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PREPARATION OF PHOTOCATALYTIC HYDROGEL-METAL OXIDE NANOPARTICLE COMPOSITE FOR TEXTILE DYE DEGRADATION

Walasinee Jitbunpot 4972476923  Adviser: Prof.Dr. Suda Kiatkamjornwong Co-adviser: Dr. Wiyong Kangwansupamonkon

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Wastewater treatment 1. Chemical coagulation

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Wastewater treatment 2. Biological Treatment

Aerated lagoon 4

Wastewater treatment 3. Activated Carbon

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Wastewater treatment 3. Ozone Treatment

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Advantages of TiO2/hydrogel composites

1. Superabsorbent polymer is able to absorb water hundreds to thousands times of its weight. 2.Photocatalyst of TiO2/hydrogel is able to degrade textile dyes. 3.This process utilizes cheaply available nontoxic materials.

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Mechanism for water absorbing of hydrogels H

O H

COO- H O H

O

COOH H COO OOC

HH

H

O

O

H -

OOC

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Photocatalysis mechanism of TiO2 Reduction

H2 O

O2,O3

O2 H2O2

eConduction band

Valence band

e-

TiO2 3.2 eV

h+

H2O

Oxidation

e- e e-

h+ h+

●OH

h+

Organic CO 2+H2O material

●OH 9

Applications of Photocatalyst NOx, SOx, CO, Formaldehyde and etc...

Air Purification

Organic chloride, Starch, Dyes and etc

Water Purification

Garbage odor, Aldehyde, Ammonia, Chloroform, Gasoline, Formaldehyde and etc

Deodorization TiO2 Photocatalyst

Bacteria, Fungal, Algae, Pest infestation and etc

Sterilization

Oil, Soil, Soot, Self clean, Anti-fogging function and etc.

Soil Proof 10

Application of Photocatalyst

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Applications of Photocatalyst Self-cleaning

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Application of Photocatalyst Indoor Applications

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Application of Photocatalyst BLACK HOLE - TiO2 MOSQUITO TRAP

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Literature Reviews Removal of some textile dyes from aqueous solutions by poly(N-vinyl-2-pyrrolidone) and poly(N-vinyl-2-pyrrolidone)/K2S2O2 hydrogels Hydrogels : Poly(N-vinyl-2-pyrrolidone) and Poly(N-vinyl-2-pyrrolidone)/K2S2O8 Gamma irradiator : 24,64, 96, and 124 kGy Temperature : ambient air Textile dyes : Cibacron Blue (CB) F3GA, Methyl Orange (MO), Congo Red (CR) Radiation Physics and Chemistry 68 (2003) 811-818

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% swelling

% swelling

Photodegradation rate of MO solution under mercury light radiation and sunlight radiation

a t (min)

b t (min)

Figure 1 photodegradation of MO under a) light radiation and b) sunlight radiation

Radiation Physics and Chemistry 68 (2003) 811-818

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Swelling equilibrium (%) of PVP and PVP/K2S2O8 hydrogels in MO solutions (10 mg/100 ml Mo)

Dose (kGy) 26 64 96 124

PVP 1264 727 576 515

PVP/K2S2O8 1498 834 636 588

Radiation Physics and Chemistry 68 (2003) 811-818

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Literature Reviews Effect of PVP on the photocatalytic behavior of TiO2 under sunlight Hydrogels : polyvinylpyrrolidone (PVP) Metal oxide : Titanium dioxide (TiO2) PVP/TiO2 : 20 wt.% (PT20), 30 wt.% (PT30) and 40 wt.% (PT40) added during the sol–gel process. Textile dyes : methylene red

W. Wang et al. / Materials Letters 57 (2003) 3276-3281

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C/C0

C/C0

Photodegradation rate of a methylene red solution under a mercury light radiation and sunlight radiation.

b

a Time (hour)

Time (hour)

Figure 2 photodegradation of Methylene red under a) light radiation and b) sunlight radiation W. Wang et al. / Materials Letters 57 (2003) 3276-3281

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Crystallite size and rutile mass fraction calculated from XRD

