Ntcc report final report shubham

1. Synthesis of Magnetic Cryptomelane-type
manganese oxide (OMS-2) nanotubes for the
removal of lead based compounds from water
samples

Submitted to
Amity Institute of Nanotechnology
Amity University, Noida
In partial fulfillment of the requirements for the degree of
B.TECH+M.TECH NANOTECHNOLOGY

By: Shubham Raina
ENROLLMENT NO.: A1223313003

Under the guidance of
Dr. Ranjit Kumar

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AMITY INSTITUTE OF NANOTECHNOLOGY

PROJECT REPORT-2015

PROJECT TITLE : Synthesis of Magnetic Cryptomelane-type manganese
oxide (OMS-2) nanotubes for the removal of lead based compounds from water
samples
PROGRAMME : B.tech + M.tech Nanotechnology
SEMESTER : 5
NAME of STUDENT : Shubham Raina
ENROLLMENT NO : A1223313003
BATCH : 2013-2018
DURATION : 30 days
NAME OF GUIDE : Dr. Ranjit Kumar




Internal Guide Student

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DECLARATION BY THE CANDIADTE

I hereby declare that the matter in the project report entitled “Synthesis of Magnetic
Cryptomelane-type manganese oxide (OMS-2) nanotubes for the removal of lead
based compounds from water samples ” submitted to Dr. Ranjit Kumar ,
Assistant Professor, Amity Institute of Nanotechnology, Amity University, and
Noida is a bonafide and genuine research project under the guidance of Dr. Ranjit
Kumar. The work done in the report is original and has not been submitted earlier
for the award of any degree, diploma, or fellowship of any other university or
institution.

Date: July 15, 2015

NAME : Shubham Raina
Enrolment no. : A1223313003

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CERTIFICATE BY THE GUIDE

This is to certify that the report entitled “Synthesis of Magnetic Cryptomelane-type
manganese oxide (OMS-2) nanotubes for the removal of lead based compounds
from water samples ” is a bonafide research work carried out by Shubham Raina,
which is submitted in partial fulfillment for the award of the degree of “B.tech +
M.tech Nanotechnology” in the Amity University, Noida .


Date: Prof. Dr. Ranjit Kumar


Place: Noida, Uttar Pradesh

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ACKNOWLEDGEMENT

I would like to thank Dr. Ranjit Kumar for giving me such
interesting and challenging topic to carry out my experimental
research project .
I would also like to thank sir for helping me , guiding me by
providing relevant and important concepts and other important
data regarding my experimental work .

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Table of contents

S.No. Topic Page no.
1.
ABSTRACT
PAGE 8

2.
INTRODUCTION
Page 8

3.
EXPERIMENTAL
PROTOCOL
Page 9



4.
SAMPLE
CHARACTERIZATION
Page 10
5.


RESULTS AND
DISCUSSION
Page 11

6.
FUTURE WORK Page 12

7. 7






























7..
CONCLUSION
Page 12
8.
REFERENCES
Page 13

8. 8
Abstract

Magnetic cryptomelane-type manganese oxide nanotubes were successfully prepared
by depositing Iron(II) oxide (magnetite/ Fe3O4) nanoparticles onto the nanotubes.
The synthesized material exhibits excellent magnetic and catalytic properties for the
degradation of lead based compounds from water samples and can be magnetically
separated from the solution with ease leaving clear water behind .


Introduction
Manganese oxide is a type of microporous transition metal oxide that can form
mixed-valent semiconducting octahedral molecular sieves (OMS) with tunnel like
structures of various sizes [2]. OMS materials have extensive applications and
advantages such as low cost, high adsorption activity, and non-toxicity [3–10].
Among these, α-MnO2 (cryptomelane, OMS-2), having an ordered tunnel structure
shared with MnO6 octahedral chains, has been extensively used as a cathode
material [11],adsorbents [8,13], and catalysts [14–17].
OMS-2 nanotubes can be easily prepared by hydrothermal treatment of KMnO4 in
the HCl solution [5, 8, 17] and has been recently revealed to possess high adsorption
capability for dye degradation and heavy metal ion removal in wastewaters [13, 16].
In most research reports it remains a challenge to develop a simplistic and
economic rout to separation or recovery of these nano- materials from
heterogeneous systems. To solve this problem magnetic separation is being
considered an ideal alternative to the removal of in situ nanomaterials via magnetic
induction [13].
In this report the successful synthesis of ferromagnetic cryptomelane-type nanotubes
have been carried out by a combination of hydrothermal and precipitation
techniques, and the prepared Fe3O4-OMS-2 nanotube composite exhibited excellent
adsorption efficiency for the degradation of lead based compounds from water
samples .

