Environmental applications of Nanotechnology:

Nano becomes “green”

G.J.A.A. Soler Illia

Gerencia de Química

Gerencia de Area Seguridad Nuclear y Medio Ambiente

CNEA – Buenos Aires – Argentina gsoler@cnea.gov.ar

FORO DE INNOVACIÓN“TECNOLOGÍAS SUSTENTABLES APROPIADAS PARA LA

PROTECCIÓN CLIMÁTICA −EL APORTE DE LA INVESTIGACIÓN Y EL DESARROLLO”

Buenos Aires, 14 de noviembre de 2008

Nanotechnology

• See, Measure, Fabricate, Manipulate, Model– Materials and Processes– Precisely, at the

nanometric scale– 1/1.000.000.000 m– 10 H atoms side by side

• Properties scale with size• “Old tricks” revisited• Multicultural, Pervasive• Crossroads

Nano

Physics Chemistry

Biology

Engineering Medicine

1 000 000 m = 107 m

1 cm

1 m

1 nm

Nanoscaleproperties change with size

• Usual materials: intensiveproperties (color, conductivity, melting point) do not change withsize

• …small dimensions (<100 nm), substantial changes

– related to quantum phenomenalarge surface : volume ratio

“Bulk” goldGolden metal

NanoParticles30-500 nm

Metallicblue-violet

Scatter light

Clusters (Au55)<1 nm, Non-metallic

orange

Atoms 0,1 nmcolourless

NanoParticles3-30 nmMetallic

RedTransparent

Nano-gold

Faraday’s gold• Faraday, 1857, the first “nanoscientist”?

“known phenomena seemed to indicate that a mere variation in the size of [gold]

particles gave rise to a variety of resultant colours”

M. Faraday. Philosophical Transactions of the Royal Society of London, Vol. 147 (1847), 145-181, p.

159

Middle Age Nanotechnology

• Gold (red or purple) or silver (blue-grey-brown)

1685 “De Auro”, Andreas Cassius, Gold colloids for glazing of windows and ware

XVth Century (Segreti per Colori)

Nano-romans…

Lycurgus Cup (400 D.C. British Museum)

Assyrian recipe?? : (Assurbanipal, VII s.AC) (red glazing)

7200 parts glass 32 SnO 20 Sb 1 Au

+ +

+

+ +

Colourful nano-gold

Electron cloud

Metallic structure

Gold Nanoparticles

Nuclei

Surface effect: plasmon

Nano-catalysis

Heterogeneous processesMore surface, faster ratesTailored surfacesOxide-supportednanometals– Self-cleaning (fridges, air

conditioning)– TWC in car exhausts

Problems ahead

1. Energy• Fossil fuels→CO2

Low carbon techs2. Water

• Availability-pollution3. Food

• Impact of farming in biodiversity

4. Environment• Waste• Pollution• Available Land

5. Poverty

Environmentally BeneficialNanotechnologies

•• Fuel Fuel AdditivesAdditives•• Solar Solar CellsCells•• HydrogenHydrogen EconomyEconomy•• BatteriesBatteries//SupercapacitorsSupercapacitors•• InsulationInsulation

•• IncreaseIncrease fuel fuel efficiencyefficiency•• CostCost effectiveeffective CellsCells•• ImproveImprove StorageStorage•• Reduce Reduce ChargeCharge timetime•• Reduce Reduce heatheat lossloss

http://www.defra.gov.uk/

DEFRA (UK) commissioned report, Aug 2007

Potential impact

Environmentally Beneficial Nanotechnologies: Barriers andOpportunities, DEFRA report, Aug. 2007

Opportunities and risks• “nanotechnology could reduce UK green house gas

emissions by up to 2 % in the near term and up to 20 % by 2050 with a similar saving being realised in airpollution.”