Sample

T

Crystallite size (nm) 16.78 Rutile ratio (vol.%) 0

PT20 14.24 15.2

PT30

PT40

12.59 17.0

14.39 24.5

W. Wang et al. / Materials Letters 57 (2003) 3276-3281

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Literature Reviews Synthesis and characterization of acrylamide-acrylic acid hydrogels and adsorption of some textile dyes Hydrogels : acrylamide (PAM) and acrylic acid mole ratios 15/85, 20/30, 30/70 Gamma irradiator : 2.6, 3, 4, 8, 12, 16, 20 kGy Temperature : ambient air Textile dyes : Janus Green B (JGB)

Nuclear Instruments and Methods in Physics Research B 151 (1999) 196-199

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Equilibrium adsorption isotherms and Langmuir plot for adsorption of Janus Green B (JGB) on poly(AAm/AAc) hydrogels. 30/70 20/80 15/85

Figure 3 Equilibrium adsorption isotherms and Langmuir plot Nuclear Instruments and Methods in Physics Research B 151 (1999) 196-199

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pH effect on poly(AAm/AAc) hydrogels

30/70

15/85 20/80

Figure 4 pH effect on poly(Aam/AAc) hydrogels Nuclear Instruments and Methods in Physics Research B 151 (1999) 196-199

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Literature Reviews Removal of methylene blue dye from an aqueous media using superabsorbent hydrogel supported on modified polysaccharide Hydrogels : Arabic gum is a cheap polysaccharide and was modified with glycicyl methacrylate, sodium acrylate and acrylamide (AGMA-AAm-AAc) (1.5-0.5-0.5) and (1.0-0.5-0.5) Textile dyes : Methylene blue

Journal of Colloid and Interface Science 301 (2006) 55-62

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Water uptake capacity for (1.5-0.5-0.5) and (1.0-0.5-0.5) SH as a function of immersion time

Figure 5 water uptake capacity for SHs as a function of immersion time Journal of Colloid and Interface Science 301 (2006) 55-62

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Formation of an ionic complex between the imine groups of MB and the carboxylic groups in hydrogels

Journal of Colloid and Interface Science 301 (2006) 55-62

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Water uptake response of (1.5-0.5-0.5) SH to changes in pH

pH = 8

pH = 2 Figure 5 water uptake capacity for (1.5-0.50.5) SH as a function of pH Journal of Colloid and Interface Science 301 (2006) 55-62

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Literature Reviews Preparation and photocatalytic degradability of TiO2/polyacrylamide composite Hydrogels : polyacrylamide (PAM) Crosslinker : N,N’-methylenebisacrylamide (MBA) Initiator : ammonium persulfate (APS) Metal oxide : Titanium dioxide (TiO2) Temperature : 80 °C Textile dyes : methyl orange

Q. Tang et al. / European Polymer Journal 43 (2007) 2214-2220

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Morphology of the photocatalyst

Q. Tang et al. / European Polymer Journal 43 (2007) 2214-2220

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Decoloration rate %

Variation of color removal with the amount of TiO2 in photocatalyst

TiO2 (relative to the mass of acrylamide, %)

Figure 6 color removal as a function of the amount of TiO2 Q. Tang et al. / European Polymer Journal 43 (2007) 2214-2220

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Research Objectives

• To synthesize poly(acrylamide-co-acrylic acid) and study swelling of superabsorbent polymers 1. To study efficiency of textile dye degradation with titanium nanoparticles immobilized poly(acrylamide-co-acrylic acid) hydrogel composites

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Preparation of TiO2/poly(acrylamide-co-acrylic acid) composites

Purge N2

Acrylamide : Acrylic acid TiO2 MBA APS TEMED 35

Preparation of TiO2/poly(acrylamide-co-acrylic acid) composites

Purge N2

Acrylamide : Acrylic acid TiO2 MBA APS TEMED 36

Characterization

FTIR NMR SEM TEM XRD

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Photocatalytic Experiments Direct Blue 71 ONa OH

O S N N

N N O NaO

O S O ONa

S

O

NH2

O S O ONa

UV-Vis Spectrophotometry 38

Photocatalytic Experiments

Congo Red NH2

NH2 N

N

SO3Na

N N

SO3Na

UV-Vis Spectrophotometry 39

Prosperity from this research 1. To obtain knowledge of synthesis of photocatalytic hydrogen-metal oxide nanoparticle composites 2. To obtain knowledge of degradability of dye textiles by photocatalytic process 3. To obtain TiO2/poly(AAm-AAc) composites as photocatalyst to degrade dye textiles 4. To apply the synthesized material to degrade dye textiles 5. To recovery and reuse the synthesized material in the next cycle 40