RESEARCH PROPOSAL

Name: Sana ullah Khan

Research Topic:
Preparation and determination of catalytic properties of Mn-Oxide nano
particle.

BACKGROUND

Manganese is the tenth most abundent metal in the earth’s layer and is used

mostly as a colour, battery material, deoxidizer, and also as adsorbents,

heterogeneous catalysts, and molecular sieves in steel manufacturing. In soils

and sediments, Manganese oxides are extremely dynamic oxides (1) and its

sorption capability has been explored in detail by a variety of scientists. In the

same way, the catalytic degradation properties of these oxides have been

studied for organic molecules/pollutant by ecological scientist. Number of

researchers found that Mn Oxide used as a catalyst in different type of

chemical reactions e.g. the oxidation of methane and carbon monoxide, the

breakdown of NO, the decrease of nitrobenzene and the catalytic combustion of

organic compounds. (2). Catalytic combustion is a chemical procedure which

uses a catalyst to speed desired oxidation reactions of a fuel and so decrease

the formation of undesired products, particularly pollutant nitrogen oxide

gases (NO) far below what can be achieved without catalysts. However, the

catalytic properties of Mn-Oxide nano particle have not been studies in great

detail. Very few studies of this kind have been performed even in the
technologically sophisticated countries. This research project purpose is to

study the preparation of the Mn-oxide nano particles, as they have greater

surface area and may be more proficient & selective catalyst for the

degradation of a variety of organic pollutant in natural system(3). The catalytic

performance of Mn-oxide depended on the oxidation state of manganese, the

oxygen mobility and the amount of surface adsorbed oxygen species. In the

present study, we will prepare Mn-Oxide nano particle by different methods

available in the literature and, after that, it catalytic properties for the

decomposition of different organic compounds will be investigated. Likewise,

the prepared nano particles will be characterized by different microscopic and

spectroscopic techniques, like surface area, FTIR, Zeta potentiometer and

Scanning and transmission electron microscopy.

METHODOLOGY

By different methods, Manganese oxide nanoparticles (-MnO2, -MnO2, -

MnO2) can be prepared. However, we will discuss only two of them because of

the simplicity, cost factor and high product yield. In the same way, when we

heated manganese oxide in the presence of air above 1000degree centigrade. [4]

then Mn3O4 are produced. Significant research has centered on making nano-

crystalline Mn3O4 and different syntheses that involves in the oxidation of MnII

or decreasing of MnVI.
Preparation of Crystalline MnO2

1. By thermal/heat treatment method the MnO nano particles can prepared

already reported in the literature (6). In a 100ml distilled deionized water

first 8.1g MnSO4•H2O and 11.0g (NH4)2S2O8 powders will be consecutively

put into a beaker. For 30 min, the solution would be magnetically stirred

at room temperature. The slurry solution will be put into a 150ml

stainless-steel autoclave with a Teflon-liner, which will be then filled with

distilled water up to 80% of the total volume. The autoclave will be sealed

which will be maintained at 120º C for different period of time up to

48hours. Then the autoclave will be allowed to cool down to room

temperature. After that, the brown products will be filtered off. In the

distilled water and absolute ethanol, it will be washed for some time and

then the air will be dried at 70ºC for 24h. The manufactured goods which

was a black powder, was obtained, is MnO 2 Nanoparticles which

contained all sort of Crystalline MnO2, i.e., etc.

2. -MnO nano particles can be prepared with simple refluxing route using

stiochiometric ratio of MnSO2.H2O, Na2S2O8 and NaOH as raw material in

500ml of dioinized water. The solution is transferred to round bottom

flasks with condenser at 160 oC for 24 hours. The dark brown material at

the bottom will be removed, wash using dialysis tubes will be used for

further studies.
 3. Another method is the combustion, in which 50% solution manganese

nitrate is first evaporated using 100W electric bulb in fuming hood and

then the solution is transferred after 3 days to electric oven at 200 oC. The

remains which has got is washed first with distilled water and then with

ethanol.

Characterization

By Transmission/scanning Electron Microscopy (TEM/SEM), X-Rays

Diffraction , Energy Dispersive X-Ray, Atomic Force Microscopy , the samples

of MnO2 nanoparticles will be characterized. All these techniques gives

sufficient information regarding the elemental analysis.

