NANOMATERIAL

SPECIAL TOPIC: NANOLAYERED AND

NANOPOROUS MATERIALS

PROF.DR.RER.NAT. KARNA WIJAYA, M.ENG

NANOMATERIAL AND ENERGY RESEARCH GROUP

LABORATORY OF PHYSICAL CHEMISTRY,
FACULTY OF MATHEMATICS AND NATURAL SCIENCES,
UNIVERSITAS GADJAH MADA, YOGYAKARTA, INDONESIA

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 MATERIALS
A material is defined as a substance (most often a solid, but other condensed phases can be
included) that is intended to be used for certain applications
Materials can be found around us, or in other words we are surrounded by materials. Our body
itself is basically material.Our ancestors used materials to make various kinds of tools, such as
axes, arrows, swords and so on

"For Authors: Nature Materials" Archived 2010-08-01 http://www.uwosh.edu/faculty_staff/mihalic

1/31/2021 3
at the Wayback Machine k/materials/CHAPTER1.pdf
 HISTORY

http://slideplayer.com/slide/7601036/

http://www.xtec.cat/monografics/cirel/pla_le/nottingham/josep_poch/p
pt_josep_poch/l1_classification.pdf
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 TYPE OF MATERIALS

http://slideplayer.com/slide/8828654/26/images/6/Institute+of+Materials+Science+and+Nanotechnology.jpg
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 CLASSIFICATION OF Functional materials” are defined as
FUNCTIONAL MATERIALS those materials that perform specific
functions. Examples : semiconductors,
magnetic materials, piezoelectrics and ionic
conductors.

1/31/2021 http://slideplayer.com/slide/7601036/
https://www.campus-fws.de/en/about-us/ 6
1/31/2021 https://www.campus-fws.de/en/about-us/ 7
 NANOMATERIAL
NANOMATERIALS DESCRIBE, IN PRINCIPLE, MATERIALS OF WHICH A SINGLE UNIT IS
SIZED (IN AT LEAST ONE DIMENSION) BETWEEN 1 AND 1000 NANOMETRES (10−9 METER)
BUT IS USUALLY 1—100 NM (THE USUAL DEFINITION OF NANOSCALE[1]) (Wikipedia)

THE MATERIAL WITH THE NANO SCALE IS A MATERIAL THAT IS VERY ATTRACTIVE BECAUSE THEY HAVE VERY
DIFFERENT CHARACTERISTICS COMPARED TO WHAT THEY SHOW IN ITS MACROSCOPIC SCALE. FOR EXAMPLE, THE
BULK PLATINUM METAL KNOWN AS INERT MATERIAL CAN BE TURNED INTO A CATALYTIC MATERIAL, IF ITS SIZE IS
REDUCED SO THAT COULD REACH INTO THE NANO-SCALE
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 NANOMATERIAL: EXAMPLES
NANOMATERIALS ARE MATERIALS WITH MORPHOLOGICAL FEATURES SMALLER THAN 100 NM IN
AT LEAST ONE DIMENSION. MATERIALS REDUCED TO THE NANO SCALE CAN SHOW VERY
DIFFERENT PROPERTIES COMPARED TO WHAT THEY EXHIBIT ON A MACRO SCALE, ENABLING
UNIQUE APPLICATIONS

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 NANOMATERIAL: DIMENSIONALITIES

Layered Nanomaterials-A G.J. E.D.T., Vol. 1(2)

1/31/2021 Review 2012:32-41 10
 Thionicotinamide capped gold Gold nanorod (copyright (2002),
nanoparticle (Rao, 2004) American Chemical Society)

Gold nanospheroid (copyright (2002),

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American Chemical Society)
 Si nanochain (Rao, 2004) SiO2 nanoribbon (Rao, 2004)

https://www.blue-scientific.com/upgrade-
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tem-sem-camera/zeolite-tem-image/
 NANOMATERIAL: PREPARATION

1/31/2021 Layered Nanomaterials-A Review G.J. E.D.T., Vol. 1(2) 2012:32-41 13

 NANOPOROUS AND NANOLAYERED MATERIALS

I. NANOPOROUS MATERIALS
A. INORGANIC NANOPOROUS MATERIALS
B. ORGANIC NANOPOROUS MATERIALS
II.NANOLAYERED MATERIALS
A. INORGANIC NANOLAYERED MATERIALS
B. ORGANIC NANOLAYERED MATERIALS

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 I. NANOPOROUS MATERIAL

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 POROUS MATERIAL

Generally porous materials have porosity (volume ratio of pore space to the
total volume of the material) between 0.2-0.95. Pores are classified into two
types: open pores which connect to the surface of the material, and closed
pores which are isolated from the outside
1/31/2021 Nanoporous Materials: an Overview, GQ.Lu 16
Nanoporous materials as a subset of nanostructured materials possess
unique surface, structural, and bulk properties that underline their
important uses in various fields such as ion exchange, separation,
catalysis, sensor, biological molecular isolation and purifications.
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Nanoporous Materials: an Overview, GQ.Lu
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 CLASSIFICATION OF NANOPOROUS MATERIAL

https://www.google.co.id/search?q=preparatio
n+of+porous+material&biw=1280&bih=599&si
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te=webhp&source=lnms&tbm=isch&sa=X&ved
 MOF: Metal Organic Framework

