Selective removal from water of emerging contaminants by ... · Imidacloprid 1.00 ± 0.06 TiO 2...
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Selective removal from water of emerging contaminants by nanomaterials for circular economy Giuliana Impellizzeri UiO: Energy Forum 2019
Transcript of Selective removal from water of emerging contaminants by ... · Imidacloprid 1.00 ± 0.06 TiO 2...
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Selective removal from water of emerging contaminants by nanomaterials for circular economy
Giuliana Impellizzeri
UiO: Energy Forum 2019
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Motivation
1. ENERGY
2. WATER
3. FOOD
4. ENVIRONMENT
5. POVERTY
2/3
by 2025 of the world populationwill live in areas of
high water stress
[R. E. Smalley, Nobel Prize in Chemistry 1996,Rice University, USA]
humanity’s top 5 problems
[United Nations]
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Traditional water treatments
• Pollutants are not eliminated• High operating costs• Generation of toxic secondary
pollutants into the ecosystem[Chong et al., Water Res. 44, 2997 (2010)]
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Heterogeneous photocatalysis
[Banerjee et al., Appl. Catal. B Environment. 176-177, 396 (2015)]
Semiconductors (e.g. TiO2, ZnO, Fe2O3, CdS, ZnS) act as sensitizers for light-induced redox processes:
• Effective in degrading refractory organic compounds and water pathogens
• Ambient operating temperature and pressure
• Complete mineralization of contaminants without secondary pollution
• Low operating costs
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Main drawback of photocatalysis
Lack of selectivity(that means highly-toxic organic pollutants at
low concentration are hardly removed)
The solution MOLECULAR IMPRINTING[Polyakov et al., Zhur. Fiz. Khim. 2, 799 (1931)]
Molecularmemory
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Matching of molecular imprinting with photocatalysis
MATERIAL SYNTHESIS(molecular imprinting)
SELECTIVE REMOVAL OF CONTAMINANTS
(photocatalysis)
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ZnO and TiO2: the catalysts of choiceHigh photocatalytic performance
Large band gap ( 3.3 eV)Easy to growth
[Wang, Mater. Today 7, 26 (2004)]
[Li et al., Chem. Soc. Rev. 45, 2603 (2016)]
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Outline
oMolecularly imprinted ZnO for selective degradation of pharmaceuticals
oMolecularly imprinted TiO2 for selective degradation of pesticides
oMolecularly imprinted ZnO for selective degradation of pharmaceuticals
oMolecularly imprinted TiO2 for selective degradation of pesticides
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Zinc acetate dihydrate(0.5 M)
Sodium Hydroxide(1.0 M)
CO-PRECIPITATION METHOD: [Sadollahkhani et al., RSC Advances 4, 36940 (2014)]
Molecularly imprinted (MI) ZnO: the synthesis
Paracetamolas template
(0.3 g)
The template was removed by simple washing
2 hrs under stirring+
140 °C for a night
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MI ZnO: morphological characterization (SEM & BET)
100 nm 200 nm
ZnO
200 nm
MI ZnO
100 nm
ZnO reference
BET surface area = 5±2 m2/g
MI ZnO
BET surface area = 6±2 m2/g
Molecularlyimprinted
ZnO nanonuts
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20 25 30 35 40 45 50 55 60
CP
S [
arb.u
nit
]
2 [degree]
ZnO
MI ZnO
MI ZnO + paracetamol
Paracetamol
(110)
(102)
(101)
(002)
(100)
20 25 30 35 40 45 50 55 60
MI ZnO
MI ZnO + paracetamol
Paracetamol
CP
S [
arb
.un
it]
2 [degree]
(110)
(102)
(101)
(002)
(100)
20 25 30 35 40 45 50 55 60
CP
S [
arb
.un
it]
2 [degree]
Paracetamol
20 25 30 35 40 45 50 55 60
CP
S [
arb.u
nit
]
2 [degree]
MI ZnO + paracetamol
Paracetamol
(110)
(102)
(101)
(002)
(100)
Paracetamol ZnO
MI ZnO: structural characterization (XRD & TEM)
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MI ZnO: photocatalytic tests
300 400 500 600 700
0.00
0.25
0.50
0.75
1.00
Ab
sorb
an
ce
Wavelength [nm]
0 min
30 min
60 min
90 min
120 min
180 min
MO 462 nm
225 250 275 300
0.0
0.2
0.4
Ab
sorb
an
ce
Wavelength [nm]
0 min
30 min
60 min
90 min
120 min
180 min
Paracemol243.5 nm
Paracetamol Methyl orange
A = l C Lambert-Beer law
= extinction molar coefficientl = optical path lenghtC = concentration of pollutantA = absorbance (@ 462 nm for MO)
UV lamp: 368 nm, 4 mW/cm2
Kept in the dark for the evaluation of physical
adsorption
Irradiation by UV lamp with a power of 8 W,
for a total time of 3 hours.
