Sustainable Synthesis of Nanomaterials for Environmental Remediation

M. N. Nadagouda & Rajender S. Varma

Sustainable Technology Division National Risk Management Research Laboratory U. S. Environmental Protection Agency Cincinnati, Ohio 45268, USA E-mail: Varma.Rajender@epa.gov

Clean Chemical Synthesis Using Alternative Reaction Methods

Alternative Energy Sources Microwave Ultrasound Sunlight / UV Alternative Reaction Media/Solvent-free Supercritical Fluids Ionic Liquids Water Polyethylene glycol (PEG) Solvent-free

Energy Efficiency

Minimum Chemical Waste

Benign Solvents

Atom Economy

Green Organic Chemistry

Efficient Isolation Processes

Renewable Feedstock Safer Catalysts & Reagents

Sustainable Synthetic Method

Microwave Assisted Green Chemistry in Aqueous Medium

Schematic model diagram of nanoparticle self-assembly in different solvents in the presence of vitamin B2 Nadagouda & Varma: Green Chemistry, 8, 516, (2006)

TEM image of Ag and Pd nanoparticles synthesized using vitamin B2. Inset shows corresponding particle size distribution, electron diffraction and UV excitation Nadagouda & Varma: Green Chemistry, 8, 516, (2006)

Reaction of vitamin B2 with silver nitrate over the time in aqueous media. The inset figure shows control vitamin B2 (from left), reduced silver nanoparticles in water and NMP solvent media after 60 minutes Nadagouda & Varma: Green Chemistry, 8, 516, (2006)

Aligned Pd nanoplates synthesized using vitamin B1 in water Nadagouda, Polshettiwar & Varma: J. Mat. Chem., 19, 2026 (2009)

(a-b) Pd nanoplates and (c-d) Pd-catalyzed polypyrrole & polyaniline

Aligned platinum nanoflowers synthesized using vitamin B1 in aqueous media

Nadagouda, Polshettiwar & Varma: J. Mat. Chem., 19, 2026 (2009)

A Greener Synthesis of Core (Fe, Cu)-Shell (Au, Pt, Pd, and Ag) Nanocrystals Using Aqueous Vitamin C

Nadagouda & Varma: Crystal Growth and Design, 7, 2582-2587 (2007)

Photographic images of ascorbic acid reduced metallic nanostructures of (a) Ag, (b) Au, (c) Pd, (d) Pt, and (e) Cu.
Nadagouda & Varma: Crystal Growth and Design, 7, 2582 (2007)

TEM images of metallic (control) noble nanoparticles synthesized using ascorbic acid (vitamin C) (a) Ag, (b) Pd, (c) Au, and (d) Pt
Nadagouda & Varma: Crystal Growth and Design, 7, 2582 (2007)

TEM images of metallic (control) noble nanoparticles synthesized using ascorbic acid (vitamin C) (a) Cu and (b) Fe. Inset shows corresponding SAED pattern image.
Nadagouda & Varma: Crystal Growth and Design, 7, 2582 (2007)

TEM images of Core (Pd)-shell with (a) In, (b) Pt, (c) Cu, and (d) Au coreshell bimetallic nanostructures.
Nadagouda & Varma: Crystal Growth and Design, 7, 2582 (2007)

TEM images of core (Cu)-shell with (a) Pt, (b) Au, (c) Pd, and (d) selected area electron diffraction pattern of Cu-Pd coreshell nanoparticles.
Nadagouda & Varma: Crystal Growth and Design, 7, 2582 (2007)

TEM images of core (Fe)-shell with (a) Au, (b) SAED of Au, (c) Pd, and (d) Pt coreshell bimetallic nanostructures.
Nadagouda & Varma: Crystal Growth and Design, 7, 2582 (2007)

UVvisible spectra of core (Fe) shell with (a) Au, (b) Pd, and (c) Pt nanostructures synthesized using ascorbic acid.
Nadagouda & Varma: Crystal Growth and Design, 7, 2582 (2007)

Green synthesis of Ag and Pd nanoparticles at room temperature using coffee and tea extract

Ag nanoparticles

Pd nanoparticles

Nadagouda & Varma: Green Chemistry, 10, 859 (2008)

Ag Nanoparticles Generated from Various Brands of Tea & Coffee

Bigelow

Folgers

Lipton

Luzianne

Sanka

Starbucks

Nadagouda & Varma: Green Chemistry, 10, 859 (2008)

Pd Nanoparticles Generated from Various Brands of Tea & Coffee

Sanka

Bigelow

Luzianne

Starbucks

Folgers

Lipton

Nadagouda & Varma: Green Chemistry, 10, 859 (2008)

TEM images of Ag and Pd nanoparticles prepared in aqueous solution using pure catechin.