SBU: Secondary Buliding

Unit

SBB: Supramolecule Building Block

https://www.semanticscholar.org/paper/Methane-storage-in-advanced-
1/31/2021
porous-materials.-Makal- 20
Li/0add761f83d5dd98f28731bcf6fc09ae3005c633/figure/0
 1.ORGANIC NANOPOROUS MATERIAL

Examples for (a) oxygen-, (b) nitrogen-, and (c) sulfur-containing structure
motives in nanoporous carbon-based materials. (a) reproduced from [21],
with permission from Wiley, 2008; (b) reproduced from [30], with
permission from RSC Publishing, 2015; (c) reproduced from [31], with
https://www.mdpi.com/2079- permission from American Chemical Society, 2012.
4991/10/4/639

1/31/2021 C 2018, 4(4), 56; https://doi.org/10.3390/c4040056 21

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Porous organic cages: soluble, modular, molecular pores
Tom Hasell and Andrew I. Cooper
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 Porous organic cages: soluble, modular, molecular pores
Tom Hasell and Andrew I. Cooper
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 CH3
2
R
O
NH2 S
2 O

C + N -
VIA CRYSTAL ENGINEERING CH3
O
NH2 S
O
Hydrogen bonds can be used to form CH3
pores for organic compounds

X-Direction
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Wijaya, 1999 Acetamidinium-dimesylamid 25
Z-Direction
 VIA CRYSTAL ENGINEERING

Wijaya, 1999 2,6-Diaminopyridinium-dimesylamid

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 POPs: Porous organic materials have attracted significant attention in the last few years due to their high surface
area and functionalizable pores. Considering the facts of
(i) the superior chemical, thermal and hydrothermal stabilities arising from strong covalent bonds,
(ii) structural and functional tunability,
(iii) lightweight because of B, C, N, O, H-based building blocks, porous organic polymers (POPs) have emerged as
an important theme in the current research. The tunable pore size with the high surface area as well as excellent
structural robustness trigger their extensive utilization from the gas storage and separation to heterogeneous
catalysis and water purification.
http://home.iiserb.ac.in/
~abhijit/research2.html
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 RSC Adv., 2019, 9, 8073-8080
https://www.x-mol.com/paper/723352
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 2. INORGANIC NANOPOROUS MATERIAL
ZEOLITE MCM41

MCM-41 (Mobil Composition of

Matter No. 41) is a mesoporous
material with a hierarchical
structure from a family of silicate
and alumosilicate solids that
were first developed by
researchers at Mobil Oil
Corporation and that can be
zeolite is a mineral that has a high abundance and used as catalysts or catalyst
widespread in Indonesia. This mineral was found more supports
than 200 years ago by Cronstedt in the rocks that used
as building material. This new species is a porous PILLARED AND DELAMINATED
crystalline aluminosilicates which later was named
CLAY
zeolite or stone that can boil.

Pillared clay is a kind of clay modified

porous materials. Chemically pillared clay
is defined as the derivative smectite that
the cations has been exchanged with bulk
sized cations and those cations plays a
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role as a pillar micelles 29
 https://www.google.com/imgres?imgurl=http%3A%2F%2Fwww.pratley.com%2Fimages%2Fproducts%2Fzeolite.
JPG&imgrefurl=http%3A%2F%2Fwww.pratley.com%2Foperating-divisions%2Fpratley-
zeolite&tbnid=682lHy3pStgo4M&vet=12ahUKEwiR8pD83L3uAhXTiuYKHWVQAbMQMygTegUIARDqAQ..i&doci
1/31/2021 d=NSMc4hWKHJoh0M&w=560&h=380&q=zeolite&safe=strict&ved=2ahUKEwiR8pD83L3uAhXTiuYKHWVQAb30
MQMygTegUIARDqAQ
PILLARED BENTONITE

http://www.sciencedirect.com/science/article/pii/S1385894717302012

Kloprogge, J.T., Duong, L.V., and Frost, R.L., 2005, A Review of the
Synthesis and Characterization of Pillared Clays and Related Porous
Materials for cracking of Vegetable oils to Produce Biofuels, Environ.
Geol, 47, 967-981. https://www.researchgate.net/publication/230692074_Recent_Advances_in_the_Synthesis_and_Catalytic
1/31/2021 _Applications_of_Pillared_Clays/figures 31
PREPARATION OF ZrO2-PILLARED BENTONITE
(INORGANIC POROUS NANOMATERIAL) The purpose of modification is to form pores within the bentonite/smectite layer

9.6 A

d001 d001

Pillar
H+
Sheet/Layer

d(001) = d(001)-9.6 A

TEM (of a,b) Na-bentonite (Suseno, 2015)

XRD diffractogram (a) bentonite (b) zirconia-bentonite
(c,d) ZrO2-bentoniteFigure
intercalation compound (c) zirconia-pillared bentonite
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(Suseno, A. et.al, 2015) 32
 Adsorption-desorption isotherm graphs of Size pore distribution on ZrO2-bentonite
(a) bentonite, (b) ZrO2-pillared bentonite

(Suseno, A. et.al, 2015, )

