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Green Tech CT - 09-Varma-Pm - Red
Green Tech CT - 09-Varma-Pm - Red
Energy Efficiency
Benign Solvents
Atom Economy
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 Greener Synthesis of Core (Fe, Cu)-Shell (Au, Pt, Pd, and Ag) Nanocrystals Using Aqueous Vitamin C
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
Bigelow
Folgers
Lipton
Luzianne
Sanka
Starbucks
Sanka
Bigelow
Luzianne
Starbucks
Folgers
Lipton
TEM images of Ag and Pd nanoparticles prepared in aqueous solution using pure catechin.
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
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
0.0 0.5 1 2 5 10 20
(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
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
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)
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.
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.
B.
Nadagouda, Castle, Murdock, Hussain & Varma: Green Chemistry, 11, in press (2009)
A.
B.
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
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
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).
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.
Bromothymol Blue Degradation with 2% HP, GT-nZVI and GTnZVI + 0.02M PdCl2 ln[BTB] vs Time
7
6.5
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
Decomposition of hydrogen peroxide using green tea synthesized nano-scale zero valent iron catalysts
6.0
5.0
(a) (b)
4.0
3.0
2.0
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
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 ~ ~ + ~ ~
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)
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)
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)
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
(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
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.
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
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)
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)
nanocomposites
with
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).
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)
Fe2O3
Mn2O3
CoO
Cr2O3
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
NiFe2O4
CoFe2O4
Photographic image of the particles in water and hexane
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
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
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
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
Optimized condition
Silver Nanoparticles
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
Gold
Platinum
Palladium
Pd Nanostructures (green)
Red Wine
White Wine
MW 50 W for 1 Minute
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