Experiment:- 01 Kaushlendra Kumar

B191287MT

Synthesis of Ce0.6Zr0.4O2 nanoparticles by co-precipitation method

AIM:- Synthesis of Zirconium doped Ceria (Ce₀.₆Zr₀.₄O₂) nanoparticles by co-

precipitation method

Theory:- The coprecipitation technique involves the precipitation of metal

in the form of hydroxide from a salt precursor with the help of a base in a
solvent. The controlled release of anions and cations assists to regulate the
nucleation and particle growth kinetics, which helps to synthesize
monodispersed nanoparticles. This technique is used in the synthesis of
compounds containing two or more metals.

Materials Required:
Cerium nitrate hexahydrate, Zirconium oxychloride octahydrate, Ammonium
hydroxide, DI water

Equipment required:- PH paper, Butter paper, pipette, Silica Crucible,

Centrifuge, Centrifuge Tube, Magnetic Stirrer, Vortex Shaker, Hot Air Oven,
Muffle Furnace.
Calculations:-

Weight of 0.06 M cerium nitrate hexahydrate in 50 ml water

M = Molarity = 𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 (𝑛)/𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑣𝑒𝑛𝑡(𝑣)

n = MV (molarity of cerium nitrate hexahydrate = 0.06 M)

= 0.06 x 50 x 10^−3

Weight of sample:-
n = 3 x 10 moles −3
N = 𝑀𝑎𝑠𝑠(𝑊)/𝑀𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠(𝑚)

W=nxm
= 3 x 10^-3 x 434.22
W = 1.302 g

Weight of 0.06 M cerium nitrate hexahydrate in 50 ml water

M = Molarity = 𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 (𝑛)/𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑣𝑒𝑛𝑡(𝑣)
n = MV
= 0.04 x 50 x 10−3
n = 2 x 10^ −3 moles
N = 𝑀𝑎𝑠𝑠(𝑊)
𝑀𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠(𝑚)
W=nxm
= 2 x 10^-3 x 322.251
W = 0.6445 g

Volume of 3M Ammonium Hydroxide for 100ml solution (25% Ammonia was

taken for synthesis)
Density = 𝑀𝑎𝑠𝑠/𝑉𝑜𝑙𝑢𝑚𝑒
0.91 = 𝑀𝑎𝑠𝑠/25
Mass = 22.75 g
Number of moles = 22.75/17
= 1.338 moles

Molarity = 1.338 *1000 /100

= 13.38 M

As number of moles are equal

M₁V₁ = M₂V₂
V₂ = 3 𝑥 100/13.38
= 22.42 ml
• Procedure:- The process is carried out in following steps to obtain ceria –
zirconia mixed metal Oxides.

1. Co- precipitation reaction- The Precursor for ceria is cerium nitrate

hexahydrate and precursor for zirconia is zirconium oxychloride
octahydrate. Before preparing, ensure that the beaker is clear and air dried
by using a hot air oven. Weigh 1.3g of ceria precursor for preparing 0.66M
solution in 50 ml of DI water. Keep the solution in a magnetic stirrer for
complete mixing of the solution for 5 minutes. then add 0.6445g of
zirconium oxychloride octahydrate in 50 ml of water and mix it using a
magnetic stirrer. 3M Ammonium hydroxide is then added to the mixture as
a reducing agent. It is added slowly till the pH of the solution becomes 10.
After reaching pH of 10, the colour of the solution changes to red.

2. Centrifugation and washing of hydroxide intermediate: - Now, Add the

solution to centrifuge tubes and keep the tubes in the centrifuge.
Centrifuge tube of 50 ml capacity is used for centrifuging purpose with
setting of 4000 rpm, deceleration value is 60 m/s^2 and temperature is
28degs for 15 Minutes. Once it is completed, open the centrifuge and the
rotor. Now the particles have settled down at the bottom and sides of the tube and clear
solvent at the top.

3. Drying of intermediate product to remove the excess solvent present: -

Add distilled water to the precipitate and mix it properly using a vortex
mixer and again centrifuge to remove the impurities present in the
precipitate. After 15 minutes, take off the tube from the centrifuge and
remove the supernatant and continue this process 2-3 times. Shift
precipitate to watch glass for drying. Put holes on aluminium foil and cover
it over precipitate and put it under hot air oven. Dry it for 12 hours at 70ᵒC.
 4.Sintering - To reduce the hydroxide form to oxide form: - The product is
transferred to Silica crucible in a muffle furnace for 5 hrs. at 500ᵒC with a heating
rate of 10 A.
Final product is mixed metal oxide.

Reaction mechanism:
𝐶𝑒(𝑁𝑂3)3. 6𝐻2𝑂 (𝑎𝑞) + 𝑍𝑟𝑂𝐶𝑙2. 8𝐻2𝑂 (𝑎𝑞) + 𝑁𝐻4𝑂𝐻 (𝑎𝑞) →
𝐶𝑒𝑥𝑍𝑟 1−𝑥(𝑂𝐻) (𝑠) + 𝑁𝐻4𝑁𝑂3 (𝑎𝑞) + 𝑁𝐻4𝐶𝑙 (𝑎𝑞)

Results and Discussions: -

• Using the Scherrer Equation, the diameter of the particle is

Estimated from the plot data above.
D=Kλ/Δx Cosθ.
Where constants are, K = 0.94 λ = 0. 154 nm

In above graph peaks are situated at:-

• 17.604
• 5.113
• 7.291
• 5.819

Central angle Δx (Radian) Diameter (nm)

(radian)
0.263 0.023 6.797

0.278 0.026 5.618

0.445 0.031 5.245

0.464 0.036 4.030

Conclusion: - So, Zirconium doped ceria nanoparticles have

synthesized by co-precipitation method.
Reference-
[1] A. Joseph, K.P. John Mathew, S. Vandana, Zirconium-Doped Ceria
Nanoparticles as Anticorrosion Pigments in Waterborne Epoxy-Polymer
Coatings, ACS Appl. Nano Mater. 4 (2021) 834–849.
https://doi.org/10.1021/acsanm.0c03162.

2. https://www.sciencedirect.com/topics/engineering/coprecipitation