Technological concepts and future applications of Ag and TiO2 anatase nanoparticles

produced by Green methods

Sustainable Nanotechnology Organization Conference

November, 2017

Guadalupe de la Rosa, Víctor M. Escalante-Gómez, María C. García-Castañeda, J. Antonio Reyes-Aguilera, Edgar Vázquez-Núñez, J. Jesús Ibarra-Sánchez

http://www.cnano.fr/spip.php?article8&lang=en“I don't know how to do this on a small

scale in a practical way, but I do know thatcomputing machines are very large; theyfill rooms. Why can't we make them very

small, make them of little wires, littleelements, and by little, I mean little?” R.F.

Nu

mb

er

of

pro

du

cts

Project on Emerging Nanotechnologies http://www.nanotechproject.org/cpi (Tomado el 19 de mayo del 2014)

Ag

and

TiO2 NPs

4

Aplications

Any given method to obtain NPs

– Advantages

– Disadvantages

http://www.cell.com/trends/biotechnology/fulltext/S0167-7799(16)00040-8

Green Chemistry

– If NPs are intended for biomedical

purposes

– No toxic chemicals

– If medicinal plants are used…….

07/61

Using plant

extracts:

DISADVANTAGES:- Available Resouce

throughout the year

- Concentration of metabolites in the plant

- Modification of chemicalstructure of metabolitesduring the process

- Reproducibility

9

Optimization

Reproducibility

Target

19/61

Synthesis and characterization

Surface modification

Applications

Nanoparticles

09/61

1. Ag

1. Biosynthesis optimisation determining the most favorable

conditions: pH, metabolite extractant, precursor

concentration.

2. TiO2

1. Biosynthesis optimisation: pH, Relationship

extractant/TIPO; Water/TIPO, using alfalfa extracts

(isopropanol)

3. Potential applications

Obje

ctiv

es

(NPs)

22/61

Ag NPs

– Plant metabolite extractant

– H2O

– Isopropanol

– Methanol

– pH

– [Ag]

Particle size (nm)

5 10 15 20

Rela

tive F

requency

0

5

10

15

20

25

30

35

9.0 2.6 nm

σP = 0.29

20 nm

20 nm

Particle size (nm)

5 10 15 20 25 30

Rela

tive F

requency

0

10

20

30

40

12.7 5.2 nm

σP = 0.41S05

20 nm

Particle size (nm)

5 10 15 20

Rela

tive F

requency

0

5

10

15

20

25

30

8.9 2.7 nm

σP = 0.31

(c) (d)

S08

20 nm

Particle size (nm)

5 10 15 20 25 30 35

Rela

tive F

requency

0

10

20

30

40

12.1 2.9 nm

σP = 0.24S10

(e)

20 nm

Particle size (nm)

5 10 15 20

Rela

tive F

requency

0

5

10

15

20

25

30

35

8.9 2.5 nm

σP = 0.28

(f)S11

50 nm

Particle size (nm)

10 15 20 25 30 35 40 45

Rela

tive F

requency

0

5

10

15

20

25

24.1 12.0 nm

σP = 0.50S12

(g)

50 nm

Particle size (nm)

5 10 15 20 25 30

Rela

tive F

requency

0

5

10

15

20

25

30

14.9 4.7 nm

σP = 0.32S01

(a)

S02(b)(a) pH = 10, [Ag+] = 5.5 mM

and agua como PMES (S01);

(b) pH = 7, [Ag+] = 5.5 mM y

agua como PMES (S02);

(c) pH = 7, [Ag+] = 5.5 mM e

Isopropanol–Agua como

PMES: (S05);

(d) pH = 7, [Ag+] = 5.5 mM,

and Metanol–Agua como

PMES (S08);

(e) pH = 7, [Ag+] = 10 mM y

agua como PMES (S10);

(f) pH = 7, [Ag+] = 5.5 mM y

agua como PMES (S11);

(g) pH = 7, [Ag+] = 1 mM y

agua como PMES (S12).

28/61

Ag NPs synthesis

TD: Thermal decomposition; S11: H2OS08: MethanolS05: Isopropanol

Preliminary micro XAS/EXAFS

– Mixture AgCl, Ag, Ag2O

– Different proportions

– Reproducibility to be

determined

18

https://ec.europa.eu/jrc/en/science-update/intercomparison-study-silver-nanoparticles-

food-simulants

Ag NPs

–Leather fungi

–Cancer cells

TiO2

– Anatase

– Patents:

– TiCl4

– Ti hydroxide

– PMES, TIPO/H2O

40/61

https://www.nature.com/articles/srep01959

Conditions21

(a) pH: 1, 3, 6(b) IsOH/ TIPO; 1.5:1(c) Extract/ TIPO; 0.1, 0.2, 0.3(d) TIPOReflux

Particle size (nm)

6 7 8 9 10 11 12 13

Rela

tive F

requency

0

5

10

15

20

25

9.2 2.5 nm

σP = 0.27

Particle size (nm)

11.0 11.5 12.0 12.5 13.0 13.5 14.0 14.5 15.0

Rela

tive F

requency

0

2

4

6

8

10

12

14

16

18

20

13.3 1.9 nm

σP = 0.14

Particle size (nm)

7.0 7.5 8.0 8.5 9.0

Rela

tive F

requency

0

5

10

15

20

25

8.2 1.5 nm

σP = 0.18

Particle size (nm)