Nadagouda & Varma: Green Chemistry, 10, 859 (2008)

NRMRL/WSWRD-Aquatic Toxicity of Inorganic Nanoparticles-Silver

Assay: DmagnaAcute 48HrNoFood3-2007_05_09.a Toxicant: Coated Ag Nanoparticles Dose Response Curve
1.0
EC 50 = 11.31 +/- 1.04 EC 25 = 8.94 +/- 1.21 EC 10 = 7.07 +/- 1.33

0.8

Daphnia magna-48 hour exposure to commercially available nanoparticles Coated Ag particle LC50=11.311.04g/L Uncoated particle LC50=1.010.06g/L These LC50 values are similar to those for ionic silver

Mortality

0.6

0.4

0.2

Current studies emphasize:

0.0 0.05 0.5 5 50

Coated Ag Nanoparticles ppb

Assay: DmagnaAcute 48HrNoFood5-2007_07_16 Toxicant: UnCoated Ag Nanoparticles Dose Response Curve
1.0
EC 50 = 1.01 +/- 0.06 EC 25 = 0.94 +/- 0.06 EC 10 = 0.88 +/- 0.08

Characterization of the Ag nanoparticles (collaboration with LRPCD and Argonne Natl Lab) Identification of Ag species which cause toxic effects Standard laboratory protocols for the analyses of nanoparticles in controlled aquatic systems
(Collaboration with NERL researchers on genotoxic effects of inorganic nanoparticles)

0.8

Mortality

0.6

0.4

0.2

Toxicity of lab-synthesized Ag nanoparticles

(Collaboration with Sustainable Technology Division)

0.0 0.5 1 2 5 10 20

UnCoated Ag Nanoparticles ppb

Toxicity of Silver NP in Mouse Keratinocytes: MTS Assay Viability

(Silver with Tea Extract)
50ug/ml dose
160

(Uncoated Silver)
% Control

140 120 100 80 60 40 20 Control 3.8nm and 25.9nm 49.8nm 6nm and 77nm 9.2nm and 59.0nm 47.0nm

120 100
MTT Reduction ( % of control )

80 60 40 20 0 0 10 25 50

Ag15 Ag25 Ag80

0 1

100ug/ml Dose
180 160 140 Control 3.8nm and 25.9nm 49.8nm 6nm and 77nm 9.2nm and 59.0nm 47.0nm

Dose ( g/ml)
% Control

120 100 80 60 40 20 0

Collaboration with Dr. Saber Hussain Air Force Research Laboratory Dayton, Ohio

*MTS measures mitochondrial function

UV spectra of (a) Fe, (b) tea extract and (c) reaction product of Fe(NO3)3 and tea extract. Inset shows the photographic image of the reaction.
Nadagouda, Castle, Murdock, Hussain & Varma: Green Chemistry, 11, in press (2009)

Representative XRD pattern of iron nanoparticles synthesized using tea extract

A.

24h MTS results No significant decreases

in cell proliferation after a 24h exposure to NZVI (Figure A.)

B.

No significant reductions in cell proliferation after a 24h exposure to control particles (Figure B.)
Nadagouda, Castle, Murdock, Hussain & Varma: Green Chemistry, 11, in press (2009)

A.

48h MTS results

in cell proliferation after a 48h exposure to NZVI (Figure A.)
B.

No significant decreases

No significant reductions in cell proliferation after a 48h exposure to control particles (Figure B.)
Nadagouda, Castle, Murdock, Hussain & Varma: Green Chemistry, 11, in press (2009)

A.

24h LDH results

leakage in the T2 particles at 50l/ml concentration after a24h exposure to NZVI ,but this could be due to size or the increases conc. (Figure A.) No significant changes in LDH leakage after a 24h exposure to control particles (Figure B.)
Some slight increases in LDH

B.

Nadagouda, Castle, Murdock, Hussain & Varma: Green Chemistry, 11, in press (2009)

A.

48h LDH results

Increases in LDH leakage in the T6 and T7 particles at exposure to NZVI ,but this could be due to the large size of the particles or the increased concentration (Figure A.) No significant changes in LDH leakage after a 48h exposure to control particles (Figure B.)
Nadagouda, Castle, Murdock, Hussain & Varma: Green Chemistry, 11, in press (2009)

B.

