AISSMS COE PUNE DEPT. OF CHEMICAL ENGG.

SYNTHESIS OF IRON MOLYBDATE CATALYSTUSING SOLVOTHERMAL PROCESS

FOR PHOTOCATLYTIC APPLICATIONS

BY MR.GANDHAR GHANEKAR (B80215917) & MR. KAPIL DESHMUKH (B80215914)(B.E Chemical)

UNDER THE GUIDANCE OF PROF. P..N DANGE

AND DR. RAJENDRA PANMAND(C-MET,PUNE)

CONTENTS

• Abstract• Introduction• Procedure• Future scope • Application• Data Analysis • Optimization Techniques

Abstract

• Monoclinic and Orthorhombic Iron(II) Molybdate micro-sized particles selectively prepared by Solvothermal process.

• Product obtained on basis of pH, temperature & reaction time.

• 3D architectures of Iron(II) Molybdate nanoparticles with unique geometry can be used as a catalyst in photo-catalytic fields.

Mechanism of homogeneous catalyst

• First utilized by Davy around 1816 in the mine safety lamp and defined by Berzelius in 1835

• Models were first used in the early 1920s to understand the mechanism involved.

• It employs the phenomenon of adsorption which involves three steps-

a. Attachment of reactants to catalyst substrateb. Surface reaction on the surface of the catalystc. Desorption of the products formed from the catalyst surface

Mechanism of heterogeneous catalyst

• Cation exchange resins – insoluble polymer matrix that can exchange ions with the adjacent mixture.(eg. Amberlyst 15H)

• The use of heterogeneous catalysts has the following inherent advantages over homogeneous catalysts

a) They eliminate the corrosive environment.b) The catalyst can be easily removed from the reaction mixture

by decantation or filtrationc) The purity of the products is higher since the side reactions

can be completely eliminated or are less significant.

Nanocatalysis

• A catalyst is a substance which accelerates the rate of the chemical reaction or changes the product distribution without participating in it.

• It lowers the Activation Energy for efficient product formation.

[4]

Nano-catalysis

• Advantages

Introduction

• Size, shape & dimensionality are directly related with the properties of the material in areas of nanoparticles.

• Synthesis of molybdates is a growing interest over the past 20 years.

• Applications include: Industrial Catalysts, Optical Fibres &

Humidity Sensors

Hydro- & Solvothermal Method

• Hydrothermal synthesis can be defined as a method of

synthesis of single crystals that depends on the solubility of

minerals in hot water under high pressure.

• Solvothermal synthesis is a method of producing chemical

compounds. It is very similar to the hydrothermal route (where

the synthesis is conducted in a stainless steel autoclave), the

only difference being that the precursor solution is usually not

aqueous.

Experimental Procedure

• Raw Materials: Fe(NO3)3 ∙9H2O (98%) and (NH4)6Mo7O24∙7H2O (99%).

• Solvent used for Sample 1: Water• Solvent used for Sample 2: Ethylene Glycol + Methanol• Raw materials and solvents are mixed with magnetic stirring

until complete dissolution.• Components are transferred to teflon-lined reactor which is then

kept in stainless-steel autoclave.• Autoclave kept in oven for ‘x’ hours at temperature ‘T’.• XRD, UV-Visible and FESEM analysis carried out after

generation of final dried product.

Monoclinic and Orthorhombic system

Shape Evolution

Experimental Result

• It was observed that parameters like pH & concentration play a crucial role in synthesis of the product.

Hydro- & Solvothermal Method

• Uses : A large number of compounds belonging to practically all classes have been synthesized under hydrothermal conditions: elements, simple and complex oxides, tungstates, molybdates, carbonates, silicates etc.

Parallel Researches

• Bismuth molybdate is also catalyst developed on the same lines as iron molybdate

• Methylene blue photo decomposition.

• Nano structure and band gap manipulation .

FESEM images

FESEM Images

Iron Molybdate Catalyst

Optimization• With time

• With temperature

• Precursor variation

Applications

• Photo-Degradation of industrial dyes.

• Oxidation of Methanol to Formaldehyde

Application

• Here we have considered only one application i.e Degradation

of industrial dye using photo-catalyst.

• The data required to execute the application is analysed using

various parameters.

• Temperature & Time-Synthesis of catalyst.

• Degradation of dye- Collection frequency, Composition of

catalyst, etc.

Degradation of Dye

Degradation of Dye

Degradation of Dye

UV Data For Degradation

UV Data For Degradation

Optimization

• Initially , 0.1 g of the catalyst was used for a 10 ppm

methylene blue dye solution.

• But the degradation was too rapid.

• Quantity was reduced to 0.05 g.

• Recycle of catalyst: 3 times (RE)

Future Plans

• Successful dye degradation.

• Implementing on industrial scale.

• Optimization for maximum efficiency.

• Testing for other applications.

References

[1]. Yi Ding, Shu-Hong Yu, Chen Liu, and Zheng-An Zang: Chem. Eur. J. 2007, 13, 746 – 753

[2]. Dazheng Jhing-Catalytic Partial Oxidation of Methane over Fe2(MoO4)3 Catalysts ‘Master‘s Thesis in Materials and Nanotechnology Programme’ ,Chalmers University of Technology ,Göteborg, Sweden 2010

[3]. Liang Zhou, Minmin Yu, Jie Yang, Yunhua Wang & Chengzhong Yu:Nanosheet based Bi2MoxW(1-x)O6 solid solutions with adjustable band-gaps and enhanced visible light driven Photocatalytic activities,2010

References

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References

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[8] S.J. Yang, H.P. He, D.Q. Wu, D. Chen, X.L. Liang, Decolorization of methylene blue by heterogeneous Fenton reaction using Fe3−xTixO4 (0≤x≤0.78) at neutral pH values, Appl. Catal. B: Environ. 89 (2009) 527–535.

[9] W. Luo, L.H. Zhu, N. Wang, H.Q. Tang, M.J. Cao, Y.B. She, Efficientremoval of organic pollutants with magnetic nanoscaled BiFeO3 as a reusable heterogeneous Fenton-like catalyst, Environ. Sci. Technol. 44 (2010)-1786–1791.

References[10] H. Zollinger (Ed.), Color Chemistry. Synthesis, Properties and

Applications of Organic Dyes and Pigments, 2nd Revised Edition, VCH, 1991.

[11] D.M. Blake, Bibliography of work on the photocatalytic removal of hazardous compounds from water and air. NREL/TP-430-22197, National Renewable Energy Laboratory,Golden Co., 1997.

[12] N. Serpone, E. Pelizzetti (Eds.), Photocatalysis: Fundamentals and Applications, Wiley/Interscience, New York, 1989.

Thank you………