Ex.

No CHEMICAL SYNTHESIS OF NANOMATERIALS Date:

ZERO-VALENT IRON NANOPARTICLES

1. Synthesis of Zero-valent iron nanoparticles

Zero-valent iron nanoparticles (NZVI) are more effective than macroscale ZVI, iron
powder or iron filings, under similar environmental conditions. Zero-valent iron is
inexpensive, non-toxic and a moderate reducing reagent (standard reduction potential E0 =
−0.44 V).

Zero-valent iron nanoparticles (Fe0) are of tremendous use in environmental cleanup

especially in reducing soil and ground water contamination can be reduced. Fe0 enters
oxidation-reduction (redox) reactions that degrade certain contaminants, particularly
chlorinated hydrocarbons such as trichloroethylene (TCE), tetrachloroethylene, Chromium
etc. Fe0 also has been used to treat arsenic and certain metals. In the presence of oxygen, Fe 0
can oxidize organic compounds such as phenol.

Principle:
Addition of the NaBH4 to the FeCl3 solution in the presence of vigorous
magnetic stirring resulted in the rapid formation of fine black precipitates as the ferric iron
reduced to Fe0 and precipitated according to the following reaction:

FeCl3(H2O)3 + 3NaBH4 + 3H2O → Fe0↓+3H3BO3 + 3 NaCl + 10H2

Reagents required:

1. 0.16M Sodium borohydride (NaBH4) solution: NaBH4 solids of 0.6053 g dissolved in

100 mL of 0.1 M NaOH solution.

2. 0.1M Ferric or Iron (III) Chloride (FeCl 3.6H2O) solution: 2.7030g of FeCl3.6H2O
was dissolved into 100-mL pure distilled water.

(NaBH4 solution should be made in NaOH solution, as the NaBH 4is unstable in water and can
quickly result in a loss of reduction power).

Procedure

Nanoscale ZVI (nZVI) particles were prepared freshly each day by adding 0.16M
NaBH4 (98%, Aldrich) aqueous solution dropwise to a 0.1 M FeCl 3.6H2O (98%, Aldrich)
aqueous solution at ambient temperature. The synthesis of nZVI is performed under
atmospheric conditions. The particles were washed 3 to 4 times with a 10 −4 M HCl (pH 4)
solution and stored as a 5mg Fe/mL concentrate at pH 4 and kept in a cooling room (< 4◦C).

Dry particles for characterization were obtained by washing the wet precipitates with
10 M HCl 3 to 4 times, followed by rinsing with pure water, and then separating using a
−4

centrifuge at 3000 rpm for 5 min to remove the remaining moisture. The ZVI particles were
then quickly frozen using liquid nitrogen and freeze dried under vacuum for more than 20
hrs. Compared with freeze drying under vacuum, drying under air resulted in the color of Fe
particles changing from black to reddish-brown within a few hours, indicating significant
surface oxidation.

Characterization of freeze-dried Fe0 particles:

S. Instruments Character of Fe0 analyzed

No
1. Scanning Electron Microscope (SEM) Particle size of the nanomaterial
2. Transmission Electron microscope (TEM) Particle size of the nanomaterial and
crystalline structure
3. XRD analysis using a X-ray diffractometer Dried Nanoparticle identified as
elemental iron
4. Brunauer–Emmett–Teller (BET) analysis Surface area of the particle
by N2 adsorption
5. Zeta Plus particle charge analyzer Surface charge of the particles at
different pH and zeta potential

Fig. Experimental set up for iron nanoparticle synthesis

2. Synthesis of cadmium sulfide Nano particles

Semiconductor nanoparticles (NPs) have shown extra ordinary florescence properties

and high quantum efficiency. Mostly II–IV semiconductor NPs of dimensions below Bohr
diameter exhibit interesting optoelectronic properties due to quantum size effect and are
potential candidates for several of applications.
Cadmium sulfide (CdS) belongs to the II–VI group, a direct bang gap (Eg = 2.42 eV)
semiconductor and is one of the promising materials for use in photoelectric conversion in
solar cell, thin film transistor (TFT), nonlinear optics, semiconductor laser and flat panel
display. 

Reagents Required
1. 0.01 M Cadmium Sulphate (CdSO4.8H2O) – Weight of 0.7695g of CdSO4.8H2O is
dissolved in 100 mL of distilled water.
2. 0.02 M Thiourea (CH4N2S) – Weight of 0.152g of CH4N2S dissolved in 100 mL of
distilled water
3. Ammonia solution

Procedure:
Equal amount of 0.01 M CdSO4.8H2O and 0.02 M Thiourea is dissolved in 50 ml
distilled water. pH of the reaction mixture is raised from 8 to 10 by adding Ammonia.
Reaction mixture is heated by using hot plate and temperature is maintained at 50 - 60 oC is
stirred for 1 hour. Yellow colored cadmium sulfide crystals are obtained
and are allowed to filter, washed with distilled water and dried.
 
Powder-XRD, SEM, HRTEM and micro-Raman spectrum were employed to
characterize the structure and morphology of the synthesized CdS. The optical properties
were studied through UV-Vis absorbance and micro-PL spectrum. The synthesized CdS
Nanoparticles could catalytically degrade organic dyes under the irradiation of UV light.

3.Synthesis of Zinc Oxide Nanoparticles

Zinc oxide Nanoparticle, with its unique physical and chemical properties, such as high
chemical stability, high electrochemical coupling coefficient, broad range of radiation
absorption and high photostability, is a multifunctional material. 

Reagents Required
1. Zinc nitrate (Zn NO3.3H2O) - Weight of 13.386g of Zn NO3.3H2O dissolved in
100mL of deionized water.
2. 0.95 M NaOH – Weight of 3.8g of NaOH dissolved 100mL of deionized water.
3. Ethanol

Procedure:
Aqueous solution of 0.45 M Zn NO3.3H2O and 0.95 M NaOH is prepared separately
using 100 ml of deionized water. Beaker with 0.95 M NaOH is heated at 55 oC. ZnNO3
solution was added drop by drop to the heated solution under vigorous stirring. The solution
is heated for 2 hours, and precipitate of Zn Nanoparticle obtained.
Then product was centrifuged at 5000 rpm for 20 min and washed three times with
distilled water and washed with absolute alcohol at last. The obtained product was calcined at
500 °C in air atmosphere for 3 hr. The existence was proved by Uv-vis spectroscopy (300 –
550 nm) whereas morphology and size were determined by the transmission electron
microscopy (TEM), and Dynamic light scattering (DLS) analysis.