PMS by Self-Assembly

Fabrication of PMS by self-assembly
PMS on the SWCNT and Graphene
Zh.E. Sartova
al-farabi Kazakh National University, Almaty, Kazakhstan
Almaty 2017
Classification of porous materials
Depending on pore size Depending on building

framework
Micropoorus Mesoporous Macroporous
<2nm 2-50 nm >50nm

ZSM-5 MCM-41 Sponge
Purely inorganic Organic Inorganic Purely
hybrid organic
Silica MOF organic
porous polymers
Mesoporus Materials
Meso a Greek prefix in between - micro and macro
porous system
Mesoporous materials may be ordered or disordered.
They possess high

Surface area -400 -1000 m2/g
Large pore volume
High stability -500 -600 C
They are usually synthesized by the use of Soft template

method.
Ex: MCM-41,SBA-16,FDU-11,IITM-56 etc.

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 used as catalysts or
catalyst supports.
Processing
The processes by which nanoparticles self-assemble are
widespread and important. Understanding why and
how self-assembly occurs is key in reproducing and
optimizing results. Typically, nanoparticles will self-
assemble for one or both of two reasons: molecular
interactions and external direction. Recently,
researchers are more interested in the latter of these
two reasons, and are able to apply external directing to
a large variety of systems.
Self-assembly of nanoparticles
Self-assembly is a phenomenon where the components of a
system assemble themselves via an interaction to form a
larger functional unit. This organization can be due to direct
specific interaction or indirectly through their environment.
Due to the increasing technological advancements, the study
of materials in the nanometre scale is becoming more
important. The spatial arrangements of these self-assembled
nanoparticles can be potentially used to build increasingly
complex structures leading to a wide variety of materials that
can be used for different purposes.
At the molecular level, intermolecular force hold the
spontaneous gathering of molecules into a well-defined and
stable structure together. In chemical solutions, self-assembly
is an outcome of random motion of molecules and the affinity
of their binding sites for one another. In the area
of nanotechnology, developing a simple, efficient method to
organize molecules and molecular clusters into precise, pre-
determined structure is crucial.
Self Assembly
A very thin layer of material is deposited onto a

substrate of other material.
Stresses occur as a result of the mismatch of crystal

lattices between two different materials.
The thin material tends to clump up forming quantum

dots.
Synthesis
To achieve a defined pore diameter surfactants are used
that form micelles in the synthesis solution. These form
templates that help build up the mesoporous framework.
For MCM-41 mostly cetyltrimethylammonium
bromide (CTAB) is used.
The surfactant first forms rod-like micelles that
subsequently align into hexagonal arrays. After adding
silica species these cover the rods. Later, calcination leads
to a condensation of the silanol groups so that the silicon
atoms are bridged by oxygen atoms. The organic template
is oxidized and disappears.
Complete synthesis summary
Silica self-assembly
In the top part of the figure you see a diagram of the time
evolution of the synthesis that leads to periodic mesoporous
silicas. The synthesis involves the co-assembly of surfactants and
hydrolyzed TEOS molecules that condense on the outer walls of
the micelles formed by the surfactants. This leads eventually to a
solid amorphous framework possessing a regular array of holes
defined by the micelles. Upon calcination the surfactants and
their micelles can be burnt off and the silica composing the walls
of the porous material can be further condensed. Below you see
from the left: a high resolution SEM microphotograph showing
clearly the pores and the hexogonal symmetry with which they
are assembled; the gas adsorption isotherm and adsorption-
desorption hysteresis show the typical shape.
Characterization of mesoporous materials
1. Low angel XRD