Remediation using Nanomaterials Synthesized Under Green Conditions

New CRADA with VeruTEK Technologies, Inc.

VeruTEKs focus is to develop sustainable and green remediation, water and waste treatment processes VeruTEKs core uses food grade cosolvents and surfactants from citrus and plant extracts to simultaneously solubilize LNAPLs and DNAPLs and destroy with free radical chemistries (S-ISCOTM Process) CRADA involves advancing green synthesis manufacture of nanomaterials for application to remediation, water and waste treatment and biological and chemical agent treatment

Manufacture of Nanoscale Zerovalent Iron Particles with Ferric Chloride and Ferric Nitrate using Green Tea

nZVI Formed

nZVI Formed

Formation of Nanoscale Zero Valent Iron Green Tea Extract with Ferric Chloride

Formation of Nanoscale Zero Valent Iron Green Tea Extract with Ferric Nitrate

Notes: Green Tea extract made by heating a 20 g/L solution of Dry Chumnee Tea for 20 minutes at 90oC then filtering with paper filter. Green Tea extract added to 0.1 M Ferric solutions on a 1:2 (v/v) basis.

In Situ Formation of Nanoparticle Zerovalent Iron in Soils with Lemon Balm Extract and Fe(NO3)3

nZVI Formation in Soil Column

Control Column Fe(NO3)3 Feed Pump

Lemon Balm Extract Feed Pump

In Situ Generated Nanoparticle Zerovalent Iron in Effluent of Soil Column

Zerovalent Iron Nanoparticles Synthesized using Green Tea with 0.1 M Ferric Chloride and 0 g/L VeruSOLTM-3

100 nm

Zerovalent Iron Nanoparticles Synthesized using Green Tea with 0.1 M Fe(III)-EDTA and 5 g/L VeruSOLTM-3

100 nm

Green Synthesis of Au Nanostructures at Room Temperature using Biodegradable Plant Surfactants

Representative photographic images of Au Nanostructures

Nadagouda, Hoag, Collins & Varma: Crystal Growth & Design, 9, in press (2009)

XRD pattern of Au nanostructures obtained using various surfactants

Nadagouda, Hoag, Collins & Varma: Crystal Growth & Design, 9, in press (2009)

SEM Images of Au Nanostructures Synthesized Using Plant Surfactants

Nadagouda, Hoag, Collins & Varma: Crystal Growth & Design, 9, in press (2009)

TEM Images of Au Nanostructures Synthesized Using Plant Surfactants

Nadagouda, Hoag, Collins & Varma: Crystal Growth & Design, 9, in press (2009)

UV-Vis Spectra (Absorbance v Wavelength) of bromothymol blue in the absence of a catalyst Notes: 1) No Reaction of uncatalyzed hydrogen peroxide (2%) with bromothymol blue. Initial bromothymol blue concn. was 500 mg/L in the acidic pH range (<6).

J. Mater. Chem. in press (2009)

UV-Vis Spectra (Absorbance v Wavelength) of bromothymol blue over time for an initial solution containing 500 ppm bromothymol blue (pH 6), 2% H2O2, and 0.06 mM GT-nZVI.

J. Mater. Chem. in press (2009)

Bromothymol Blue Degradation with 2% HP, GT-nZVI and GTnZVI + 0.02M PdCl2 ln[BTB] vs Time
7

E1 - 0.33mM GT-nZVI + 0.02M PdCl2 E2 - 0.12mM GT-nZVI + 0.02M PdCl2

6.5

A3 - 0.12mM GT-nZVI A4 - 0.33mM GT-nZVI

6 ln[BTB]

5.5 y = -0.5182x + 5.9788 R = 0.9998 5 y = -0.2712x + 6.0927 R = 0.9988 y = -0.0449x + 6.2459 R = 0.9938 y = -0.1448x + 6.3966 R = 0.9925

4.5

4 0.0 2.0 4.0 6.0 8.0 10.0 Time (min) 12.0 14.0 16.0 18.0 20.0

J. Mater. Chem. in press (2009)

Decomposition of hydrogen peroxide using green tea synthesized nano-scale zero valent iron catalysts
6.0

5.0

Hydrogen Peroxide (%)

(a) (b)

4.0

3.0

2.0

(c) (d) (e)

0 5 10 15 20 25 30

1.0

0.0

Time (hour)

Decomposition of H2O2 catalyzed with green-tea synthesized zero valent iron (GTnZVI). (a) 5% peroxide solution control, (b) 5% peroxide treated with 0.26mM (as Fe) GT-nZVI, (c) 5% peroxide treated with 0.53mM (as Fe) GT-nZVI, (d) 5% peroxide treated with 1.33mM (as Fe) GT-nZVI, (e) 5% peroxide treated with 2.66mM (as Fe) GT-nZVI.