With Fourier Transform Infrared Spectroscopy (FTIR) techniques and XPS

techniques, the surface morphologies of the synthetic oxide nanoparticles will

be investigated. The thickness of the layered manganese oxide if form during

combustion method will be evaluated with small angle X-ray scattering

techniques (SAXS). Likewise, dissolution of MnO 2 sample can be checked using

Atomic absorption spectrophotometer.

CATALYTIC STUDIES.

Mn Oxide nanoparticles synthesized will be used as a catalyst. These oxides

have greater surface area and high surface charge density; therefore, it is

actively catalyzed and causes degradation of different organic substances. Most

of the organic compounds such as acryl amide, various pesticides, Para Nitro
Phenols, other phenolic compounds, dyes like ethylene blue are continuously

adding into the biosphere and are causing water/soil pollution. All these

compounds are highly toxic and need to be removed or changes into another

non-toxic species. MnOxide nanoparticles have catalytic property and can

change these compounds into other compounds which are non-toxic or less

toxic. Likewise, these oxides have a lot of active site and can shown sorption

properties as well. Now-a-days, Metal oxides such as MnO 2 and FeO Nano

particles have been the subject of demanding research as of their potential

uses in electronics, photonics, and catalysis. For the reduction of nitrobenzene,

Mn oxide have been used effectively as catalyst. It is evident that the Mn oxide

catalyst has the most active redox behavior favored, the manufacturing of

highly condensed product (e.g. aniline etc) but the catalyst, having the slightest

active redox behavior showed meager catalytic activity. It was suggested that

the catalytic and the redox behavior of Mn 3O4 might be connected to the Jahn-

Teller result [5].

Objectives of the project

The present study has the following aims to study;

1: The mechanism of the Mn-oxide nano particles preparation.

2: To determine the catalytic mechanism of oxide nanoparticles for the

degradation of various volatile organic pollutants especially in air emitted from

industrial process and automobiles exhaust.

3: To evaluate the kinetic and thermodynamics parameters of catalytic process

in organic pollutant degradation.

4: To compare the catalytic activity of the prepared Mn-oxide nano particles

with other metal and metal oxide catalyst reported in the literature.

SCOPE OF THE STUDIES

In the current years, a significant attention has been paid to metal oxide nano

particle particularly, in studying their magnetic properties because of their

application in semiconductor, biosciences, drug delivery, in targeting

pathogenic activities. Yet, there has been done a very little work in studying the

catalytic behavior of these nanoparticles. Furthermore, the current

application of bimolecular customized magnetic nano particles Mn oxide and

Fe oxide to detect pathogens, decontamination and strain identifications, since,

several bacteria use mammalian cell surface carbohydrates anchors to attach

to the cell surfaces resulting infections. The high surface/volume ratio and

following higher surface area of the nano particles not only allows higher

sorption of different toxic compound but also cause degradation of these

organic compound via affective catalytic action.

REFERENCES:
1. Tonkin, J.W.; Balistrieri, L.S.; Murray, J.W. (2004) Modeling sorption of

divalent metalcations on hydrous manganese oxide using the diffuse

double layer model. Applied Geochem., 19: 29–53.

2. Qing, F. D., Tie, Z.R., Zhoung, Y.Y. (2013) Mesoporous Mn-Oxide nano

particles catalytic total oxidation of toluene., Reaction Kinetics

Mechanism Catalysis, 108, 507-518.

3. Zaman, M.I, Mustafa, S, Sadullah, K, M.I.Khan,A. Niaz, (2013) The effect

of phosphate adsorption on the surface characteristics of Mn-Oxide,

Separation Science and Technology, 48,1709-1716.

4. Hausmannite Mn3O4 nanorods: synthesis, characterization and

magnetic properties Jin Du et al. Nanotechnology, (2006),17 4923-4928,

5. W.Weimin, Yang, y., Zhang, J., Selective reduction of nitrobenzene to

nitrosobenzene over different kinds of trimanganese tetroxide catalysts

(1995), 133, 81-93.

6. Li. L., Pan. Y., Chen. L., Li. G., Journal Solid state Chemistry, 180, 2896-

2904 (2007)