• “Platform technology”• Barriers: behavioural changes

– Energy distribution (local vs central)– Safety issues (production of NP or NT)– Access to a new, sophisticated tech platform– Investment for tech replacement

• Incremental vs. Breakthrough technology

Some Critical Applications ofNanotech-Nanomaterials

• Clean Energies– Solar– Hydrogen and Fuel Cells– Rational use of Energy

• “Smart” windows• Reducing Greenhouse Effects• “Green” processes

• Environment– Cleaner technologies– Trapping of poisons/fixation of species– Sensing (materials and systems)– Catalysis/Photocatalysis

Some examples ofthe use of

NanoTech for a better

environment

Env. Sci. Tech. 2003, 37, Special Issue

Energy

• USA: 20% of energy → lighting• NP-based LEDs : 50% energy

savings for 2025• Nanotubes: withstand 20mA;

equivalent to 100x106 A/cm, improvement in transportefficiency, saving of4x1010 kWh

Source: NNI and EPA http://www.epa.gov/ncer

Renewable Energy

• More compact and efficient Solar Cells (Grätzel, 10% efficiency; mass production by G24 Innovations)

• Fuel Cells (nanostructuredmembranes, electrodes, catalysts)

• High power and density batteries(nanostructured electrodes, improved cyclability).

• Direct H2 production (catalysis, photodissociation of water)

calor

ánodo cátodomembranaconductora

CH3OH H2O

e e

e

O2 (aire)CO2

H+

Source: NNI and EPA http://www.epa.gov/ncer

Lightweight materials = efficiency

Source: NNI and EPA http://www.epa.gov/ncer

Example: Nanocomposites• Hybrid Material

– Polymer + NP– Tailored properties

• Mechanical (wear reduction)• Optical (less energy waste)• Chemical (less waste)

MRS Special Issue Hybrids 2005

NP for remediation

• Metallic NP• High reactivity• Reducing agents• Injected in the soil, reactive

towards pollutants (Cr(VI), RX, etc)

• Low cost per sq m

4000m2/$1000m2/$20m2/$200.000m2/kg25.000m2/kg10m2/kg

$ 50/kg$ 25/kg$ 0.5/kg

Porous N-Fen-FeFe

WX Zhang Lehigh University

Brief summary of NT in Argentina

L /μm0 1 2 3 4 5

z /n

m

0100200

L /μm0 1 2 3 4 5

z /n

m

0100200

(a)

(b)

(c)Imprinted Cu surface

Micromolded TiN Stamp(d)

(e)

NAD+ + H+

NADH

2 e-

NAD+ + H+

NADH

2 e-

N&NN&N InitiativeInitiative in Argentinain Argentina

4 Nano Networks (Human Resources, equipment)

Red Nacional de Nanotecnología Molecular, Supramolecular e Interfaces (RENAMSI)

Materiales Nanoestructurados (MaN)

Laboratorio en Red Dispositivos MicroElectroMecánicos (MEMS) / “Red LabMEMS”

Red de Bionanomateriales

Centro Interdisciplinario de N&N (CINN=CNEA+UBA+INIFTA)

Instituto de Nanociencia y Nanotecnologia CNEA (INN-CNEA)

PME projects (Equipment)

FAN (MCyT, towards applications and commercial products)

ca. 200 researchers, ca. 10 MUS$ funding (2007-2008)

N&N networks in Argentina

http://www.agencia.secyt.gov.ar/convocatorias/documentosconvocatorias/pav2004_informe.pdf

Meetings+ networks

Effect ofnetworking

2000

2005

H. Charreau, R. Barrere, O. Wald, SECyT y CAICyT2007

Red Nacional de Nanotecnología Molecular, Supramolecular e Interfaces

(RENAMSI)Director: Dr. Roberto Salvarezza, UNLProbsalva@inifta.unlp.edu.ar

Modelos y simulaciones computacionalesUNC (Córdoba) – Departamento de MatemáticasCoord. Dr. Ezequiel LeivaAutoensamblado y sistemas de baja dimensionalidadCAB-CNEA (Rio Negro) – Laboratorio de Física de SuperficiesCoord. Dr. O. GrizziAplicaciones de Films AutoensambladosCAC-CNEA (Buenos Aires)- Departamento de Química Coord. Dr. Galo Soler-IlliaAplicaciones de sistemas nano/mesoestructuradosUNRC (Córdoba)- Departamento de QuímicaCoord. Dr. C. BarberoDesarrollo de nuevos métodos de nano/microfabricaciónCONICET-UNLP (Buenos Aires) INIFTACoord. Dr. R. SalvarezzaDispositivos en nanoescalaUNSL (San Luis)- Departamento de QuímicaCoord. Dr. R. OlsinaNanobiotecnologíaUBA (Ciudad de Buenos Aires)- InquimaeCoord. Dr. E. J. Calvo 50 Investigadores y 40 estudiantes, 7 nodos.