6.00

5.00

(a)

4.00

3.00

(b) (c) (d) (e)

2.00

1.00

0.00 0 5 10 15 20

(f)
25 30

Concentration of HP (%) vs Time with GT-nZVI at 1.33 mM as Fe (a) Control 1 5% H2O2 (no GT-nZVI) (b) 10 g/L VeruSOL-3, (c) 5 g/L VeruSOL-3, (d) 2 g/L VeruSOL-3, (e) 1 g/L VeruSOL-3, and (f) Control 2 5% peroxide with GT-nZVI at 1.33 mM as Fe (no VeruSOL-3)

Use of Green Methods and Applications to Destroy Toxic Organics and Inorganic Compounds in the Environment
Problem: There are over 500,000 contaminated sites across the United States. Current cleanup technology requires excavation and may even generate toxic by-products. Remediating or destroying various organic and inorganic environmental toxins in the subsurface and in water at or around these sites is a complex challenge. Description: EPAs world-renown scientists in Cincinnati are trained and educated to develop innovative cleanup strategies that restore contaminated sites to productive use, reduce associated costs, and promote environmental stewardship. Through a Cooperative Research and Development Agreement (CRADA) between EPAs National Risk Management Research Laboratory (NRMRL) and the private company VeruTEK in Bloomfield, Connecticut, EPA green-synthesis technology is being used to further improve VeruTEKs green remediation and treatment technologies used in environmental cleanup. This project combines EPAs expertise in green synthesis of nanoparticles with VeruTEKs expertise with surfactant enhanced in situ chemical oxidation and reduction methods. As a result, new environmentally-friendly applications and methods have been developed. The anticipated benefits from the new green-synthesis methods over conventionally used processes are: only natural materials are used; no hazardous waste is produced; reduced processing is required; materials are more stable, easily stored, and transported; and, materials can be more easily produced around the world. Impact: The Cooperative Research and Development Agreement between the EPA and VeruTEK will provide: -Production of nanoiron using various plant extracts and iron sources -Catalytic activation of hydrogen peroxide -Destruction of contaminated soils

IP Position: VeruTEK filed a provisional U.S. Patent with co-inventors from the EPA in 2008. The project covers the method of synthesis of metal nanoparticles using plant extracts and their application as catalysts for oxidation reactions, and also as reductants to treat organic and inorganic chemicals.
Technology Status: The CRADA reinforces the collaboration between the EPA and VeruTEK and will greatly enhance how nanoscale technologies are applied for site remediation. It is anticipated that using the new greener synthetic pathways, the cost of nanoscale iron and other nanoscale metals will be reduced, along with the elimination of toxic byproducts often generated in the conventional process. While the green-synthesis process is new, it is expected that it will be used in the field in 2009.

Dr. Rajender S. Varma, National Risk Management Research Laboratory; Phone 513-487-2701; varma.rajender@epa.gov Dr. George Hoag, Senior Vice President, Director of Research & Development; Phone 860-617-5106; ghoag@verutek.com
The EPAs National Risk Management Research Laboratory and its partners are developing new environmental technologies that provide unique opportunities for green job creation and enhanced protection of human health and the environment.

MW Heating Mechanism
~ ++++++++ + ________ ~ No constraint Continuous electric field ~ ~ + ~ ~

Alternating electric field with high frequency

Two mechanisms: Dipolar rotation / polarization Ionic Conduction mechanism

Microwave Dielectric Heating Mechanisms

Dipolar Polarization Mechanism Conduction Mechanism

Dipolar molecules try to align to an oscillating field by rotation

Ions in solution will move by the applied electric field

Dextron Templated Microwave-Assisted Synthesis of Porous Titanium Dioxide

The synthesis of carbon coated titania as well as spongy kind of titania by microwave combustion method The process is very simple and eco-friendly protocol which utilizes renewable polymer dextrose to create spongy kind of materials.

