ADVANCES IN NANOTECHNOLOGY & GREEN CHEMISTRYSanjeev K. Manohar

DEPARTMENT OF CHEMICAL ENGINEERING

This work was supported by the University of Massachusetts Lowell Nanomanufacturing Center of Excellence (NCOE), NSF-funded Center for High-rate Nanomanufacturing (CHN, NSFaward #0425826), The Massachusetts Center for Biomanufacturing and the Green Technology Laboratory.

Sensors Using Ink-Jet Printed Graphene

Developed a new green chemistry method tosynthesize graphene, including the construction of aflexible, chemical warfare agent detector.

Research Outputs:

1. Publication: Angewandte Chemie 49 2154 (2010).2. Patent: Provisional application filed (2010).3. Collaboration: Prof. Rodney Ruoff, Univ Texas Austin

TX-100

a b

c

d

Vitamin-C

reduction dispersion

-20

-10

0

10

20

30

NO

2

Cl 2

CH

3O

H

C2H

5O

H

C6H

5C

H3

C6H

14

NH

3

CH

2C

l 2

R

/R%

Research in Frontier MaterialsOur research is in the synthesis andcharacterization of materials exhibiting novel andunexpected properties with application innanotechnology, biotechnology, and sustainableengineering and chemistry. Lines of inquiry include:

1. Sensors for detecting chemical warfare agentsusing soft nanotechnology (carbon nanotubes,graphene and conducting polymers).

2. Synthesis and characterization of nanostructuredmaterials using green chemistry approaches.

3. Sensors for detecting endotoxins and biologicalthreat agents.

4. Conversion of waste cellulose to biodegradableplastics.

www.frontiermaterials.net

Conducting Polymer Nanoclips

New method to synthesize conducting polymers in theform of nanosized clips using a very simple, water-based oxidative approach.

Research Outputs:

1. Publication: Journal of the American ChemicalSociety 132, 13158 (2010).

2. Collaboration: Prof. Xinyu Zhang, Auburn University.

Green Synthesis & Lead-Free Soldering

Developed a new green chemistry method tosynthesize a nanostructured conducting polymersurface finish for lead free electronics.

Research Outputs:

1. Publication: Green Chemistry 12 585 (2010).2. Collaboration: Benchmark Electronics, TURI.

3. Award: TURI, and citations form MA State House

Green Synthesis of Synthetic Metals

Developed a new green chemistry method tosynthesize nanostructured conducting polymersusing hydrogen peroxide (no toxic byproducts).

Research Output:1. Publication: Journal of the American Chemical

Society 131 12528 (2009).

NH2 + 5x H2O2 + 2x HCl4x

1M HCl/satd. NaCl

HN

HN

x

HN

HN

+Cl Cl+

- 10x H2O

- -

DNH2 + 5x H2O2 + 2x HCl4x

1M HCl/satd. NaCl

HN

HN

x

HN

HN

+Cl Cl+

- 10x H2O

- -

DNH2 + 5x H2O2 + 2x HCl4x

1M HCl/satd. NaCl

HN

HN

x

HN

HN

+Cl Cl+

- 10x H2O

- -

DNH2 + 5x H2O2 + 2x HCl4x

1M HCl/satd. NaCl

HN

HN

x

HN

HN

+Cl Cl+

- 10x H2O

- -

D

2 µm

Polyaniline: A Warfare Agent Sensor

Described a new method to detect highly oxidizingand toxic vapors like nitrogen dioxide using aconducting polymer film (chemiresistor).

Research Output:1. Publication: Sensors and Actuators B 143 454

(2009).

Nanofiber Growth Puzzle Solved

Uncovered evidence for a new mechanism fornanofiber formation in conducting polymers. Solves a10 year old puzzle in polymer chemistry.

Research Output:1. Publication: Macromolecules 42 1792 (2009).

Polythiophene: A Warfare Agent Sensor

Described a new method to detect chemical warfareagent vapors using thin films of the conductingpolymer polythiophene as the main sensing element..

Research Output:1. Publication: Macromolecules 42 5414 (2009).