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 ZrO2-pillared bentonite and Cation analysis result
bentonite porosity on bentonite

Parameters Bentonite ZrO2-Bentonite Cation type (%)

Surface area 52,830 (m2/g) 269,165 (m2/g)

Na+ 0,60

Porous volume 0,152 (cc/g) 0,204 (cc/g)

Ca2+ 0,04

(Suseno, A. et.al, 2015 )

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 II.NANOLAYERED MATERIAL

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 1a. ORGANIC (SUPRAMOLECULAR) NANOLAYERED MATERIAL

2,6-Diamino-4-phenyl-1,3,5-triazin-1-ium-
Wijaya, 1999
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dimesylamid
36
 1b. ORGANIC-LAYERED NANOMATERIALS

Graphite :
(https://cmi.epfl.ch/metrology/img/dan
http://pubs.rsc.org)
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 2a.INORGANIC-LAYERED NANOMATERIALS

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 2b.INORGANIC-LAYERED NANOMATERIALS

Hydrotalcite is a layered double

hydroxide of general formula
Mg6Al2CO3(OH) 16· 4(H2O), whose
name is derived from its
resemblance with talc and its high
water content.

CLAY/SMECTITE

Clay or often called nanoclay, is an

layered aluminosilicate compounds HYDROTALCITE
with interlayers cations are generally
interchangeable
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 CLAY MINERALS

3D Geostatistical Modeling and Uncertainty Analysis of Clay Minerals

1/31/2021 Distribution in Reservoir Rocks 40
BENTONITE BENTONITE IS A TYPE OF CLAY THAT THE
MAIN CONTENT IS MONTMORILLONITE. COMPARED TO
OTHER CLAYS, MONTMORILLONITE HAS EXCELLENT
ABSORBABILITY IN THE INTER-LAYERED SPACE AS
WELL AS ON ITS OUTER SURFACE.
MONTMORILLONITE HAS A HIGH ION-EXCHANGE
CAPACITY THAT IS ABLE TO ACCOMMODATE CATIONS
IN THE INTER-LAYERED SPACE IN LARGE QUANTITIES.
Zhirong, L., Uddin, Md.A., Zhanxue, S., 2011, FT-IR and XRD Analysis of Natural Na-
Bentonite and Cu(II)-Loaded Na-Bentonite, Spec. Acta Part A, 79, 1013-1016.

Bentonite Structure
BENTONITE
https://www.researchgate.net/publication/ CHARACTERISTIC
1. High thermal stability
2. Expandable layer
3. Easily modified
4. High surface area
https://www.researchgate.net/publication/227148102_ChemInform_Abstract_Synthesis_of_Smectites_an
d_Porous_Pillared_Clay_Catalysts_A_Review
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(Wijaya,et.al, 2014)
 American Journal of Materials Synthesis and Processing https://commons.wikimedia.org/wiki/File:Structure_of_Cl
Volume 1, Issue 2, July 2016, Pages: 10-20 ay_Sheets.jpg
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KAOLINITE MONTMORILLONITE

S.K. Haldar, Josip Tišljar, in https://ceramicartsnetwork.org/ceramics-

Introduction to Mineralogy and Mat. Res. vol.20 supl.2 São
1/31/2021 Petrology, 2014 Carlos 2017 Epub May 11, 2017 monthly 43
 Biomedical applications of cationic clay minerals
M. Ghadiri,a W. Chrzanowskiab and R. Rohanizadeh

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TRANSITION METALS/BENTONITE

d001
9.6 A TRANSITION METAL (Ni, Cr, Pt, etc) HAS A STRONG
ATTRACTION POWER DUE TO THE VACANCY OF
ELECTRON PAIRS IN THE d-ORBITAL. TRANSITION
METAL SUCH AS Cr METAL IS VERY EFFECTIVE IN THE
d001 CATALYTIC REACTION. Cr METAL IS EASY TO FORM
COVALENT COORDINATE BONDS SO THAT THE
FORMATION OF INTERMEDIATES ON THE SURFACE
OF THE CATALYST BECOMES EASIER (Jujarama, Wijaya, K.,
Fahrurrozi M., and Suheryanto., 2014, Synthesis of Biogasoline from Used Palm
Cooking Oil Through Catalytic Hydrocracking by Using Cr-activited Natural Zeolite
H+ as Catalyst, Asian J. of Chem., 26(16), 5033-5038)

Transition metals
Sheet/Layer

d(001) = d(001)-9.6 A

http://ask.learncbse.in/t/why-are-chromium-and-copper-
Nickel-containing hydrocracking catalyst , US 4816538 A exceptions-to-electronic-configuration/
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XRD Diffraction Analysis, Cr/Bentonite (Wijaya, 2017)
d001
9.6 A d001

d001

Intensity (a.u)
d001

d001
H+
Chrom sheet

Basal Spacing (d001 ) of Catalyst

Sample 2θ (º) d001 (Å) ∆d001 (d001 – 9,6 Å)

XRD DIFFRACTOGRAM
Bentonite 5.78 15.27 5.67 a) Bentonite
H-bentonite 5.19 17.00 7.40 b) H-bentonite
c) Cr/bentonite
Cr/bentonite
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 (Wijaya, 2017)
FTIR-Spectra) bentonite b) H-bentonite c) Cr/bentonite

