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FACOLTA' DI SCIENZE MATEMATICHE FISICHE E NATURALI

Universit degli Studi di Trento

Facolt di Scienze MM FF NN Corso di Fisica Sessione di Laurea 18 Luglio 2012

PHOTOCATALYTIC NANOSTRUCTURES FOR WATER PURIFICATION


Production of an innovative heterogeneous photocatalyst Laureando Giovanni Girelli

Laureando Giovanni Girelli Relatore Antonio Miotello

Relatore Antonio Miotello


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PHOTOCATALYTIC NANOSTRUCTURES FOR WATER PURIFICATION


Universit degli Studi di Trento

Introduction improper treatment of industrial waste nitrogen oxides produced during the combustion of fossil fuels that cause acid rains alga infestations due to the fertilizers used in agriculture Solution Advanced Oxidation Processes (AOP) AOP are reactions in which a hydroxyl radical is involved

Facolt di Scienze MM FF NN Corso di Fisica Sessione di Laurea 18 Luglio 2012

Laureando Giovanni Girelli Relatore Antonio Miotello

Problem: water pollution


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PHOTOCATALYTIC NANOSTRUCTURES FOR WATER PURIFICATION


Universit degli Studi di Trento

Facolt di Scienze MM FF NN Corso di Fisica Sessione di Laurea 18 Luglio 2012

We want to achieve the degradation of the pollutants, a process that might be complex and may require many steps. It is necessary to investigate this degradation processes, to ensure that there are no toxic products

Laureando Giovanni Girelli Relatore Antonio Miotello

PHOTOCATALYTIC NANOSTRUCTURES FOR WATER PURIFICATION


Universit degli Studi di Trento

Direct Photolysis of H2O2


Facolt di Scienze MM FF NN Corso di Fisica Sessione di Laurea 18 Luglio 2012

Photoexcitation of TiO2

Laureando Giovanni Girelli Relatore Antonio Miotello

Light dissociate water peroxide to give a hydroxyl ion and a hydroxyl radical High quantum efficiency

Light creates a electron-hole couple, which dissociates water No need for an additional oxidant

Absorption is limited to the ultraviolet


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PHOTOCATALYTIC NANOSTRUCTURES FOR WATER PURIFICATION


Universit degli Studi di Trento

Fenton and photo Fenton

Facolt di Scienze MM FF NN Corso di Fisica Sessione di Laurea 18 Luglio 2012

A transition metal like Iron or Cobalt participates in the following reactions: Co2++H2O2Co3++OH-+OHradical Co3++H2O2Co2++HO2 radical+H+ In the complete reaction the metal behaves like a catalyst. The second reaction can be slow. Visible Light Faster reduction Co3++H2O+hvCo2++HOrad+H+

Laureando Giovanni Girelli Relatore Antonio Miotello

An oxidant is necessary in Fenton reactions


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PHOTOCATALYTIC NANOSTRUCTURES FOR WATER PURIFICATION


Universit degli Studi di Trento

Homogeneous catalyst

Heterogeneous catalyst

Facolt di Scienze MM FF NN Corso di Fisica Sessione di Laurea 18 Luglio 2012

The catalyst dissolves into the water

Laureando Giovanni Girelli Relatore Antonio Miotello

The catalyst is in a different phase, e.g. deposited on a substrate

It must be recovered, continuous flow is difficult

Easy to reuse, environment-friendly, continuous flow possible


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PHOTOCATALYTIC NANOSTRUCTURES FOR WATER PURIFICATION


Universit degli Studi di Trento

Our goal: a heterogeneous photocatalyst, that absorbs visible light

Facolt di Scienze MM FF NN Corso di Fisica Sessione di Laurea 18 Luglio 2012

Co3O4 nanoparticles, deposited on glass or silicon. Co3O4 is a photo Fenton catalyst, active in the visible region.

Laureando Giovanni Girelli Relatore Antonio Miotello

Which deposition technique should we use?


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PHOTOCATALYTIC NANOSTRUCTURES FOR WATER PURIFICATION


Universit degli Studi di Trento

Facolt di Scienze MM FF NN Corso di Fisica Sessione di Laurea 18 Luglio 2012

Varying the substrate T, we can control the droplets dimension

Pulsed Laser Deposition (PLD)

We can tailor the stoichiometry carefully choosing the oxygen pressure

Laureando Giovanni Girelli Relatore Antonio Miotello

The deposition with PLD is a one-step process. The laser superheats material that evaporates abruptly, expelling a plume composed of gas and liquid droplets: Phase explosion
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PHOTOCATALYTIC NANOSTRUCTURES FOR WATER PURIFICATION


Universit degli Studi di Trento

Facolt di Scienze MM FF NN Corso di Fisica Sessione di Laurea 18 Luglio 2012

Laureando Giovanni Girelli Relatore Antonio Miotello

The superheated state is metastable. It exists between the Eq. Vap. line and the Spinodal, which equations are