9. 9
Experimental Protocol
Preparation of OMS-2 Nanotubes

To synthesize MnO2 nanotubes, a hydrothermal method was carried out [17].
0.9 g of KMnO4 and 2.0 mL of HCl (37 wt%) were added to 40 mL of deionized
water under magnetic stirring to form the precursor solution.
After stirring the solution for about 20 min, it was transferred into an autoclave with
a capacity of 100 mL. The autoclave was sealed and heated in an oven at 110 °C for
24 hrs . The product was filtered, washed with distilled water and ethanol, dried at
80 °C.
Preparation of Fe3O4/OMS-2 Nanotubes

To fabricate the magnetic manganese oxide nanotubes, nanoparticles of Fe3O4 were
deposited onto OMS-2 nanotubes using a chemical co-precipitation method [13]. 0.1
M urea extract was added to an equimolar solution of ferric chloride (FeCl3) . The
resulting solution was left for stirring for 2 hours at 85-90°C . 0.1 M solution of
ferrous sulphate heptahydrate (FeSo4.7H2O) was added to the solution with
continuous stirring for 10-15 minutes. For the formation of magnetic Fe3O4 pH of
the solution was increased to maximum by addition of 0.3 M NaOH solution with
continuous stirring. After 20 minutes of continuous stirring , 0.5g of the OMS-2
precursor (powder) was added to the solution. The final solution so obtained was
sonicated for 15 minutes. The solution was then left for overnight aging. The
product was then washed several times with distilled water till pH became neutral
( before being separated using a magnet – for magnetic separation test ). The product
was then dried in an oven at 80°C for 1 hour in a petridish. The dried product was
scraped of with the help of a spatula , ground into a fine powder using a pestle and
mortar and stored in a cellophane pouch .

Adsorption Property Measurement

The reaction was carried out in 3 boiling tubes , which contained varying
concentrations of lead acetate solution (0.1 M ,0.01 M ,0.05 M) prepared by
dissolving appropriate quantity of lead acetated powder (analytical reagent) in
distilled water, and 100 mg of composite . The mixture was allowed to react at

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room temperature with continuous stirring. The solutions were kept on stirring for
about 20 minutes and then left undisturbed .
After about 30-60 minutes of keeping the boiling tubes undisturbed , it was
observed that that the composite completely adsorbs lead acetate , settles down at the
bottom of each tube leaving clear water above .

Sample Characterization
The changes of absorptions at 221 nm were applied to identify the concentrations of
lead acetate in each tube , using a LabindiaT60 UV/VIS Spectrophotometer .





Plot showing concentration vs absorbance at 221nm UV radiation


UV-Visible spectroscopy is used to study the interaction of the Fe3O4/OMS-2 with
the lead ions. Absorption spectra recorded in the region of 200-300 nm for 0.1 M
and 0.05 M lead acetate and composite-lead acetate solution are shown in above
Figure. The absorption spectrum of lead acetate90.1 M, 0.05 M) shows the
characteristic peaks at 221 nm. The spectra of lead adsorbed in both cases ( original

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lead acetate solution and clear water obtained after composite-lead acetate reaction)
show difference absortion peaks signifying significant reduction of lead ions from
the solution leaving clear water

Result and Discussion

It takes about 30 mins for all suspended particulates in the aqueous phase to
be attracted and accumulated at the magnetic region (Fig. 4), indicating that the
as-prepared Fe3O4/OMS-2 nanotubes exhibited remarkable magnetic separability.
The sorptive degradation of heavy metals for clear water is one important
wastewater treatment method nowadays. Herein, the as-prepared Fe3O4/OMS-2
nanotubes were tested for their adsorptive efficiency in the adsorption of lead acetate
under controlled conditions (Fig. ). The prepared Fe3O4/OMS-2 nanotubes showed
complete stability during the reaction, and 98.45 % and 99.91%(0.1 M and 0.05 M
respectively) of the lead acetate was decomposed . 
lead acetate in 3 varying concentrations (0.1 M, 0.01 M, 0.05 M)


Solutions after addition of Fe3O4-MnO2 nanotube composite (image after sedimentation of composite
and lead acetate

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Samples after magnetic separation of sediment(composite-lead acetate mixtures)


Future work
Due to unavailability of X-Ray diffractometer , SEM and due to shortage of time -
the characterization( XRD, SEM , DLS) of the Fe3O4-MnO2 nanotube composite and
UV analysis of clear water obtained after reaction between the Fe3O4-MnO2
nanotube composite and 0.01 M lead acetate solution was not completed . I plan to
follow up on these tasks in the current semester or in the semester break before next
semester whenever time permits .




Conclusion
In conclusion, Fe3O4-MnO2 nanotube composite was successfully prepared by
grafting Fe3O4 nanoparticles onto the OMS-2 MnO2 nanotubes. The nanotube
composite showed excellent adsorption activity for the degradation of lead based
compounds from water samples , showed 98.45% and 99.91% reduction in the
concentration of lead ions from solution . The residues left at the bottom of the
boiling tubes were then magnetically separated from the solution with ease leaving
clear water behind . Because of its simple manipulation, the prepared composite may
have potential applications in water purification technology.

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References

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