Wave Length (cm-1)

Bentoni H- Cr/benton Assignments
te bentonite ite
3626 3626 - Stretch Vib of
O-H (aluminol)
Transmitance (a.u)

3448 3448 3425 Strech Vib of

O-H (silanol)
1635 1635 1627 Bend Vib of H-
O-H (water)
1041 1041 1056 Ass Strech Vib
of Si-O-Si
918 918 -
794 794 794 Streching Al-O-
Al
532 524 - Bend Vib of Si-
462 462 470 O-Si (quartz)
Bend Vib of Si-
O-Al
Bend Vib of Si-
O-Si

1/31/2021 Wave Number (cm-1) 47

XRF Characterization Acidity (Wijaya, 2017)

Acidity
Composition (%) No Catalyst
(mmol/g)
Catalyst
A Bentonite 5.392
Cr Al Si

B H-bentonite 6.940
Bentonite 0.13 ± 0.003 8.6 ± 0.003 48.7 ± 0.4

C Cr/bentonite 8.789

H-bentonite 0.06 ± 0.002 9.7 ± 0.05 55.6 ± 0.1

The synthesis of Cr/bentonite catalyst was

successfully, performed by increasing the surface
Cr/bentonite 1.11 ± 0.007 9.9 ± 0.09 55.6 ± 0.2 area of bentonite from 56.103 m2/g to 60,239 m2/g,
the mean of pore radius from 105.707 Å to 117.918 Å
and total pore volume from 14.83 cc/g to 17.76 cc/g
and acidity test to 8.789 mmol/g.
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TEM Characterization (Wijaya, 2017)

Bentonite 100 nm Cr/bentonite100 nm

1/31/2021 Bentonite 20 nm 49
Cr/bentonite 20 nm
BET/Isothermal Characterization (Wijaya, 2017)

Specific Surface Area, Average Pore Diameter, Total Pore Volume

Sample Specific Average Pore Total Pore

Surface Diameter (Å) Volume (10-2
Area cc/g)
a
(m2/g)

volume STP (cc/g)

Bentonite 56.103 105.707
14.83

Cr/bentonite 60.239 117.198 17.76

0 0.2 0.4 0.6 0.8 1 1.2

tekanan relatif (p/p0)

Isoterm adsorption-desorption of N2 on (a) Bentonite, (b)

Cr/bentonite
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 LAYERED DOUBLE HYDROXIDE

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 Hydrotalcite is a Layered Double Hydroxide whose name is derived from its resemblance
with talc and its high water content. Layered double hydroxides (LDH) comprise an unusual
class of layered materials with positively charged hydroxide layers and charge balancing,
mobile anions located in the interlayer region. This structure gives these material anion-
exchange properties. The natural form of hydrotalcite is mined in small quantities in the
Snarum area of Norway and the Ural area of Russia. Carl Christian Hochstetter (1842) was
the first to report about hydrotalcite, which was attached firmly to a schist. He described a
white material with a pearl like luster, with the formula Mg6Al2(OH)16CO3 . 4H2O.

A Short Review on the Catalytic Activity of

Hydrotalcite-Derived Materials for Dry
Progress on layered hydrotalcite (HT) materials as potential support and catalytic materials
Reforming
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of Methane Thangaraj Baskaran,a Jayaraj Christopherb and Ayyamperumal Sakthivel
52
1/31/2021 53
 SYNTHESIS AND MODIFICATION OF POROUS AND LAYERED MATERIAL

POROUS MATERIALS
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LAYERED MATERIALS54
1. HYDROTHERMAL PROCESS

Hydrothermal synthesis can be defined as a method of synthesis of single crystals that depends on the
solubility of minerals in hot water under high pressure. The crystal growth is performed in an apparatus
consisting of a steel pressure vessel called an autoclave,

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1/31/2021 http://hompi.sogang.ac.kr/zeolite/egall2.htm
56
2. SOL-GEL PROCESS

The sol-gel process is a wet-chemical technique

used for the fabrication of both glassy and ceramic
materials. In this process, the sol (or solution)
evolves gradually towards the formation of a gel-
like network containing both a liquid phase and a
solid phase.
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1/31/2021 58
3.INTERCALATION, ION EXCHANGE, IN CHEMISTRY, INTERCALATION IS THE REVERSIBLE
INCLUSION OR INSERTION OF A MOLECULE (OR ION) INTO
IMMPRAGNATION, ETC COMPOUNDS WITH LAYERED STRUCTURES

http://www.dept.edu.waseda.ac.jp/ogawal
ab/INDEX_Eng/Our_Research.html
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 Adv. Sci. 2017, 4,
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Fig. 5 The change in the interlayer spacing of K- and Li-
intercalated graphite obtained using DFT calculation.

Fig. 4 XRD patterns of inorganic salt-intercalated

graphite obtained via KCl and LiCl intercalation.
The inset image shows the shift of the (002) peak.