Nadagouda & Varma: J. Smart Materials and Structures, 15, 1260 (2006)

Objective
An alternative route to the preparation and formation of porous titania powders and carbon coated titania using microwave irradiation Dextrose was used as a capping agent or a template for the following reasons:
High water solubility when compared to other sugar templates or capping agents Combustible material at low temperature Inexpensive material

Nadagouda & Varma: J. Smart Materials and Structures, 15, 1260 (2006)

SEM images of TiO2 synthesized using (a-c) 1:1, 1:3 and 1:5 (titania:dextrose) by conventional heating furnace, (d) EDX spectra

SEM images of TiO2 synthesized using (a-c) 1:1, 1:3 and 1:5 (titania:dextrose) by MW initiated combustion, (d) EDX spectra

(a-c) X-ray mapping images of 1:1, 1:3 and 1:5 (titania: dextrose molar ratio) carbon coated titania synthesized using MW combustion synthesis. Green region shows titania and red region shows carbon Nadagouda & Varma: J. Smart Materials and Structures, 15, 1260 (2006)

SEM images of ZrO2 synthesized using: (a) MW-initiated followed by conventional heat treatment at 850 0C for 1 h and (b) Only conventional heating furnace at 850 0C for 1 h Nadagouda & Varma: J. Smart Materials and Structures, 15, 1260 (2006)

Microwave-Assisted Reactions Using Sugar Solutions

Noble salt (0.1 M) Sugar MW 30-40 sec Noble Nanostructures

Examples : Sucrose, Maltose, glucose etc.

Nadagouda & Varma: International Microwave Power Institute Symposium Proceedings, Boston, pp 217-219 (2006).

Gold Nanostructures

TEM image of gold nanostructures obtained using high concentration of sugars under microwave irradiation condition (a) Glucose, (b) Maltose and (c) Sucrose Nadagouda & Varma: Crystal Growth and Design, 7, 686 (2007)

TEM image of (a-d) gold nanostructures obtained using low concentration of sugar solution under microwave irradiation Nadagouda & Varma: Crystal Growth and Design, 7, 686 (2007)

Comparison of Microwave and Oil Bath Heating Methods

MW Method
Fast reaction rate (30-40 sec) Uniform size and shape Less energy consumption

Oil Bath Method

Slow reaction rate (minimum 2 h) Particle size growth More energy consumption

Bulk Synthesis of Silver Nanorods in Poly(ethylene glycol) using Microwave Irradiation

Nadagouda & Varma: Crystal Growth and Design, 8, 291-295 (2008)

Schematic of experimental mechanisms that generate: Silver (a) Nanoparticles, (b) Nanorods, and (c) Nucleated Nanorods and Nanoparticles.
Nadagouda & Varma: Crystal Growth and Design, 8, 291-295 (2008)

SEM image of Ag nanoparticles prepared via MW method Using (a) PG-6 (6 mL PEG + 2 mL AgNO3), and (b) PG-1 (1 mL PEG + 7 mL AgNO3).
Nadagouda & Varma: Crystal Growth and Design, 8, 291-295 (2008)

(A)

(B)

(A) UV spectra of (a) PG-8, (b) PG-4 and (c) PG-1, and (B) SEM image of mixture of Ag nanorods and particles prepared from PG-4 for 2 minutes under MW irradiation.
Nadagouda & Varma: Crystal Growth and Design, 8, 291-295 (2008)

SEM image of Ag nanorods prepared via MW irradiation for one hour using PG-9 composition (4 mL of PEG + 3 mL of AgNO3 + 1 mL of HAuCl4).
Nadagouda & Varma: Crystal Growth and Design, 8, 291-295 (2008)

SEM image of Ag-Pd composite (PG-10, 4 mL of PEG with 3 mL of AgNO3 and 1 mL of PdCl2) prepared using MW irradiation at 100 0C for 1h
Nadagouda & Varma: Crystal Growth and Design, 8, 291-295 (2008)

Bulk Synthesis of Silver Nanorods in Poly(ethylene glycol) using Microwave Irradiation

SEM images of silver nanorods synthesized via MW irradiation using (a) 4/4, (b) 5/3 , (c) 3/5 and (d) 2/6 PEG:AgNO3 volume (mL) ratio

Nadagouda & Varma: Crystal Growth and Design, 8, 291-295 (2008)

(a) (b)

Precipitated silver nanorods under MW irradiation for 2 min using PEG and Control reaction of the using oil bath at 100 0C for 1 hr. same reaction composition

Nadagouda & Varma: Crystal Growth and Design, 8, 291-295 (2008)

TEM images of Ag nanorods from (a) 4 mL PEG with 4 mL of aqueous AgNO3 under MW conditions and (b) its SAED pattern obtained from a bundle of silver nanorods randomly deposited on the TEM grid.