PHOTOCATALYTIC NANOSTRUCTURES FOR WATER PURIFICATION


Universit degli Studi di Trento

Liquid
Facolt di Scienze MM FF NN Corso di Fisica Sessione di Laurea 18 Luglio 2012

Slow heating

Normal boiling

Vapor

Laureando Giovanni Girelli Relatore Antonio Miotello

Fast heating

Heterogeneous process: needs impurities or defects to begin nucleation Metastabl Vapor Phase e + explosion state droplets Homogeneous process: the available free energy is enough to create an enormous number of nucleation points

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PHOTOCATALYTIC NANOSTRUCTURES FOR WATER PURIFICATION


Universit degli Studi di Trento

The deposition has been repeated with different substrate temperatures: RT, 100 C, 150C, 200C and 250C. SEM image: 150C Narrow particle dimension distributio n peaked at about 25 nm. 150C

Facolt di Scienze MM FF NN Corso di Fisica Sessione di Laurea 18 Luglio 2012

Laureando Giovanni Girelli Relatore Antonio Miotello

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PHOTOCATALYTIC NANOSTRUCTURES FOR WATER PURIFICATION


Universit degli Studi di Trento

The deposition has been repeated with different substrate temperatures: RT, 100 C, 150C, 200C and 250C. SEM image: 250C Surface diffusion is enhanced, particles aggregate

Facolt di Scienze MM FF NN Corso di Fisica Sessione di Laurea 18 Luglio 2012

Laureando Giovanni Girelli Relatore Antonio Miotello

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PHOTOCATALYTIC NANOSTRUCTURES FOR WATER PURIFICATION


Universit degli Studi di Trento

By changing the temperature, we are also changing the structure of the deposited Co3O4, as is revealed by the XRD spectra

Facolt di Scienze MM FF NN Corso di Fisica Sessione di Laurea 18 Luglio 2012

(2) Crystallization is complete

Laureando Giovanni Girelli Relatore Antonio Miotello

(1) Crystallization (cubic spinel) begins as the circled peaks appear


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PHOTOCATALYTIC NANOSTRUCTURES FOR WATER PURIFICATION


Universit degli Studi di Trento

Which temperature is optimal?

Facolt di Scienze MM FF NN Corso di Fisica Sessione di Laurea 18 Luglio 2012

Laureando Giovanni Girelli Relatore Antonio Miotello

Study the catalytic activity of the samples, by comparing the degradation ratio of methylene blue reached after a fixed time The sample produced at 150 C leads to the best result High activity of the crystal-amorphous phase boundaries
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PHOTOCATALYTIC NANOSTRUCTURES FOR WATER PURIFICATION


Universit degli Studi di Trento

Other tests have been performed to verify that the process is actually a photo Fenton reaction. Catalyst+MB+ Light+H2O2 Catalyst+MB+ Light MB+Light+ H2O2 Catalyst+MB+ H2O2
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Facolt di Scienze MM FF NN Corso di Fisica Sessione di Laurea 18 Luglio 2012

Laureando Giovanni Girelli Relatore Antonio Miotello

PHOTOCATALYTIC NANOSTRUCTURES FOR WATER PURIFICATION


Universit degli Studi di Trento

The effect of different concentrations of H2O2 and pH has been studied, to find the optimal range:

Facolt di Scienze MM FF NN Corso di Fisica Sessione di Laurea 18 Luglio 2012

Laureando Giovanni Girelli Relatore Antonio Miotello

Best results in neutral pH, while in an acid medium the degradation is negligible due to the H+ ions.

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PHOTOCATALYTIC NANOSTRUCTURES FOR WATER PURIFICATION


Universit degli Studi di Trento

The effect of different concentrations of H2O2 and pH has been studied, to find the optimal range:

Facolt di Scienze MM FF NN Corso di Fisica Sessione di Laurea 18 Luglio 2012

Too much H2O2 scavenges the hydroxyl ions, while too little of it is not enough to produce a sufficient amount of radicals
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Laureando Giovanni Girelli Relatore Antonio Miotello

PHOTOCATALYTIC NANOSTRUCTURES FOR WATER PURIFICATION


Universit degli Studi di Trento

The last test performed is on reusability, measuring the degradation ratio of the same sample used six times The reduced effectiveness is putable to the loss of catalytic material from the surface

Facolt di Scienze MM FF NN Corso di Fisica Sessione di Laurea 18 Luglio 2012

Laureando Giovanni Girelli Relatore Antonio Miotello

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PHOTOCATALYTIC NANOSTRUCTURES FOR WATER PURIFICATION


Universit degli Studi di Trento

Conclusion Neutral pH Visible light

Facolt di Scienze MM FF NN Corso di Fisica Sessione di Laurea 18 Luglio 2012

Co3O4 heterogeneou s catalyst

Laureando Giovanni Girelli Relatore Antonio Miotello

Continuos flow

With better adhesion, reusability


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