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 Fig. 10 The change in the layer spacing
of SO42−-intercalated graphite obtained
Fig. 9 XRD patterns of inorganic salt-intercalated graphite obtained by
Li2SO4 and LiCl intercalation. The inset image shows the shift of the
by DFT calculations.
(002) peak and the left image shows the diffraction peaks near 18°.

| RSC Adv., 2017, 7,

52252–52260
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4.PILLARIZATION: Porous Nanomaterial Preparation

Pillared clays is synthesized through the ion exchange and intercalation

techniques various oxides such as Al2O3, Fe2O3, TiO2 and Cr2O3 into the area
between layers or gallery clay so that form the pores with a certain dimension

1/31/2021 TIO2 -PILLARED MICA 63

(http://pubs.rsc.org/services/images/)
5. COCRYSTALLISATION: COCRYSTALLISATION BETWEEN THE TWO SPECIES THAT IS
COMPLEMENTER IS THE MOST POPULAR TECHNIQUE IN CRYSTAL
PREPARATION OF ENGINEERING IN THE SYNTHESIS OF NANOMATERIAL OR POROUS AND
POROUS AND LAYERED LAYERED NANOSUPRAMOLECULE WITH THE BASE OF ORGANIC
MATERIALS
ORGANIC NANOMATERIAL

D H A

A H D

COCRYSTALISATION (D: DONOR PROTON, H: PROTONS, A: (WIJAYA,1999).

PROTON ACCEPTOR) BETWEEN 2.6-AND DIMESYALAMINE
DIAMINOPYRIDINE

Cocrystallisation is the crystallization of two or more

chemical species in a particular solvent simultaneously.
Cocrystalisation product is a single crystal. Through the
careful selection, the best single crystal was taken and
then analyzed using single crystal X-ray analysis
techniques
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 CRYSTAL ENGINEERING
Crystal engineering, the design of molecular solids, is the synthesis of
functional solid-state structures from neutral or ionic building blocks, using
intermolecular interactions in the design strategy

Hydrogen bonds, coordination bonds, and other less directed interactions define substructural
patterns, referred to in the literature as supramolecular synthons and secondary building units

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REPRESENTATIVE SUPRAMOLECULAR SYNTHONS. 65
WEAK BOND USED IN CRYSTAL ENGINEERING

http://www.intechopen.com/source/html/41103/media/image5_w.jpg)

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 CHARACTERIZATION

XRD
FT-IR SEM/TEM

BET/Isothermal
1/31/2021 Particle Size Thermal Analysis 67
 X-Ray Diffraction
Give information about catalyst
structure and paricle size

Nano Hybrids and Composites Submitted: 2017-11-06

https://www.researchgate.net/post/Can_anyone_t ISSN: 2297-3400, Vol. 19, pp 46-54
ell_me_what_the_information_of_FWHW_in_XRD
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_spectra_can_tell_us
 SEM and TEM
Key Engineering Materials Submitted: 2017-03-20
ISSN: 1662-9795, Vol. 757, pp 131-137
1/31/2021
Transmission electron microscopy (TEM) is a
microscopy technique in which a beam of electrons is
transmitted through a specimen to form an image. The
specimen is most often an ultrathin section less than 100
nm thick or a suspension on a grid.
Fig. 3. Morphology of the catalyst (a) Al2O3-
bentonite resolution of 100 nm, (b) Al2O3-bentonite
resolution of 20 nm,
Nano Hybrids and Composites Submitted: 2017-11-06
ISSN: 2297-3400, Vol. 19, pp 46-54
69
 SURFACE AREA AND PORE SIZE ANALYZER

https://slideplayer.com/s
lide/4143065/ Nano Hybrids and Composites Submitted: 2017-11-06
ISSN: 2297-3400, Vol. 19, pp 46-54
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 FT IR SPECTROPHOTOMETER

https://slideplayer.com/s Nano Hybrids and Composites Submitted: 2017-11-06

lide/4143065/ ISSN: 2297-3400, Vol. 19, pp 46-54

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 PARTICLE SIZE ANALYZER

https://www.azonano.com/article
https://slideplayer.com/s
.aspx?ArticleID=4457
lide/4143065/
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 THERMAL ANALYZER
Thermal analysis is a branch of materials science where the
properties of materials are studied as they change with
temperature.

https://www.researchgate.net/publication/271920
640_Thermal_analysis_to_assess_pozzolanic_activi
ty_of_calcined_kaolinitic_clays/figures?lo=1
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 APPLICATION OF
NANOCATALYST

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 CATALYST AND CATALYSIS

Catalyst, in chemistry, any

substance that increases the
rate of a reaction without itself
being consumed

Catalysis is the process of

increasing the rate of a chemical
reaction by adding a substance
known as a catalyst, which is not
consumed in the catalyzed
reaction and can continue to act
repeatedly.
"Catalyst". IUPAC Compendium of Chemical Terminology. 2009.
https://www.britannica.com/science/catalyst
doi:10.1351/goldbook.C00876.
1/31/2021 ISBN 978-0-9678550-9-7 75
TYPE OF CATALYST

Catalysts can be heterogeneous or homogeneous, depending on whether a

catalyst exists in the same phase as the substrate.

https://www.tes.com/lessons/XIIMGpz6hw4gjQ/industrial-catalyst
1/31/2021 76
Heterogeneous catalysts
Heterogeneous catalysts act in a different phase than the reactants. Most
heterogeneous catalysts are solids that act on substrates in a liquid or
gaseous reaction mixture.