TEM image of Pt nanocubes decorated on Ag nanorods by metal displacement reaction using PG-11 composition (PG-4 Nanorods + 4 mL of Na2PtCl6 XH2O).
Nadagouda & Varma: Crystal Growth and Design, 8, 291-295 (2008)

SEM images of Fe nanorods obtained from PG-12 composition (4 mL of PEG + 4 mL Fe(NO3)3 XH2O) under MW conditions; inset shows SAED pattern.

Noble Metal Polymer Nanocomposites

Polymer nanocomposites are the class reinforced polymers with low quantities nanometric-sized metal nanoparticles. Applications: - fire resistance and strength - coating materials in automobile - improved barrier properties - civil and electrical engineering - Packaging etc. of of

SEM image of polyaniline synthesized using (a-b, low and high magnification) 3M, (c) 1M and (d) 1M acetic acid (TEM image) Nadagouda & Varma: Green Chemistry, 9, 632-637, (2007)

TEM images of different shape noble metal-polyaniline nanocomposites obtained from polyaniline nanofibers (synthesized using 1M acetic acid): (a) Ag, (b) Pd, (c) Au and (d) Pt Nanocomposites. (b) Inset shows corresponding electron diffraction patterns Nadagouda & Varma: Green Chemistry, 9, 632-637, (2007)

Polypyrrole Nanocomposites
Pd Pt

Au

Ag

Nadagouda & Varma: Green Chemistry, 9, 632-637, (2007)

Preparation of Novel Metallic, Bimetallic and Carbon Nanotube Cross-Linked Poly(vinyl alcohol) Nanocomposites under Microwave Irradiation

Poly (vinyl alcohol)-reduced metals: (ab) Ag after 1 and 5 h reaction, (cd) Pd and Fe after 1 h reaction time at 100 0C (maximum pressure ~280 Psi)

Nadagouda & Varma: Macromol. Rapid Commun., 28, 842 (2007)

Novel Metallic, Bimetallic Cross-Linked Poly(vinyl alcohol) Nanocomposites under Microwave Irradiation Conditions

Cross-linked poly (vinyl alcohol)- with various metallic and bimetallic systems: (a) Pt, (b) Pt-In, (c) Ag-Pt, (d) Cu, (e) Pt-Fe, (f) Pt with higher concentration ratio, (g) Cu-Pd, (h) In, (i) Pt-Pd and (j) Pd-Fe. Nadagouda & Varma: Macromol. Rapid Commun., 28, 465 (2007)

SEM image of bimetallic (a) Pt-In, (b) Pt-Fe, and (d) Pd-Fe in 3 wt.-% PVA matrix. (c) X-ray-mapping image of Pt-Pd in 3 wt.-% PVA matrix. Inset in (a) shows X-ray mapping of In-Pt (green: In, red: Pt). Nadagouda & Varma: Macromol. Rapid Commun., 28, 465472 (2007)

SEM images of (a) pure SWNT carbon nanotubes, (b-c) 25 mg SWNT crosslinked PVA and (d) 50 mg SWNT cross-linked PVA nanocomposites. Nadagouda & Varma: Macromol. Rapid Commun., 28, 842847 (2007)

SEM images of (a-b) 75 mg SWNT cross-linked PVA nanocomposites Nadagouda & Varma: Macromol. Rapid Commun., 28, 842847 (2007)

PVA coating

TEM images of (a) pure SWNT carbon nanotubes obtained from Bucky Inc., USA, (b) 25 (c) 50, (d) 75 mg SWNT cross-linked PVA nanocomposites. Nadagouda & Varma: Macromol. Rapid Commun., 28, 842847 (2007)

Synthesis of Thermally Stable Carboxymethyl Cellulose/Metal Biodegradable Nanocomposite Films for Potential Biological Applications

(a)

(b)

(c)

(d)

Carboxymethyl cellulose (a) Cu, (b) In, (c) Fe and (d) Ag

nanocomposites

with

Nadagouda & Varma: Biomacromolecules, 8, 2762-2767 (2007)

Carboxymethyl cellulose (CMC) reduced Au, Pt and Pd (from left to right) synthesized using MW at 100 0C for 5 minutes Nadagouda & Varma: Biomacromolecules, 8, 2762-2767 (2007)

UV spectra of CMC-reduced (a) Au, (b) Pt, and (c) Pd synthesized using MW irradiation for 5 min at 100 C.
Nadagouda & Varma: Biomacromolecules, 8, 2762-2767 (2007)

TEM images of CMC-reduced (a) Au and (b) Pd, and SAED pattern of (c) Au and (d) Pd nanostructures.
Nadagouda & Varma: Biomacromolecules, 8, 2762-2767 (2007)

SEM image of CMC nanocomposite films with (a) Cu, (b) In, (c) Fe and (d) Ag. Red spotted area corresponds to metal and green area represents carbon. Inset corresponds to their respective energy dispersive X-ray analysis (EDX).

