USE OF NANO-STRUCTURAL MATERIALS FOR POLLUTANTS REMOVAL IN WATER TREATMENT

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Universitity of Turin

Department of Chemistry

chimica

Teamwork:

Dr. G. Costamagna, Dr. S. Mariotti, Dr. M. Turco, Dr. A. Mariani Migliore, Dr. M. Ginepro,

1

Dr. C. Cecone, Prof. F. Trotta

2

1_{Analytical Chemistry}

2_{Organic Chemistry}

Dr. Giulia Costamagna

giulia.costamagna@unito.it

Bari, September 23

th

2019

USE OF NANO-STRUCTURAL MATERIALS FOR POLLUTANTS REMOVAL

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Heavy metals

(Cd, Pb, Ni, Hg,

Cr(VI), As (V), As (III) etc.)

Herbicides

(Glyphosate)

Nanostructural biopoymers

NANOSPONGES

as potential

innovative solution

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Nanosponges: definition

The term Nanosponge (NS) refers to a class of

insoluble materials with distinctive nanometric

porosity and superior absorption/complexation

properties

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Syntesis

Initiator

Unit base

DABCO

1,4-diazabicyclo[2.2.2]octane

Choline

Maltodextrine

Functionalisation

with positive charge

BDE

1,4-Butanediol

diglycidyl

ether

Epoxide

Cross linker

GLUCIDEX® waxy corn maltodextrin is a plant-based texturizer providing

chewiness in gelatin-free chews, thickness to cakes and helps to reduce

calories in an extensive variety of food applications – Roquette® Product

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Syntesis: mechanism suggested

DABCO

1,4-diazabicyclo[2.2.2]octane

Choline

(to have more positive charge)

Experimental conditions:

 Basic acqueos enviroment

 Temperature: 70°C

Maltodextrine

Nucleofile Ion alcoxide Nucleofile

Main Mechanism:

1

3

Nucleofile .. BDE

1,4-Butanediol diglycidylether

Epoxide

2

“Initiation of anionic polymerization of acrylonitrile with tertiary amines and ethylene or propylene oxide: some mechanistic aspects” Yakov I. Estrin, Alexander E. Tarasov,* Alexander A. Grishchuk, Alexander V. Chernyak and Elmira R. Badamshina*, Royal Society of Chemistry, 2016

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Byopolimers synthetized

GLUBDE:

GLUCIDEX 2 + BDE (1,4-Butanediol diglycidyl ether)

GLUBDE:

GLUCIDEX 2 + BDE (1,4-Butanediol diglycidyl ether)

GLUCHOBDE:

GLUCIDEX 2 + Choline cloride + BDE (1,4-Butanediol diglycidyl ether)

GLUCHOBDE:

GLUCIDEX 2 + Choline cloride + BDE (1,4-Butanediol diglycidyl ether)

BDE

GLUTTE:

GLUCIDEX 2 + TTE (Trimethylolpropane triglycidyl ether)

GLUTTE:

GLUCIDEX 2 + TTE (Trimethylolpropane triglycidyl ether)

GLUCHOTTE:

GLUCIDEX 2 + Choline cloride+ TTE (Trimethylolpropane

triglycidyl ether)

GLUCHOTTE:

GLUCIDEX 2 + Choline cloride+ TTE (Trimethylolpropane triglycidyl ether)

TTE

GLUNGDE:

GLUCIDEX 2 + NGDE (Neopentyl glycol diglycidyl ether)

GLUNGDE:

GLUCIDEX 2 + NGDE (Neopentyl glycol diglycidyl ether)

GLUCHONGDE:

GLUCIDEX 2 + Choline cloride + NGDE (Neopentyl glycol diglycidyl ether)

GLUCHONGDE:

GLUCIDEX 2 + Choline cloride + NGDE (Neopentyl glycol diglycidyl ether)

NGDE

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Compounds tested

Anions

Nitrates

Sulfates

Metals

Cr (VI) as

CrO

₄

2-As (V) as

AsO

4

3-As (III) as

AsO

₂

-Organic

Compounds

Organic

Compounds

Glyphosate

Batch tests: anions solution

For the characterisation several

batch tests were performed.

Abatement tests were carried out

at different concentrations:

100 ppb -1000 ppm

Final aim of this work:

General screening to test the

efficiency of different types of

biopolymers.

1 gr of material + 100 ml of contaminant solution

Stirring for 24h and analytical check.

*Ion chromatography

ICP-OES

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Results: Nitrates

100 200 300 400 500 600 700 800 900 1000 0.0 10.0 20.0 30.0 40.0 50.0 60.0 70.0 80.0 90.0

Nitrates – Abatement %

GLUBDE GLUCHOBDE GLUTTE GLUCHOTTE GLUNGDE GLUCHONGDE Concentration (mg/L) A b at e m e n t %

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Results: Sulfates

Sulfates were tested for a peculiar application in a biomedical field

Absolute absorbed amount: 9,8 - 32 mg SO

₄ 2-

_{/g NS}

100 200 300 400 500 600 700 800 900 1000 0.0 20.0 40.0 60.0 80.0 100.0 120.0

Sulfates – Abatement %

GLUBDE GLUCHOBDE GLUTTE GLUCHOTTE GLUNGDE GLUCHONGDE Concentration (mg/L) A b at e m e n t %

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Results: Cr (VI)

Limit of Detection of ICP-OES: 10 ppb

0 10 20 30 40 50 60 70 80 90 100 50.0 60.0 70.0 80.0 90.0 100.0

Cr (VI) – Abatement %

GLUBDE GLUCHOBDE GLUTTE GLUCHOTTE GLUNDGE GLUCHONGDE Concentration (mg/L) A b at e m e n t %

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Results: As (V) and As (III)

GLUBDE GLUCHOBDE GLUTTE GLUCHOTTE GLUNGDE GLUCHONGDE 0.0 5.0 10.0 15.0 20.0 25.0 30.0 35.0 40.0 45.0 50.0 As (III) 10 ppm - Abatement % GLUB DE GLUC HOBD E GLUT TE GLUC HOTT E GLUN GDE GLUC HONG DE 0 20 40 60 80 100 120

As (V) Abatement %

100 ppb 1 ppm 10 ppm

Limit of Detection of ICP-OES: 10 ppb

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Results: Glyphosate

Limit of Detection of ICP-OES (as Glyphosate): 500 ppb

Preliminar tests – High Concentration of Glyphosate: good results

...Work in progress...

GLUBDE GLUCHOBDE GLUTTE GLUCHOTTE GLUNGDE GLUCHONGDE 0.0 20.0 40.0 60.0 80.0 100.0 120.0

Glyphosate 100 ppm - Abatement %

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These nanostructural biopolymers are:

 Innovative materials for some polluntants abatement

 Vegetable matrix as material source

 Good abatement for different contaminants:

-

Nitrates

: maximum abatement 50-80%

-

Sulfates

: maximum abatement 60-100%

-

Cr (VI)

: maximum abatement 90-100%

-

As (V)

: maximum abatement 80-100%

- Glyphosate: maximum abatement 80-100%

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There are a lots of work to do...

• Kinetic evaluation

• Improve the syntesis, also using other alternative initiators

• Test lower pollutant concentration and do other batch

tests and column tests

• Test different pollutants in the same solution to evaluate a

possible absorption competiont among them.

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