Knözinger, Helmut and Kochloefl, Karl (2002) "Heterogeneous Catalysis and Solid Catalysts" in Ullmann's Encyclopedia of Industrial
Chemistry, Wiley-VCH, Weinheim. doi:10.1002/14356007.a05_313
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 Heterogeneous catalysts are typically "supported," which means
that the catalyst is dispersed on a second material that enhances
the effectiveness or minimizes their cost. Supports prevent or
reduce agglomeration and sintering small catalyst particles,
exposing more surface area, thus catalysts have a higher specific
activity (per gram) on a support. Sometimes the support is merely a
surface on which the catalyst is spread to increase the surface area.
More often, the support and the catalyst interact, affecting the
catalytic reaction. Supports can also be used in nanoparticle
synthesis by providing sites for individual molecules of catalyst to
chemically bind. Supports are porous materials with a high surface
area, most commonly alumina, zeolites or various kinds of activated
carbon.

Knözinger, Helmut and Kochloefl, Karl (2002) "Heterogeneous Catalysis and Solid Catalysts" in Ullmann's Encyclopedia of Industrial
Chemistry, Wiley-VCH, Weinheim. doi:10.1002/14356007.a05_313
1/31/2021 78
 Homogeneous catalysts
Homogeneous catalysts function in the same phase as the reactants, but the mechanistic principles involved in
heterogeneous catalysis are generally applicable. Typically homogeneous catalysts are dissolved in a solvent with the
substrates. One example of homogeneous catalysis involves the influence of H+ on the esterification of carboxylic acids,
such as the formation of methyl acetate from acetic acid and methanol.[12] One high-volume process requiring a
homogeneous catalyst is hydroformylation, which adds carbon monoxide to an alkene to produce an alkyl aldehyde. The
aldehyde can be converted to various products such as alcohols or acids (for e.g. detergents) or polyols (for plastics such
as polycarbonate or polyurethane). For inorganic chemists, homogeneous catalysis is often synonymous with
organometallic catalysts.

Knözinger, Helmut and Kochloefl, Karl (2002) "Heterogeneous

Catalysis and Solid Catalysts" in Ullmann's Encyclopedia of https://pubs.rsc.org/en/content/articlelan
Industrial Chemistry, Wiley-VCH, Weinheim.
1/31/2021 ding/2019/cy/c9cy01997a#!divAbstract 79
doi:10.1002/14356007.a05_313
Biocatalyst
Biocatalysts can be thought of as intermediate between homogeneous and
heterogeneous catalysts, although strictly speaking soluble enzymes are homogeneous
catalysts and membrane-bound enzymes are heterogeneous. Several factors affect the
activity of enzymes (and other catalysts) including temperature, pH, concentration of
enzyme, substrate, and products. A particularly important reagent in enzymatic
reactions is water, which is the product of many bond-forming reactions and a reactant
in many bond-breaking processes.

Nelson, D.L. and Cox, M.M. (2000) Lehninger, Principles of Biochemistry 3rd Ed. Worth Publishing: New York. ISBN 1-57259-153-6.

https://commons.wikimedia.org/wiki/File:227_Steps_in_an_Enzymatic_Reaction-01.jpg
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 Photocatalysis
In chemistry, photocatalysis is the acceleration of a photoreaction in the presence of a
catalyst. In catalysed photolysis, light is absorbed by an adsorbed substrate. In
photogenerated catalysis, the photocatalytic activity (PCA) depends on the ability of the
catalyst to create electron–hole pairs, which generate free radicals (e.g. hydroxyl radicals:
•OH) able to undergo secondary reactions. Its practical application was made possible by
the discovery of water electrolysis by means of titanium dioxide (TiO2)

https://www.researchgate.net/publication/282948982_Evaluation_on_the_Photocatalytic_Degradation_A
1/31/2021 81
ctivity_of_Reactive_Blue_4_using_Pure_Anatase_Nano-TiO2/figures?lo=1 http://fotokataliza.pl/
Nanocatalyst
sNanocatalysts are nanomaterials with catalytic activities. They have been
extensively explored for wide range of applications. Among them, the
nanocatalysts with enzyme mimicking activities are collectively called as
nanozymes

https://www.researchgate.net/publication/2
64798243_Mechanistic_Understanding_of_T
oxicity_from_Nanocatalysts/figures?lo=1
1/31/2021
https://www.researchgate.net/publication/31142359
7_Water_Oxidation_Mediated_by_Ruthenium_Oxide
_Nanoparticles_Supported_on_Siliceous_Mesocellula
82
r_Foam/figures?lo=1
Solids that possess acidic properties on their surfaces function as catalysts just like liquid acids, such
as sulfuric acid and hydrochloric acid. By using solid acid catalysts, chemical processes become more
productive and more environment-friendly. Actually solid acids are being used in many industrial
chemical processes from the largest chemical process of catalytic cracking in petroleum refining to
synthesis of various fine chemicals.

https://www.sciencedirect.com/science/article/abs/pii/S0920586114003186

https://www.researchgate.net/publication/290977850_Solid_acid_catalysis_From_fun
damentals_to_applications
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 Sulfated Alumina Sulfated SnO2

