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 [email protected]
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, [email protected]
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 [email protected]
RED ARGENTINA DE NANOCIENCIA Y NANOTECNOLOGIA: Materiales nanoestructurados y Nanosistemas (MaN)
I.- Nanomagnetismo y Espintrónica. Nodo: Centro Atómico Bariloche-IB, CNEA-UNCCoordinador: Carlos [email protected]
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
[email protected]. 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