Incluye químicos, físicos ingenieros y bioquímicos

L /μm0 1 2 3 4 5

z /n

m

0100200

L /μm0 1 2 3 4 5

z /n

m

0100200

(a)

(b)

(c)Imprinted Cu surface

Micromolded TiN Stamp(d)

(e)

Nanopartículas Materiales Aplicaciones nanoestructurados biomédicas

catálisisbiosensores microanálisis

Películas moleculares Stampers Nanotubos

NAD+ + H+

NADH

2 e-

NAD+ + H+

NADH

2 e-

Proyecto Laboratorio en Red para el Diseño, la Fabricación y Caracterización de Dispositivos MicroElectroMecánicos (MEMS) / “Red LabMEMS”

CNEA Constituyentes y BarilocheCoNAEFacultad de Ingenieria-UBAEscuela de Ciencia y Tecnología -UNSAMCentro de Tecnologías Analogicos-Digitales - UNLPINTEC-CONICET(Santa Fe )Instituto de Tecnología-UNSAM Univ. Nacional de Entre RíosCIOP-CONICET

Director:Dr. Alberto Lamagnaalamagna@cnea.gov.ar

RED ARGENTINA DE NANOCIENCIA Y NANOTECNOLOGIA: Materiales nanoestructurados y Nanosistemas (MaN)

I.- Nanomagnetismo y Espintrónica. Nodo: Centro Atómico Bariloche-IB, CNEA-UNCCoordinador: Carlos Balseirobalseiro@cab.cnea.gov.ar

II.- Superficies y Recubrimientos Nodo: Universidad Nacional de San LuisCoordinador: Giorgio Zgrablich

V.- Nueva Instrumentación Nodo: Universidad Nacional de Buenos AiresCoordinador: Oscar Martínez

III.- Propiedades electrónicas y optoelectrónicasde Sistemas Nanoestructurados:Nodo: Universidad Nacional de CórdobaCoordinador: Horacio PastawskiIV.- Películas Delgadas y Nanoestructuras :Nodo: Centro Atómico Constituyentes, CNEACoordinador: Alberto Regazzoni

Some Examples in Environmentally-oriented

N&N in Argentina

NOO

O

O

O

O

Ti

Ti

OTi

O

OTiOH

OTi...

OT

OTi.

OTi...

OTi...

Nano oxide and light activateO2+pollutant ⇒ CO2

Photocatalysis

Pollutant molecules adsorb on thesurface and light helps to destroy them

(Pilkington self-cleaning glass)

Photocatalysis onnanostructured TiO2

M. A. Blesa; M. Litter (CNEA)S. A. Bilmes; R. J. Candal (FCEN, UBA)O. Alfano, A. Cassano (INTEC, CONICET)

hνh+

e-

O2

H2O

CO2

ORG

Nanotech for water purification

Sullivan, C.A., (2001) The potential for calculating a meaningfulWater Poverty Index. Water International, 26: 471-480

SOLWATER reactor

C. Navntoft, P. Araujo, M.I. Litter, M.C. Apella, D. Fernández, M.E. Puchulu, M. del V. Hidalgo and M.A.

Blesa. J. Sol. Energy Eng. 129, 127-134

Composite TiO2/binder(PDMS)/sensitizer

0,00

0,05

0,10

42

43

0 30 60 90 120 1500

2

4

6

8

log

(UFC

mL-1

)

Tiempo / min

TFF

/ n

M m

in-1

mg-1

viability

Respiratoryactivity

Exposure to 4 h solar treatment leads towater disinfection. Most bacteria are eliminated.