Sulfated Titania Sulfated Alumino Silicate

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1/31/2021 85
1/31/2021 86
In chemistry, photocatalysis is the acceleration of a
photoreaction in the presence of a catalyst. In
catalysed photolysis, light is absorbed by an adsorbed
substrate.

https://www.researchgate.net/figure/Photodegradation-of-Congo-red-dye-for-120-min-under-solar-radiation-for-
different-pH_fig6_327442306
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 PHOTOCATALYST OF TiO2/Al2O3-PILLARED SAPONITE

1/31/2021 Fatimah, I.et.al, 2015, Arabian Journal of Chemistry 88

1/31/2021
 Fig. 6 （left）Change in the XRD pattern of cationic azo dye（AZ ＋ ） -modified Kunipia F by
phenol intercalation and by subsequent photoirradiations. （right）Schematic drawing of the
photoinduced intercalation of phenol: Reprinted from ref. 50 with permission from The Royal
Society of Chemistry.

https://www.researchgate.net/publication/313233576_Intercalation_of_Organic_Compounds_into_Layere
1/31/2021 90
d_Clay_Minerals/figures?lo=1
 HYDROCRACKING PROCESS
Hydrocracking is a cracking process in which higher-molecular-weight hydrocarbons
pyrolyze to lower-molecular-weight paraffins and olefins in the presence of hydrogen

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 BIOGASOLINE PREPARATION

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 BIOGASOLINE PREPARATION

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 The SEM images obtained for the nano
ZrO2, nano ZrO2–SO4 and Pt/nano
ZrO2–SO4 are shown in Fig.1. It can be
seen that the surface morphology of
the nano ZrO2 precursor was not
signicantly changed after the addition
of sulphate and Pt. However, the nano
ZrO2–SO4 does exhibit increased
agglomeration. The nano ZrO2 surface
topography after acid modification
shows a typical porous material that
has a rough structure with irregular
shapes. It has been reported that the
calcination step in the process used to
make the sulphate facilitates the
coalescence of primary particles,
leading to a significant increase in the
particle size of the nano ZrO2. For
nano ZrO2–SO4 sample, some
particles with different size and
disordered shape were obtained from
The Pt/nano ZrO2–SO4 shows a typical inner surface morphology with smaller and more regular particle the incorporation of very small
size. The EDX spectrum of the Pt/nano ZrO2–SO4 clearly shows Pt particles on the surface (Fig. 1d). crystallites during the calcination
This observation indicates the homogeneous dispersion of Pt over the nano ZrO2–SO4 support and the process.
size of Pt particles fit into the range of 2–5 nm. The size of the metallic Pt and support plays a crucial role
in the reaction pathway to obtain the optimum catalytic activity and selectivity. The impregnation of Pt via
a hydrothermal
1/31/2021 method significantly inhibited the particle agglomeration, thus stabilized the catalyst
surface.
 XPS was used to obtain additional insights into the Pt
composition, based on comparisons of the binding energy
values, so asto examine the metal loading mechanism.
Fig. 2 presents the deconvoluted Pt 4f spectrum acquired
from the Pt/nano ZrO2– SO4, which contains Pt0 4f7/2 and
Pt0 4f5/2 peaks, centered at 71.5 and 74.8 eV,
respectively. Peak is also present at 73.1 eV (Pt2+ 4f7/2)
due to the presence of Pt2+ species. This result indicates
that the Pt particles had diameters on the scale of several
nm, such that electron interactions occurred between
these particles and the nano ZrO2–SO4 surface.28–30 In
addition, Table 1 shows the relative area of the
deconvoluted Pt0 4f7/2, Pt0 4f5/2 and Pt2+ 4f7/2 spectra. This
result indicates that the reduction of Pt4+ under a
hydrogen gas stream was successfully formed Pt0
particles with the total composition of 81.8%.

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 Conclusions
The catalyst characterizations indicate that Pt loading via
a hydrothermal method inhibited particle agglomeration
and thus increased the surface area of the Pt/nano ZrO2–
SO4. The acid treatment and Pt loading increased the
activity and selectivity for hydrocracking of waste LDPE
due to a significant increase in catalyst acidity. The data
show that Pt was successfully impreg_x0002_nated with
the total composition of Pt0 was 81.8% and
homoge_x0002_neously dispersed on the nano ZrO2–
SO4 surface, producing a highly active and selective solid
acid catalyst in the hydro_x0002_cracking reaction under
low temperature reaction conditions.Liquid, solid and gas
yields of 69.7, 0.2 and 30.1 wt% were obtained from
waste LDPE hydrocracking under the optimized
conditions (a temperature of 250 oC, a reaction time of
60 min and a catalyst-to-feed proportion of 1 wt%). The
liquid fraction con_x0002_tained as much as 56.0 wt%
gasoline-type products and 13.7 wt% diesel-type
products. In addition, the Pt/nano ZrO2–SO4 showed high
stability and maintained its activity up to the sixth cycle
for the conversion of waste LDPE into gasoline-range
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 BIOGASOLINE PREPARATION