0.5 -5 -2theta
- orederness / disorder.
2. N2 sorption measurements BJH

(Barrett-Joyner-Halenda) method
Surface area/pore diameter /pore
volume
3. TEM images
Order ,Morphohology ,
Wall thickness
Single-walled carbon nanotubes catalytically
grown from mesoporous silica thin film
A new technique of synthesizing single-walled carbon
nanotubes (SWNTs) from a thin film of SBA-16 type
mesoporous silica (MPS) on a Si substrate was developed.
The alcohol catalytic CVD method was employed for the
low temperature synthesis of SWNTs to minimize the
sintering of catalytic metals and damaging of the MPS
structure. The role of MPS layer is discussed based on SEM
and Raman analyses, in comparison with the reference
experiments made using Si substrates coated with silica
thin films. This technique suggests a possibility of
synthesizing SWNTs at welldefined intervals utilizing the
periodic structures of MPS.
This approach has resulted in the occasional
production of multi-walled nanotubes (MWNTs) due to
a sintering of deposited/sputtered catalytic metals,
which can be caused by their higher CVD temperature
(typically 900 C) and almost perfect flatness of Si
surface. From this concern, mesoporous silica (MPS)
could be an ideal material for achieving well-
regularized synthesis of carbon nanotubes with an
expected effect of preventing sintering of catalytic
metals.
Here described a new methodology of synthesizing
high-quality SWNTs employing a thin film of cubic type
SBA-16 that has accessible pores on the surface. This
method of metal loading differs from any of the past
work, where the catalytic metal was pre-mixed in the
stage of silica formation. SWNTs have been synthesized
from MPS thin film on a Si substrate using the alcohol
catalytic CVD method was developed, by which was able
to produce high-quality SWNTs at temperature as low as
550 C.
Preparations
1. Tetraethyl-ortho-silicate (TEOS), ethanol, H2O, and HCl were
mixed and stirred for 1 h at 65 C to form a solgel solution. This
solution was mixed with an ethanol solution of amphiphilic triblock
copolymer [(C2H2O)106(C3H4O)70(C2H2O)106] (BASF, F127)
and stirred for another 2 h at room temperature. The self-
assembled polymers served as a structure-directing agent (SDA) in
the formation of mesopores. The overall composition of prepared
mixture was fixed to
{TEOS:H2O:HCl:ethanol:polymer=1:9.2:0.021:40:7.2x10-3} in molar
ratio. The solution thus prepared was mounted on a piece of Si
substrate (2 cmx2 cm) by the dip-coating method at a constant pull-
up rate of 6 cm/min. After the coating, the piece was dried in air at
80 C overnight and calcinated in air at 500 C for 4 h to remove the
polymers, by which an MPS thin film with a typical thickness of 50
nm was formed.
Subsequently, catalytic metal was loaded on the MPS-coated Si
substrate (referred to as MPS/Si substrate). Iron acetate
(CH3CO2)2Fe and cobalt acetate (CH3CO2)2Co-4H2O were dissolved in
ethanol (typically 20 ml) to form a metal acetate solution so that the
weight concentration of both metals were made equal, either 0.01 or
0.001 wt% in this report. The MPS/Si piece was placed on the
bottom of a beaker containing the metal acetate solution and was
then transferred into a desiccator for evacuation by a rotary pump
for 1 h. It is crucial to set the initial solution level below 10 mm to
avoid sudden boiling during the evacuation. With this process, air
remaining inside the mesoporous film was replaced with the
solution. The pieces surface was washed immediately after drawn-
out from the solution with ethanol by two different procedures, as
described in a later section. The metal-loaded MPS/Si piece was
heated up to about 400 C in the flow of He/O2 (5% O2) to remove
organic residues and to form oxidized bimetallic particles inside (or
partly on the surface) of the thin film. As reference experiments,
silicacoated Si substrates (referred to as Silica/Si substrate)
without mesoporous structure were employed to examine the role of
the mesopores. This Silica/Si piece was fabricated by identical
procedures for the metal loading process but without addition of the
polymers.
The MPS layer provides an additional volumetric
capacity for holding catalytic metals inside it, and a
physical potential for prevention of sintering. The
present CVD process at relatively low temperature
contributes to the prevention of metallic sintering at
the same time to the preservation of the MPS
structure. This study has suggested a possibility of
growing SWNTs regularly in well-defined intervals by
utilizing the periodic structure of MPS.
Thank you for your attention!!!
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Fabrication of PMS by self-assembly

PMS on the SWCNT and Graphene

Depending on pore size Depending on building

Micropoorus Mesoporous Macroporous

<2nm 2-50 nm >50nm

They possess high

They are usually synthesized by the use of Soft template

Ex: MCM-41,SBA-16,FDU-11,IITM-56 etc.

A very thin layer of material is deposited onto a

Stresses occur as a result of the mismatch of crystal

The thin material tends to clump up forming quantum

1. Low angel XRD

2. N2 sorption measurements BJH

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