8.0 8.5 9.0 9.5 10.0

Rela

tive F

requency

0

5

10

15

20

25

8.9 1.9 nm

σP = 0.21

Particle size (nm)

9.0 9.5 10.0 10.5 11.0 11.5 12.0

Rela

tive F

requency

0

5

10

15

20

25

10.8 1.1 nm

σP = 0.10

Particle size (nm)

6 7 8 9 10 11 12 13

Rela

tive F

requency

0

5

10

15

20

25

30

9.3 2.4 nm

σP = 0.26

Particle size (nm)

6 7 8 9 10 11

Rela

tive F

requency

0

2

4

6

8

10

12

8.1 1.2 nm

σP = 0.15

Particle size (nm)

22 24 26 28 30 32 34 36

Rela

tive F

requency

0

5

10

15

20

25

30

9.4 2.1 nm

σP = 0.22

S35

S10

S34

S02

S14 S25

S33S30

20 30 40 50 60 70 80

0

25

50

75

100

125

150

175

200

u.a

.

2*Theta

20 30 40 50 60 70 80 90

0

25

50

75

100

125

150

175

200A (101)

A (004) A (200) A (105) A (213)

A (116) A (215)

S10

S06

S02

R (101)R (111)

S34

S30

S28

S27

S26

S25

S22

S18

S14

Yield24

1.Removal of colorants in water using NPs de TiO2

2.Tannery effluent treatment

3.Kinetic studies

TiO

2te

st

https://www.google.com/search?tbm=isch&q=tannery+industry&sa=X&ved=0ahUKEwjcreDuxqnXAhUF1WMKHe5

MC6EQhyYIJg#imgrc=KIdYCJmlPlTWfM:

Concentration (mg/L)

NP size (nm)

500 1500

Average SD Average SD

300 97.9967 0.4179 95.2967 0.2701

560 95.7267 1.1091 93.2833 0.6035

WTHT NPs 3.7633 0.6258

% o

range

meth

ylre

moval

46/61

Concentration (mg/L)

NP size (nm)

500 1500

Average SD Average SD

300 97.7300 0.4004 97.7533 0.4315

560 55.4367 1.4981 95.2367 0.1274

Wtht NPs 5.6300 3.2509

% re

movalm

eth

yle

ne

blu

e

47/61

4000 3600 3200 2800 2400 2000 1600 1200 800 400

0

50

100

150

200

250

% T

ran

sm

ita

ncia

Numero de onda (cm-1)

Azul de metileno

TiO2

TiO2 con azul

Teneria

TiO2 con naranja

4000 3600 3200 2800 2400 2000 1600 1200 800 400

0

50

100

150

200

250Befo

reand a

fter

degra

datio

n

1hr12620 .k Cin

étic

a d

e d

egra

dació

n

1hr16820 .k

Methyl orange

Methylene blue

▪ Summary of findings, Ag

▪ Size and size distribution depend on pH, PMES, and initial Ag

concentration

▪ best numbers were obtained when PMES was water, pH 7 (8.9 ± 2.5

nm, σP = 0.28)

▪ Kinetics indicated a complex reaction

▪ NPs contain a mixture of Ag, AgCl, Ag2O 38/61

▪ Summary of findings, TiO2

▪ Size and size distribution depend on pH, H2O/TIPO, Extracts/TIPO

▪ Crystal phase may be controled (mostly, anatase is obtained)

▪ Best conditions to obtain anatase are pH 6, hydrolisis ratio 500, Extract/TIPO

ratio of 0.1

▪ Colorant degradation depends on particle size

44/61

What are we up to?

– Bouganvillea

– Vainillin

– guayacol

32

20 30 40 50 60 70

Inte

nsid

ad (

U.A

)

Ángulo de difracción (2)

TiO2 sol gel

B-agua 06

B-OH06

B-agua 03

B-OH03

20 30 40 50 60 70

Inte

nsid

ad (

U.A

)

Ángulo de difracción (2)

TiO2 sol gel

V-agua 06

V-OH 06

V-agua03

V-OH03

R. Vijayalakshmi and V. Rajendran. Arch.Appl.Sci.Res; 2012, 4(2): 1183-1190

Bouganvillea Vainillin

SEM

VANILLIN

Tannery effluent35

ZHANG Hui;ZHANG Guoliang*;YANG Zhihong;CHEN Jinyuan;NI Lijia; Degradation of Azo Dye Wastewater in a TiO2 Photocatalysis and Membrane

Separation Hybrid System ; Chinese J of Catalysis, 2009

J. Jesús IbarraVíctor EscalanteIturiel Arias

Gustavo CruzHiram Castillo

Ma. Concepción GarcíaEdgar VázquezSusana FigueroaRosalba Fuentes

37

QUESTIONS?

38

0 5 10 15 20 25 30 35

6

9

12

15

18

Data

Model

[Ag

+] (m

mo

l/L

)

Time (min)

99922.0

mol/L1033.7

6.4

2

6.36.36

R

sk

n

Cin

étic

ade re

acció

npara

la b

iosín

tesis

de la

SN

Ps

29/61

40

4000 3600 3200 2800 2400 2000 1600 1200 800

0

20

40

60

80

100

% T

ran

sm

ita

nce

Wave number, (cm-1)

IsOH-Water

MeOH-Water

Water

4000 3600 3200 2800 2400 2000 1600 1200 800

0

20

40

60

80

100Esp

ectro

s de IR

para

los d

istinto

s extra

cto

s

24/61

42