Every 30 minutes of irradiation the solutions were
measured with a UV-VIS spectrophotometer.
ZnO ZnOMI ZnO MI ZnO
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MI ZnO: selective degradation of paracetamolParacetamol Methyl orange
0 30 60 90 120 150 1800.0
0.2
0.4
0.6
0.8
1.0
Paracetamol
ZnO
MI ZnO
C/C
0
Time [min]
0 30 60 90 120 150 1800.0
0.2
0.4
0.6
0.8
1.0
Paracetamol
ZnO
MI ZnO
MO
ZnO
MI ZnO
C/C
0
Time [min]k [min-1] Paracetamol k [min-1] Methyl Orange
ZnO (1.12 ± 0.06) x 10-3 (1.22 ± 0.06) x10-3
MI ZnO (1.32 ± 0.06) x10-2 (9.71 ± 0.05) x10-4
𝑙𝑛𝐶
𝐶0= − kt
Langmuir Hinshelwood model
M. Cantarella… and G. Impellizzeri, Appl. Catal. B: Environ. 238, 509 (2018)
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Outline
oMolecularly imprinted ZnO for selective degradation of pharmaceuticals
oMolecularly imprinted TiO2 for selective degradation of pesticides
oMolecularly imprinted ZnO for selective degradation of pharmaceuticals
oMolecularly imprinted TiO2 for selective degradation of pesticides
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Molecularly imprinted (MI) TiO2: the synthesis
Precursors:
Titanium (IV) butoxide, ethanol, glacial acetic acid
Peticides:
2,4D herbicide
Imidacloprid insecticide
1) Formation of gel
2) Drying (100 °C for 12 h)
3) Calcination (500 °C for 6 h)
SOL-GEL SYNTHESIS
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MI TiO2: morphological characterization (SEM & TEM)
• Rough morphology with heterogeneous shaped particles.
• No substantial variation due to MI process.
• Granular morphology.
• Polycrystalline anatase phase.
• No substantial variation due to MI process.
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4000 3500 3000 2500 2000 1500 1000 500
TiO2 MI/2,4D
2,4 D
TiO2 MI/2,4D Not Removed
TiO2
Tra
nsm
itta
nce
[ar
b. unit
]
Wavenumber [cm-1
]
MI TiO2/2,4D: structural characterization (FTIR)
1736 cm-11312 and 1092 cm-1
1290 and 1081 cm-1 1719 cm-1
No 2,4D peaks after the removal
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4000 3500 3000 2500 2000 1500 1000 500
TiO2 MI/Imid. Not Removed
TiO2 MI/Imid.
TiO2
Tra
nsm
itta
nce
[ar
b. unit
]
Wavenumber [cm-1]
Imidacloprid
MI TiO2/Imid.: structural characterization (FTIR)
1539 cm-1
No Imidacloprid peaks after the removal
1569 cm-1
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MI TiO2/2,4D: selective degradation of 2,4D
0 30 60 90 120 150 1800.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
C/C
0
Time [min]
2,4D
TiO2
TiO2 MI/Imid.
TiO2 MI/2,4D
Sample k (min-1) ·10-4
2,4 D 1.01 ± 0.06
TiO2 6.09 ± 0.06
TiO2MI/Imid. 6.08 ± 0.06
TiO2MI/2,4D 36.15 ± 0.06
• Highest 2,4D degradation rate for the TiO2MI/2,4D sample
UV lamp: 368 nm, 4 mW/cm2
𝑙𝑛𝐶
𝐶0= − kt
Langmuir Hinshelwood model
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MI TiO2/Imid.: selective degradation of Imid.
0 30 60 90 120 150 1800.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Imidacloprid
TiO2
TiO2MI/2,4D
TiO2MI/Imid.