0 10 20 30 40 50 60

NO2

5 ppm

1 ppm

500 ppb

250 ppb

10 ppm

45

44

Re

sist

an

ce

(10

4Ω

)

43

42

41

0 2 4 6 8 10

0

2

4

6

8

ΔR

/R%

Conc. (ppm)

0 2 4 6 8 10

0

2

4

6

8

ΔR

/R%

Conc. (ppm)

Time (min)0 10 20 30 40 50 60

NO2

5 ppm

1 ppm

500 ppb

250 ppb

10 ppm

45

44

Re

sist

an

ce

(10

4Ω

)

43

42

41

0 2 4 6 8 10

0

2

4

6

8

ΔR

/R%

Conc. (ppm)

0 2 4 6 8 10

0

2

4

6

8

ΔR

/R%

Conc. (ppm)

Time (min)0 10 20 30 40 50 60

30

Re

sis

tance

(10

4Ω

)

27

24

21

Time (min)

10075

5025

25 50 75 1005

10

15

20

25

Conc. (ppm)

ΔR

/R%

25 50 75 1005

10

15

20

25

Conc. (ppm)

ΔR

/R%

NO2

0 10 20 30 40 50 60

30

Re

sis

tance

(10

4Ω

)

27

24

21

Time (min)

10075

5025

0 10 20 30 40 50 60

30

Re

sis

tance

(10

4Ω

)

27

24

21

Time (min)0 10 20 30 40 50 60

30

Re

sis

tance

(10

4Ω

)

27

24

21

Time (min)

10075

5025

25 50 75 1005

10

15

20

25

Conc. (ppm)

ΔR

/R%

25 50 75 1005

10

15

20

25

Conc. (ppm)

ΔR

/R%

NO2

0 10 20 30 40 50 60

NO2

5 ppm

1 ppm

500 ppb

250 ppb

10 ppm

45

44

Re

sist

an

ce

(10

4Ω

)

43

42

41

0 2 4 6 8 10

0

2

4

6

8

ΔR

/R%

Conc. (ppm)

0 2 4 6 8 10

0

2

4

6

8

ΔR

/R%

Conc. (ppm)

Time (min)0 10 20 30 40 50 60

NO2

5 ppm

1 ppm

500 ppb

250 ppb

10 ppm

45

44

Re

sist

an

ce

(10

4Ω

)

43

42

41

0 2 4 6 8 10

0

2

4

6

8

ΔR

/R%

Conc. (ppm)

0 2 4 6 8 10

0

2

4

6

8

ΔR

/R%

Conc. (ppm)

Time (min)0 10 20 30 40 50 60

30

Re

sis

tance

(10

4Ω

)

27

24

21

Time (min)

10075

5025

25 50 75 1005

10

15

20

25

Conc. (ppm)

ΔR

/R%

25 50 75 1005

10

15

20

25

Conc. (ppm)

ΔR

/R%

NO2

0 10 20 30 40 50 60

30

Re

sis

tance

(10

4Ω

)

27

24

21

Time (min)

10075

5025

0 10 20 30 40 50 60

30

Re

sis

tance

(10

4Ω

)

27

24

21

Time (min)0 10 20 30 40 50 60

30

Re

sis

tance

(10

4Ω

)

27

24

21

Time (min)

10075

5025

25 50 75 1005

10

15

20

25

Conc. (ppm)

ΔR

/R%

25 50 75 1005

10

15

20

25

Conc. (ppm)

ΔR

/R%

NO2

Colorful Polyaniline: Solvatochromism

Described the origins of an unusual phenomenonin polyaniline, i.e., polymers display different colorsin different solvents.

Research Outputs:1. Publication: Synthetic Metals 159 2153 (2009).2. Cover: Work featured on the cover of journal.

Explosives Vapor Sensors

Uncovered a new chemiresistor material based onconducting polymers and carbon nanotubes that candetect explosives in air.

Research Output:1. Invention Disclosures: Six disclosures filed in 2010.

Next Generation Endotoxin Sensors

Developed a new method to detect endotoxins in thebloodstream using functionalized carbon nanotubes,and conducting polymers..

Research Output:1. Invention Disclosures: Two disclosures filed in 2010.

Flexible Plastic Transistors

Fabricated a flexible, all-organic transistor devicemade using the conducting polymer polyaniline.

Research Outputs:1. Publication: Journal of Applied Physics 103

194501 (2008).

0 -10 -20 -30 -400

-50

-100

-150

-200

-250

-300

-350

-400

-200 V

-160 V

- 120 V

- 80 V- 40 V0V

VG

( V )

I DS

(A

)

VDS

( volts )

0 10 20 30 40

2.64

2.52

2.56

2.60

Resis

tance

(MΩ

)

DNT (80ppb)

DMMP (25ppm)DIMP (5ppm)

DNT(80ppb)

RDX (5ppt)

Time (min)

0 3 6 9 12

2.2

2.3

2.4

(M

)Time (min)

HN NH2

OOHN

HN H

Cl 2+1M HCl

HN

HN H

2

OO

1M HCl

HN

HN H

Cl 4+

1. Ascorbic acid

2. NH4OH (quench)

0 25 50 75 100 1251.68

1.72

1.76

1.80

1.84

1.88

500ng50g

100g

500g

Resi

sta

nce

(M

)

Time (mins)

CNT AmpBCNT