Nanocomposites and its Applications

By Sudheer Kumar Yadav

Nanoparticle
The particle having at least one dimension sized between 1 -100 nanometers.

Nanocomposite
A multiphase solid material where one of the phases must be in nano range.

(a) FESEM (b) HRTEM and TEM (inset) images of the ZnO/Cu nanocomposite.

C .Yang et al. Langmuir 2012, 28, 45804585

Importance of the Nanocomposites

1)Multifunctional Properties
Fe3O4@nSiO2@mSiO2@Au core-shell-nanocomposite

Ordered mesoporous
High magnetization NIR absorption (photo thermal therapy)

TEM image of the Fe3O4@nSiO2@mSiO2@Au nanocomposite Z. Xu et al. J. Phys. Chem. C 2010, 114, 1634316350

2) For enhancing the physical Properties of the Nanoparticles

Mechanical Electrical Thermal Optical Electrochemical Catalytic
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Different Types of Nanocomposites

Ceramic Matrix Nanocomposites

Nanocomposite s

Polymer Matrix Nanocomposites

Metal Matrix Nanocomposites

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Ceramic-matrix nanocomposites
Main part of volume is occupied by a ceramic. SiC, Al2O3, B4C, ZrO2, etc are the examples for the ceramics. Dispersion of metal, metal oxide nanoparticles etc. onto the matrix. Improved mechanical properties, hardness and fracture toughness.

SEM image of Al2O3/SiC nanocomposite P H C. Camargo et al. Materials Research, Vol. 12, No. 1, 1-39, 2009

Metal-matrix nanocomposites
Consists of a ductile metal or alloy matrix. Dispersion of metallic or ceramic nanoparticles onto the matrix. Materials with high strength in shear/compression processes and high service temperature capabilities can be produced. Potential applications in aerospace, automotive and development of structural materials.
1m 500 nm

7 TEM image of Fe/MgO nanocomposite.

Y. H. Choa et al. Journal of Magnetism and Magnetic Materials 266 (2003) 2027

Polymer-matrix nanocomposites
Incorporation of metal and ceramics into the polymer matrix. Improved mechanical properties, increased heat and impact resistance can be achieved by filling different organic and inorganic nanoscale materials. Also exhibits magnetic, electronic, optical or catalytic properties.

TEM images of SiO2/polystyrene nanocomposite particles

H. Zou Et al. Chem. Rev. 2008, 108, 38933957

Nanocomposites Different Synthetic Methods

Homogenous precipitation Chemical reduction Hydrothermal synthesis Sol gel Thermal decomposition
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Homogenous precipitation
Cu (1.5 g) Ag2CO3 (0.15 g) NH4HCO3 (14 ml) Stirring at RT Deep blue complex i) Addition of 100 ml H2O ii) Heated Turbid solution Centrifuged Precipitate Dried in vacuum oven at 75oC for 10 h Cu2(OH)2CO3 / Ag2CO3 Calcined at400oC (1.5h)
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. S. Wang et al. Materials Chemistry and Physics 108 (2008) 165169

Conc. NH3 (4.5 ml)

Mechanism for the formation of Ag / CuO nanocomposite

TEM image of Ag / CuO nanocomposite

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. S. Wang et al. Materials Chemistry and Physics 108 (2008) 165169

Chemical reduction
MWCNT (1mg) 1 wt. % HAuCl4 solution (1mL) i) Sonicated for 5min ii) Addition of 100 ml H2O

iii)Heated to boiling

iv)Sodium citrate (1.5mL)

MWCNT-Au nanocomposite
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F. J. Xiao Mater. Chem., 2012, 22, 7819-7830

hematic representation of Au Coating on MWC

Sonication

MWCNT

Dispersed MWCNT

1oo nm

Au nanoparticles coated MWCNT

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F. J. Xiao Mater. Chem., 2012, 22, 7819-7830

Hydrothermal Synthesis
ZnCl2 TiCl4 EtOH (10 ml) H2O (10 ml)

Stirring at RT Molar ratio Zn : Ti 1:1 1:2 2:1 Addition of 10 ml Urea (0.6 M)

Transparent Solution i) Heated in autoclave at 180oC for 16 h ii) Centrifuged, washed and calcined at 450oC for 2h ZnO-TiO2 nanocomposite
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D. Chen et al. J. Phys. Chem. C 2008, 112, 117-122

Sol gel
TEOS H2O C3H8O3 HNO3 HAc Pb (Ac)2

Molar Ratio TEOS:H2O:C3H8O3:HNO3:HAc:Pb(Ac)2

Stirred at RT

1:20:1:0.02:1:0.04
Sol Dried at RT gelation Gel

Calcined at 550oC for 2h

PbO / SiO2 nanocomposite

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T. Zhou et al. Anal. Chem. 2010, 82, 17051711

Applications Of Nanocomposites
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Biosensors

Energy conversion and storage

Catalysis

Nanocomposites

Gas sensors

Optical devices

Photocatalysis

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Biosensors
Pt-CNT nanocomposites --> glucose biosensors. Glucose biosensors are based on GOD enzymatic reaction. GOD identifies glucose target molecule quickly and accurately .

