Synthesis of TiO₂

• Submitted by: Preeti choudhary

• Roll No.= 17/MAP/016
• M.Sc.(Applied Physics)
• Submitted to: Dr. Ashish kumar
keshari
 Synthesis Methods

Chemical method

• Sol-Gel Method
• Hydrothermal Method
• Solvothermal Method
• Coprecipitation method
 Sol-Gel Method
reactants solvents

colloidal catalyst colloidal 3-dimns

particle time grid

liquid

Colloidal suspension of volume v wet monolith of volume v

• This process normally proceeds via an acid-catalyzed hydrolysis step of

titanium alkoxide follwed by condensation.
• The development of Ti-O-Ti chains is favored with low content of water,
low hydrolysis rates, and excess titanium alkoxide in the reaction
mixture.
• Dimensional polymetric skeltone swith close packing result from the
development of Ti-O-Ti chains.
• Nanoparticles: Case studies of their synthesis, properties and biological interaction Nils Gustav Martin Palmqvist Faculty of Naturals Resources
and Agricultural Sciences Department of Molecular Sciences Uppsala
 Sol-Gel and Drying Flowchart
Precursors, solvents,water & catalyst

Sol formation

Gel formation

Aging in mother liquor

washing

Drying process

xerogel(Evaporation) Aerogel (autoclave) cryogel (freeze-driver)

Calcination

Final material

• S. Shibata, K. Aoki, T. Yano and M. Yamane, Journal of solgel science and Technology, 11, 279, (1998).
• H. Hahn, Nanostructured Materials, 9, 3, (1997).
• H. Cheng, J. Ma, Z. Zhao, L. Qi, Chem. Mater., 7, (1995).
 Sol gel method
• Sol-gel method, as the name implies, comprises of two main
parts:
a) Firstly, the precursors form high molecular weight but still soluble
oligomeric intermediates, called a sol.
b) Secondly, the intermediates come close together to form a gel.
• sol-gel process is based on five processing steps :
i. Hydrolytic Polycondensation: Hydrolysis of alkoxide precursors which forms
a polymeric or particulate sol containing inorganic materials.
ii. Formation of a uniform suspension by deposition of substrate into the sol.
iii. Solidification of the gel with solvent and volatile compounds evaporation
process.
iv. Drying at room temperature to get a condensed inorganic network.
v. Calcination where very high temperature is involved to remove of organics
and to crystallize the solid material.

• TITANIUM DIOXIDE NANOMATERIALS, SYNTHESIS, STABILITY AND MOBILITY IN NATURAL AND SYNTHETIC POROUS MEDIA by Ghulam Raza A Thesis submitted to The
University of Birmingham for the degree of DOCTOR OF PHILOSOPHY School of Geography, Earth and Environmental Sciences The University of Birmingham December
2016
 Route of sol gel method
• ͦͦ
Take 100ml distilled water & TiCl₄ solution kept in refrigerator to cooling at -5͘͘͘͘͘͘ ͦc.

Add 25ml TiCl₄ in ice cool bath & solution releasing exothermic temp.

Beaker was taken from ice coop to room temp. with using magnetic stirring 500rpm.

Bath temp. was raised room temp. to 100 ͦc kept in the temp. till solution was
converted to thick like juice.

Solution was kept in furnace to heat treatment at 300 ͦc,400 ͦc-600 ͦc in 3 hour step
by step to eliminate contaminants

Finally TiO₂ nanopaticles are formed like Bobul egg shaped.

After ball minning TiO₂ nanoparticle are formed(500rpm , 5 hour)

• Asian Journal of Chemistry; Vol. 26, No. 3 (2014), 655-659 Synthesis and Characterization of TiO2 Nanoparticles ZIQUAN LIU*, RUMING
WANG, FANGJUN KAN and FUYI JIANG* School of Environmental and Material Engineering, Yantai Universiy, Yantai 264005, P.R. China
 Advantages and limitations of sol-gel
technique.
• Advantages: Sol-gel processes allow the synthesis of materials with:
• High purity, because organometallic alkoxy precursors can be purified by distillation
or recrystallization;
• high degree of homogeneity, because reagents are mixed at the molecular level;
• the possibility to control simultaneously the bulk properties, such as the phase
composition, and the surface characteristics, such as the surface area, the total pore
volume distribution, etc;
• low or high porosity, by using appropriate heat treatment and firing times;
• the capability of obtaining fully-dense amorphous solids at temperatures lower by
hundreds of centigrade degrees than those required for conventional
compaction/densification or for melting;
• Drawbacks:
• high cost for the majority of alkoxide precursors;
• long processing steps.

• UNIVERSITÀ DEGLI STUDI DI MILANO FACOLTÀ DI SCIENZE MM. FF. NN. DIPARTIMENTO DI CHIMICA FISICA ED ELETTROCHIMICA CORSO DI DOTTORATO DI RICERCA IN SCIENZE
CHIMICHE CICLO XXIII CH“NANOSTRUCTURED TiO2 AS A MULTIFUNCTIONAL MATERIAL: FROM PHOTOCATALYSIS TO BIOMEDICAL APPLICATIONS” PH.D. STUDENT ALBERTO
NALDONI TUTOR PROF. CLAUDIA L. BIANCHI CO-TUTOR PROF. SILVIA ARDIZZONE ACADEMIC YEAR 2009-2010
 Hydrothermal method
• Reactant are dissolved in water or another solvent
(solvothermal) in a clossed vessel.
• Bomb is heated above boiling point.
• Conventional or microwave oven.
Solvent above boiling point(supercritical water).
critical point : critical temp.- 374.15 ͦc, critical pressure -220
bar,critical density-0.321 g/cmᵌ