C/C
0
Time [min]
Sample k (min-1) ·10-4
Imidacloprid 1.00 ± 0.06
TiO2 11.05 ± 0.06
TiO2MI/Imid. 22.45 ± 0.06
TiO2MI/2,4D 11.09 ± 0.06
Highest Imid. degradation rate for the TiO2MI/Imid. sampleUV lamp: 368 nm, 4 mW/cm2
𝑙𝑛𝐶
𝐶0= − kt
Langmuir Hinshelwood model
R. Fiorenza… and G. Impellizzeri, Chem. Eng. J. 379, 122309 (2020)
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230 µm
A. Larva not-treated with metal oxide
B. Larva exposed to TiO2
C. Larva exposed to TiO2 MI/Imid.
MI TiO2/Imid.: toxicology testZebrafish embriotoxicity test (ZFET)
Neither mortality nor sublethal
effects were caused by the different powders tested
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1 µm
500 nm200 nm
Chemical precipitation(TiOSO4 + HCl)
R. Fiorenza… and G. Impellizzeri, J. Photochem. Photobiol. A 380, 11172 (20219)
MI TiO2/2,4D: changing the synthesis
UV lamp: 365 nm, 12 mW/cm2
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To take home:
• New synthesis of MI ZnO nanonuts• High performance in paracetamol photodegradation• High selectivity in paracetamol photodegradation
• MI TiO2 powders successfully synthetized• High performance in pesticides photodegradation• High selectivity in pesticides photodegradation• No toxicity
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o A. Di Mauro (CNR-IMM)o R. Fiorenza (now at the Department of Chemistry, University of Catania)o M. Cantarella (CNR-IMM)o V. Privitera (CNR-IMM)o M.V. Brundo, E.M. Scalisi (Department of Biological, Geological and Environmental Science, University of Catania),
C. Iaria (Department of Chemical, Biological, Pharmacological and Environmental Sciences, University of Messina) for the biological tests
o A. Gulino and L. Spitaleri (Department of Chemical Science, University of Catania) for the XPS measurements
o G. Nicotra (CNR-IMM) for the TEM characterization
I wish to thank:
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To remember…
Oslo, September 2013My first time in Oslo
Catania, October 2014
Lille, May 2015
Syracuse, March2013
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MI ZnO: structural characterization (FTIR)
1654, 1565 and 1072 cm-11442 cm-1
1412 cm-1 1640, 1558 and 1050 cm-1
4000 3500 3000 2500 2000 1500 1000 500
Wavenumber [cm-1]
Tra
smit
tance
[ar
b. unit
]
Paracetamol
MI ZnO + paracetamol
MI ZnO
ZnO
No paracetamol peaks after the removal
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MI TiO2/2,4D: selective degradation of 2,4D
0 30 60 90 120 150 1800.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
C/C
0
Time [min]
2,4D
TiO2
TiO2 MI/Imid.
TiO2 MI/2,4D
Sample k (min-1) ·10-4
2,4 D 1.01 ± 0.06
TiO2 6.09 ± 0.06
TiO2MI/Imid. 6.08 ± 0.06
TiO2MI/2,4D 36.15 ± 0.06
0
10
20
30
40
50
TiO2 MI/2,4DTiO
2 MI/Imid.
Deg
radat
ion [
%]
UV
TOC
TiO2
• Highest 2,4D degradation rate for the TiO2MI/2,4D sample
• Only CO2 formation
UV lamp: 368 nm, 4 mW/cm2
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MI TiO2/Imid.: selective selective degradation of Imid.
0 30 60 90 120 150 1800.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Imidacloprid
TiO2
TiO2MI/2,4D
TiO2MI/Imid.
C/C
0
Time [min]
Sample k (min-1) ·10-4
Imidacloprid 1.00 ± 0.06
TiO2 11.05 ± 0.06
TiO2MI/Imid. 22.45 ± 0.06
TiO2MI/2,4D 11.09 ± 0.06
0
10
20
30
40
50
TiO2 MI/2,4DTiO
2 MI/Imid.TiO
2
Deg
radat
ion [
%]
UV
TOC
• Highest Imid. degradation rate for the TiO2MI/Imid. sample
• Only CO2 formationUV lamp: 368 nm, 4 mW/cm2