Noble Metal Decoration and Alignment of Carbon Nanotubes in Carboxymethyl Cellulose

X-ray mapping image of Ag metal decorated CMC SWNT at room temperature.

Nadagouda & Varma: Macromol. Rapid Commun., 28, 155-159 (2007)

Dispersion of C-60 nanotubes in carboxymethyl cellulose (CMC) and decoration with noble metals under MW irradiation conditions

Control : Pure CNT nanotubes Nadagouda & Varma: Macromol. Rapid Commun., 28, 155-159 (2007)

Dispersion of C-60 nanotubes in carboxymethyl cellulose (CMC) and decoration with noble metals under MW irradiation conditions

C-60 dispersion in CMC and coating of platinum nanoparticles on the surface Nadagouda & Varma: Macromol. Rapid Commun., 28, 155-159 (2007)

Dispersion of C-60 nanotubes in carboxymethyl cellulose (CMC) and decoration with noble metals under MW irradiation conditions

C-60 dispersion in CMC and coating of gold nanoparticles on the surface Nadagouda & Varma: Macromol. Rapid Commun., 28, 155-159 (2007)

Dispersion of C-60 nanotubes in carboxymethyl cellulose (CMC) and decoration with noble metals under MW irradiation conditions

C-60 dispersion in CMC and coating of palladium nanoparticles on the surface Nadagouda & Varma: Macromol. Rapid Commun., 28, 155-159 (2007)

Synthesis of Single-Crystal Micro-Pine Structured Nano-Ferrites and Their Application in Catalysis

Polshettiwar, Nadagouda & Varma, Chem. Commun. 2008, 6318

3D Nano-Metal Oxides MW Synthesis in Water from Simple Salts

Fe2O3

Mn2O3

CoO

Cr2O3

Polshettiwar, Baruwati & Varma, ACS Nano, 3, 728 (2009)

Synthesis of Monodispersed Ferrite Nanoparticles at Water-Organic Interface Under Conventional/MW Hydrothermal Conditions
Monodispersed MFe2O4 (M=Fe, Mn, Co, Ni) nanoparticles have been synthesized via a water organic interface under both hydrothermal and MW conditions starting with readily available and inexpensive metal nitrate and halide precursors. The single phase particles are obtained at a temperature as low as 150 oC under MW conditions. The as-synthesized particles are dispersible in nonpolar organic solvents.

NiFe2O4

CoFe2O4

-Fe2O3

Baruwati, Nadagouda & Varma, J. Phys. Chem. C, 112, 18399 (2008)

Surface functionalization renders the particles dispersible in water

TEM of the particles dispersed in water

NiFe2O4

CoFe2O4
Photographic image of the particles in water and hexane

Baruwati, Nadagouda & Varma, J. Phys. Chem. C, 112, 18399 (2008)

Nano-Catalyst, What is it?

We envisioned a catalyst system,

which can bridge the Homogenous and Heterogeneous system

Also Keeping in mind; 1. It should be cheaper 2. Easily accessible (sustainable) 3. No need of catalyst filtration

Synthesis of Nano-Catalysts
NH2 H 2N H 2N H 2N NH2 NH2 NH2 NH2 NH2 H 2N NH2 NH2

HO
Fe3O4

Sonication

H 2N H 2N H 2N H2N

HO
Magnetic Nanoparticles

NH2 RT, H2O

Fe3O4

O O

NH2

NH2

= Metal (M)

M M H N H 2N 2
H 2N M HN 2 NH2

M
NH2 NH2

M HN 2

H 2N

Fe3O4

NH2 NH2 M NH2

NH2 H2N NH 2 H2N NH2 M NH2 M

V. Polshettiwar, M. N. Nadaguda & R. S. Varma, Chem. Commun. 2008, 6318.

Magnetically Recoverable Pd Nano-Catalyst for Oxidation

Polshettiwar & Varma, Org. Biomol. Chem., 7, 37 (2009)

