAXS patterns of FDU-

16 single crystals (A)
and FDU-15 (B)

https://pubs.rsc.org/en/content/articlelanding/2014/ta/c4ta00379a/unauth
https://www.researchgate.net/publication/275545331_Supplementary_Information_2007-JACS-
Mesoporous_carbon_single-crystals_from_organic-organic_self-assembly_SI
Dr. Nguyen Van Dung, Faculty of Chemical Engineering, HCMUT
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Ag/TiO2 NANOCOMPOSITE

https://link.springer.com/article/10.1007/s00339-017-1240-7

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

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Fe3O4–Ag HYBRID NANOPARTICLES

https://doi.org/10.1166/jnn.2016.11029
Dr. Nguyen Van Dung, Faculty of Chemical Engineering, HCMUT
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CELLULOSE NANOCRYSTALS

Crystallinity index
(độ tinh thể)
IAM/I002 x 100%

https://doi.org/10.1590/1980-5373-MR-2019-0192
Dr. Nguyen Van Dung, Faculty of Chemical Engineering, HCMUT