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NANOCATALYST OF Cr-ZrO2-BENTONITE
Chrom
9.6 A

d001 d001

ZrO2-Pillar
H+
Sheet/Layer

d(001) = d(001)-9.6 A

TRANSITION METAL (Ni, Cr, Pt, etc) HAS A STRONG ATTRACTION POWER DUE TO THE VACANCY OF ELECTRON
PAIRS IN THE d-ORBITAL. TRANSITION METAL SUCH AS Cr METAL IS VERY EFFECTIVE IN THE CATALYTIC
REACTION. Cr METAL IS EASY TO FORM INTERACTION WITH REACTANTS SO THAT THE FORMATION OF
INTERMEDIATES ON THE SURFACE OF THE CATALYST BECOMES EASIER
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 CHARACTERIZATION Catalyst
Cation Exchange Capacity
(meq/100 g)

X-Ray Difractogram HF bentonite 86,40

ZrO2-bentonite 39,20

Fig.1 Diffractogram of
(a) bentonite
(b) bentonite dispersed on water
(c) HF-treated
1/31/2021 bentonite
Fig.2 Diffractogram of
(a) oligocation intercalated bentonite
(b) zirconia pillared bentonite 99
 X-Ray Diffractogram FTIR Spectra
(Wijaya, K., 2017, ICIRSTM, SIngapore)

Fig.4 FTIR spectra of HF Bentonite catalyst (a),

Fig.3 Diffractogram of ZrO2-bentonite (a), Cr/ZrO2-B-1
ZrO2-bentonite (b), Cr/ZrO2-B-1 (c), Cr/ZrO2-B-2
(b), Cr/ZrO2-B-2 (c) and Cr/ZrO2-B-3 (d)
1/31/2021 (d) and, Cr/ZrO2-B-3 (e) 100
 Table 1. Results of determination on basal spacing of d001 peak, specific surface area,
average porous diameter, total porous volume and acidity of catalyst

Δd001 Surface area Average pore Total pore Number of acid

Catalyst 2θ (˚) d (Å) (m2/g) diameter (Å) volume (cc/g)
(d001-9,6) (Å) site (mmol/g)
HF Bentonite 5,676 15,56 5,96 96,64 38,31 0,22 4,46
ZrO2-bentonite 3,158 27,95 18,35 164,04 38,37 0,28 7,22
Cr/ZrO2-B-1 3,155 27,98 18,38 105,80 38,15 0,16 7,25
Cr/ZrO2-B-2 3,535 24,97 15,37 101,07 38,49 0,17 7,78
Cr/ZrO2-B-3 3,685 23,96 14,36 102,00 38,21 0,17 8,21

Table 2. XRF Analysis Results of the catalyst

Catalyst ZrO2 (%) Cr (%)

HF Bentonite - 0,078±0,012
ZrO2-bentonit 79,3±0,1 0,020±0,001
Cr/ZrO2-bentonite 1% 74,1±0,2 0,260±0,002
Cr/ZrO2-bentonite 2% 78,0±0,2 0,458±0,007
Cr/ZrO2-bentonite 3% 75,8±0,07 0,632±0,003
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 BET/ISOTHERMAL
Bentonit HF ZrO2-Bentonit
ZrO2-bentonit Cr/ZrO2-bentonnit 2%
0.007
Cr/ZrO2-bentonit 3%

0.006

0.005

dV (D) (cm3/Å/g)
0.004

0.003

0.002

0.001

Fig.5 isotherm adsorption-desorption N2 on

(a) HF/ Bentonite Pore diameter (Å)
0.000
(b) ZrO2-bentonite
20 30 40 50 60 70 80 90 100
(c) Cr/ZrO2-bentonite 1%
(d) Cr/ZrO2-bentonite 2%
(e) Cr/ZrO2-bentonite
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 TEM ANALYSIS

Fig.6 TEM image (Morphology) of

(a) ZrO2-bentonite
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(b) Cr/ZrO2-B-3 103
 BIODIESEL PREPARATION
SINGLE STEPS BIODIESEL PREPARATION

https://www.hielscher.com/biodiesel_processing_efficien
cy.htm
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 TWO STEPS BIODIESEL PREPARATION

https://www.researchgate.net/figure/Fig-3-Esterification-A-and- https://www.sciencedirect.com/science/
transesterification-B-reactions-to-produce-biodiesel_fig2_318872680 article/abs/pii/S0960852412007225
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 BIODIESEL PREPARATION

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 109
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 BIODIESEL PREPARATION

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 ALCOHOL DEHYDRATION: DEE AND DME

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 ADSORPTION STUDY
Adsorption is the adhesion of atoms, ions or
molecules from a gas, liquid or dissolved solid to
a surface. This process creates a film of the
adsorbate on the surface of the adsorbent.

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GENERAL CONCLUSIONS

IN GENERAL, WE CAN MODIFY MANY MATERIALS WITH USING

EASY METHODS TO BECOME EFFECTIVE NANOCATALYST

ACKNOWLEDMENTS

This research and publication were funded by Ministery of Research, Technology and Higher
Education, Republic of Indonesia, (KEMENRISTEK-DRPM-DIKTI) through
PUPT, INSINAS, STRANAS, MP3EI, WCR, PTUPT and PMDSU

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