Electrochemical determination of liberated H 2O2 using Pt-CNT-GOD Electrode. Detection limit is 0.oo5 mM of glucose concentration.
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Reusable Z. Wen et al. J. Phys. Chem. C 2009, 113, 1348213487

Biosensors

Typical current-time response curves of the Pt-CNTs-GOD electrode.

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Z. Wen et al. J. Phys. Chem. C 2009, 113, 1348213487

Optical Devices
ZnO-CdS nanocomposite

Absorption spectra and optical band gap of ZnOCdS nanocomposite.

Light emission from UV to visible (upto green) by changing the composition of nanocomposite.
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L. Irimpan et al. Sci. Adv. Mater. 2010, 2, 117137,

Optical Devices

Nonlinear absorption coefficient and nonlinear refractive index increase for the composite. Significant optical limiting performance.

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Laura L. Beecroft Chem. Mater. 1997, 9, 1302-1317

Catalysis
CoAl2O4/-Al2O3 nanocomposite High surface area and have surface hydroxyl group Active catalyst for the decomposition of H2O2 Oxidize a wide range of organic and inorganic pollutants

Metal oxide catalyzed Decomposition of H2O2

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A. Dandapat et al. ACS Appl. Mater. Interfaces 2012, 4, 228234

Photos of (a) CoAl2O4/-Al2O3 composite nanopowder and (b) 5 wt.% dispersion of (Co : Al=1:5)/500 C in glycerol; c) UVvisible absorption spectrum of above (b)

Self cleaning pigment Reusable catalyst Stable

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A. Dandapat et al. ACS Appl. Mater. Interfaces 2012, 4, 228234

Photocatalytic Activity
Au nanoparticle functionalized TiO2 nanotube array nanocomposite

Degradation of organic dye pollutant (e.g. Methyl orange) under UV light. Au doped TiO2 act as efficient electron trap for photogenerated electrons. Facilitates efficient separation of photogenerated e- & h+ . Holes react with H2O to generate OH radical and other active species.

Mechanism Dye + OH Dye + H2O (decolorization of methyl orange) Dye + Dye DyeDye (recombination of carbon-centered radicals) Dye + OH H2O + CO2 (mineralization) F. J. Xiao Mater. Chem., 2012, 22, 7819-7830
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Mechanism for the liquidphase photocatalytic degradation of organic dyes

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F. J. Xiao Mater. Chem., 2012, 22, 7819-7830

Gas sensors
PbO/SiO2 nanocomposite Sulfide sensor based on room temperature phosphorescence (RTP). Phosphorescence intensity of the composite is quenched by sulfide. pH 11 is found to be good working condition. Detection limit for sensor is estimated to be 0.138 M. Color of sensor and its phosphorescence intensity change with continuous addition of sulfide and could be observed by naked eye.

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T. Zhou et al. Anal. Chem. 2010, 82, 17051711

0 M

50 M

200 M

500 M

(1a) RTP photograph of PbO/SiO2 composite at different concentrations of Na 2S. (1b)Photograph of PbO/SiO2 composite at different concentrations of Na 2S. (2a) RTP photograph of PbO/ SiO2 composite before and after interaction with H 27 2S. (2b) Photograph of PbO/SiO2 composite before and after interaction with H 2S.

T. Zhou et al. Anal. Chem. 2010, 82, 17051711

Proposed Phosphorescence Quenched and Recovered Mechanism for the Sulfide Sensor Based on PbO/SiO2 Composite

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T. Zhou et al. Anal. Chem. 2010, 82, 17051711

Conclusions
Multifunctional properties can be achieved. Physical properties can be enhanced compared to the pure components. Can be synthesized by various chemical methods e.g. sol gel, homogeneous precipitation , chemical reduction, hydrothermal synthesis etc. Potential applications in catalysis, photocatalysis; used as bio sensors, optical devices, gas sensors etc.

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