Interesting water detox treatment forregions with poor access to energy

3-10 nm

MesoporousTiO2

Higher surface area (150-200m2/g)Controlled pore sizeHigh efficiency

Nanoporous titania Spheres

• Large particle size, easyseparation

• Nanopores: high andavailable area

• Results compare favorably with P-25

(b)

5 μm

(c)

5 μm

(a)

(d)

t / min

0 10 20 30 40 50 60

A/A

o (14

19:1

272

ir ba

nd)

0,0

0,2

0,4

0,6

0,8

1,0

M. Blesa, P. Araujo G. Soler Illia (CNEA)

Industrial detox

• Nanotek• Local

development• Nano-materials

and on-siteprocessing

• Removal of As(V) and otherpollutants fromgroundwater

• Linked toAcademia (CINN)

http://www.nanoteksa.com/

SensorsTransduction of physical/chemicalinformation into a signal

• Concentration• Speciation• Kinetics

In situ, massive, cheap, reliable, robust

http://www.narizelectronica.com.ar/paginas/funcionamiento.htm

E-nose project. A. Lamagna, CNEAM. Negri, FCEN, UBA

Fuel Cells

• Extremely active area• Opportunities for N&N

approaches– Catalysts– Electrodes– Membranes

• Numerous groups (CNEA, CITEFA, INIFTA, FCEN-UBA, etc)

• Core project (PAE-hydrogen)• High Temperature Cells• Polymer membrane cells

(methanol)

Our work:Mesoporous materials

• Photovoltaic cells• Fuel cells• Selective sensors• Smart windows

450 nm

Porous films: buildings with nano-windows

PO

O

OR

RSi

Ti

OTi

O

OTi

OH

OH

OTi...

OTi

OTi..

OTi...

OTi...

O

450 m

P. C. Angelomé, PhD Thesis, 2008

Nano Filters

pollutant

S

Ti

HgS

Ti

S

Ti

HgS

Ti

Modified oxides trap poisonous Hg2+

O

OH

OH

O

SH

Angelomé et al. Chem. Mater., 2005New J. Chem., 2005

J. Mater. Chem., 2006Soler-Illia et al. Chem. Commun., 2005

Perm selective membranes

-600 -400 -200 0 200 400 600 800

-0.6

-0.4

-0.2

0.0

0.2

0.4

0.6 MP TiO2

J (m

Acm

-2)

E (mV)

•TiO2 surface-modified with 2xC16•Charged probes “bounce”•Lipophylic probes are detected

•Modified selective nanomembrane

Porous film: accesible to Fe(CN)63– , Fc(OH)2

FC/DHDP mod

Fc/DHDP mod

P

O

OH

O

OCH3

CH3

Angelomé et al. Adv. Mater. 2006Otal et al. Adv. Mater., 2006

Calvo et al. Chem. Mater., 2008

Cyclic voltammetry

•Accessible MP oxide as NP template

•Nano-Au robust electrodes

• SERS active coatings(A. Fainstein)

•Intimate contact MO2-NP

•Tailorable plasmon position(n matrix)

Nanocomposites

1

2

3

CdS@SiO2M.C. Marchi

V. Della SaviaE. Otal

S. Aldabe-Bilmes

Pérez et al., Langmuir 2004Fuertes et al., Small 2008

Pérez et al., Langmuir 2004Fuertes et al., Small 2008

Ultra sensitive sensors

A. Wolosiuk, S. A. Bilmes. N. Tognalli, A. Fainstein et al., submitted, 2008

A. Wolosiuk, S. A. Bilmes. N. Tognalli, A. Fainstein et al., submitted, 2008

800 900 1000 1100 1200 1300

3000

4000

5000

6000

7000 1) Zr1 2) Zr2 3) Zr3 4) Zr4

Inte

nsity

[cou

nts]

Raman shift [cm-1]

1)

2)

3)4)

Thiopyridine@ 514nm, 10mW, 120s, 3x

Aims of our groupExpertise in synthesis of nanomaterials

Nanomaterials forapplications in

– Environment• Pollutant trapping• Photocatalysis• Sensing membranes

– Energy• Solar cells• Fuel cells

– Nuclear Materials• Selective ion separation• Novel fuels

Conclusion:• N&N useful for “green” approach

– Harness nanomaterials → Efficiency– Fields of application: Environment, Energy, sustainable processes

• Advances in Nanotechnology– Today: incremental– Tomorrow: breakthrough (depends on funding)

• Nano in Argentina– Mostly Nanoscience but applications upcoming

• Sensors• Detoxification• Fuel Cells

– Networking creates contacts– Formation of Highly trained Human Resources– Equipment (critical)– Next steps

• Accurate assessment of possibilities (dialogue)• Jump to appliocations (academia-industry)

Thank you!

2008

2006

2004