• Asian Journal of Chemistry; Vol. 26, No. 3 (2014), 655-659 Synthesis and Characterization of TiO2 Nanoparticles ZIQUAN LIU*, RUMING
WANG, FANGJUN KAN and FUYI JIANG* School of Environmental and Material Engineering, Yantai Universiy, Yantai 264005, P.R. China
 Hydrothermal Method
Titanium precursor water

Stirring & refluxing

Hydrothermal treatment by varying time and

temperature

Filtration and
washing

Air drying for 24 hour, powder TiO₂

• Asian Journal of Chemistry; Vol. 26, No. 3 (2014), 655-659 Synthesis and Characterization of TiO2 Nanoparticles ZIQUAN LIU*, RUMING
WANG, FANGJUN KAN and FUYI JIANG* School of Environmental and Material Engineering, Yantai Universiy, Yantai 264005, P.R. China
 Hydrothermal method
• Hydrothermal synthesis is normally conducted in
steel pressure vessels called autoclaves with or
without Teflon liners under controlled temperature or
pressure with the reaction in aqueous solutions.
• The temperature can be elevated above the boiling
point of water, reaching the pressure of vapor
saturation.
• The temperature and the amount of solution added
to the autoclave largely determine the internal
pressure produced.
• It is a method that is widely used for the production
of small particles in the ceramics industry .

• Asian Journal of Chemistry; Vol. 26, No. 3 (2014), 655-659 Synthesis and Characterization of TiO2 Nanoparticles ZIQUAN LIU*, RUMING
WANG, FANGJUN KAN and FUYI JIANG* School of Environmental and Material Engineering, Yantai Universiy, Yantai 264005, P.R. China
 Solvothermal method
• The solvothermal method is almost identical to the
hydrothermal method except that the solvent used here is
nonaqueous.
• However, the temperature can be elevated much higher than
that in hydrothermal method, since a variety of organic
solvents with high boiling points can be chosen.
• The solvothermal method normally has better control than
hydrothermal methods of the size and shape distributions and
the crystallinity of the TiO2 nanoparticles.
• The solvothermal method has been found to be a versatile
method for the synthesis of a variety of nanoparticles with
narrow size distribution and dispersity.

• Asian Journal of Chemistry; Vol. 26, No. 3 (2014), 655-659 Synthesis and Characterization of TiO2 Nanoparticles ZIQUAN LIU*, RUMING
WANG, FANGJUN KAN and FUYI JIANG* School of Environmental and Material Engineering, Yantai Universiy, Yantai 264005, P.R. China
 Routes of hydrothermal method
1M of titanium tetra isopropoxide mixed with 4M of acetic acid.

Solution mixed with 10M of distilled water & stirred vigorously for 1h to clear
solution & aging period 24h.

solution transferred to stainless steel autoclave & placed into oven at 180 ͦc to 12h.

Autoclave cooled down to room temp.

Solution dried 100 ͦc to get TiO₂ crystal.

Crushed into fine powder & annealed at 600 ͦ for 1 h.

• Asian Journal of Chemistry; Vol. 26, No. 3 (2014), 655-659 Synthesis and Characterization of TiO2 Nanoparticles ZIQUAN LIU*,
RUMING WANG, FANGJUN KAN and FUYI JIANG* School of Environmental and Material Engineering, Yantai Universiy, Yantai 264005,
P.R. China
 Co-precipitation method
• Co-precipitation: reactions involve the simultaneous occurance of
nucleation, growth, coarsening and agglomeration processes.
• Co-precipitation reactions exhibits following characteristics:
1. the product are generally insoluble species formed under
conditions of high supersaturation.
2. Nucleation is a key step, and a large number of small particles
will be formed.
3. Secondary processes, such as ripening and aggregation, affect
size, morphology, and properties of products.
4. The supersaturation conditions necessary to include
precipitation are result
xA(aq)+yB(aq) → AB(s)

• Asian Journal of Chemistry; Vol. 26, No. 3 (2014), 655-659 Synthesis and Characterization of TiO2 Nanoparticles ZIQUAN LIU*, RUMING
WANG, FANGJUN KAN and FUYI JIANG* School of Environmental and Material Engineering, Yantai Universiy, Yantai 264005, P.R. China
Co-precipitation method
Anion solution Cation solution

Nucleation and
growth

precipitation

filteration

calcination

grinding
 Route of Co-precipitation method
Prepare dilute solution of TiCl₄ at temp. 10 ͦc →add excessive H₂O₂ it. Solution turn
red after some time black.

Under magnetic stirring add ammonia & adjust PH to 10.→ yellow semi-solid.

Heat 50 ͦc temp for 30min & left 18h & after wash it →several layer formed.

Clear solution removed & rest solution into microburette & centrifugation for 5min &
add deionised water & repeat centrifugation 3 times.

Put 60 ͦc drying box for 30 min & white powder formed.

Heat 500 ͦc muffle for 2h & white TiO₂ produced.

• Asian Journal of Chemistry; Vol. 26, No. 3 (2014), 655-659 Synthesis and Characterization of TiO2 Nanoparticles ZIQUAN LIU*, RUMING
WANG, FANGJUN KAN and FUYI JIANG* School of Environmental and Material Engineering, Yantai Universiy, Yantai 264005, P.R. China
 Problem in co-precipitation

• Co-precipitation requires:
1. Similar salt solubilities
2. Similar precipitation rates
3. Avoid super-saturation as poor control of co-
precipitation
disadvantage: difficult to prepare high purity.

• Asian Journal of Chemistry; Vol. 26, No. 3 (2014), 655-659 Synthesis and Characterization of TiO2 Nanoparticles ZIQUAN LIU*, RUMING WANG, FANGJUN KAN and FUYI JIANG* School of Environmental and Material
Engineering, Yantai Universiy, Yantai 264005, P.R. China
Thankyou