Magnetically Recoverable Ruthenium Hydroxide Nano-Catalyst

Polshettiwar & Varma, Chem. Eur. J. 15, 1582 (2009)

No Organic SolventEven in the Work-Up Step

Reaction in Pure Aqueous Medium

Synthesis of Ni-Nano-Catalysts
NH2 H 2N H2N H 2N NH2 NH2 NH2 NH2 NH2 H 2N NH2 NH2

H 2N H 2N H 2N H 2N

Fe3O4

NH2

NH2

NiCl2, NH2NH2
Ni Ni H N 2
H2N Ni H2N H2N NH2

Ni
NH2 NH2 Ni NH2 NH2 Ni NH2 NH2

Ni

H 2N H2N H 2N H 2N Ni

Fe3O4

Ni

Single-phase Fe3O4 nanoparticles Size range = 10-13 nm Nickel concentration = 8.3 % (ICP-AES)

NH2

NH2NH2

Ni

Ni

Ni

Magnetically Recoverable Ni Nano-Catalyst for Reduction

Polshettiwar, Baruwati & Varma, Green Chem., 11, 127 (2009)

Glutathione as a Reducing and Capping agent for the Synthesis of Metal Nanoparticles
HO HN
HS

O HN O H 2N OH O

Glutathione reduced

Choice of Glutathione because

An ubiquitous tripeptide and antioxidant present in human and plant cells Presence of a highly reactive thiol group that can be used to reduce the metal salts Completely benign nature

Baruwati, Polshettiwar, Varma, Green Chem. 11, p 926 (2009)

Baruwati, Polshettiwar, Varma, Green Chem. 11, p 926 (2009)

Optimized condition

Metal nanoparticles in less than a minute under MW conditions

50 W power level 45-60 seconds exposure time 1:0.15 silver nitrate to glutathione mole ratio

Silver Nanoparticles

50 Watt, 60 seconds with silver nitrate to glutathione mole ratio 1.0:0.15

75 Watt, 60 seconds with mole ratio 1.0:0.15

100 Watt, 60 seconds with mole ratio 1.0:0.15

Silver trees formed on the TEM grid when silver nitrate is not fully reduced Formation of dendritic structures are due to the carbon and copper in the TEM grid

Silver trees: Dendritic nanostructures

Gold, Platinum and Palladium Nanoparticles

Gold

Platinum

Palladium

X-Ray Mapping Images of Various Nanostructures Obtained Using Sorghum Bran

Pd Nanostructures (green)

Ag Nanostructures from Sorghum

Ag Nanoparticles from Sorghum Bran

Au Nanowires from Sorghum Bran

XRD Pattern of Au Nanostructures from Sorghum Bran

XRD Pattern of Ag Nanostructures from Sorghum Bran

Baruwati, Varma, ChemSusChem, 2, in press (2009)

Gold Nanoparticles Using Wine

Red Wine

White Wine

Baruwati, Varma, ChemSusChem, 2, in press (2009)

Gold Nanoparticles Using Red Grape Pomace

MW 50 W for 1 Minute

Room Temp. for 3 hours

Baruwati, Varma, ChemSusChem, 2, in press (2009)

Acknowledgements
Green Chemistry and Engineering, Sustainable Technology Division, NRMRL, U.S. EPA, Cincinnati, Ohio, USA CRADA with VeruTEK Technologies, Inc. CRADA with CEM Corporation.
Dr. George Hoag (VeruTEK, CT) Dr. Saber Hussain (WPAFB, Dayton, OH) Dr. Babita Baruwati Dr. Dalip Kumar Dr. Harshadas Meshram Dr. Vasu Namboodiri Dr. Yuhong Ju Dr. Vivek Polshettiwar Dr. Mallikarjuna Nadagouda Dr. Sudhir Kumar Dr. Unnikrishnan R. Pillai Dr. Yong-Jin Kim

Dr. Raj Varma with Mrs. Patil, The President of India & Dr. Shekhawat in Rashtrapati Bhawan, Delhi, Feb. 2008

Dr. Varma Presenting Green Chemical Approaches to Mrs. Patil, the President of India in Rashtrapati Bhawan, Delhi, Feb. 2008

Dr. Varma Presenting Green Nano Concepts to Mrs. Patil, the President of India in Rashtrapati Bhawan, Delhi, Feb. 2008

Astra Zeneca Research Foundation Kavitha Printers, Bangalore, India, 2002 azrefi@astrazeneca.com

Rajender S. Varma,
Microwave Technology -Chemical Synthesis Applications 2003 John Wiley & Sons, Inc