Nanomaterials Design: Challenges Nanomaterials Design: Challenges and Opportunitiesand Opportunities
Professor G.Q. Max Lu Professor G.Q. Max Lu Professor G.Q. Max Lu Professor G.Q. Max Lu Fed Fellow FTSEFed Fellow FTSEFed Fellow FTSEFed Fellow FTSE
ARC Centre for Functional NanomaterialsARC Centre for Functional NanomaterialsARC Centre for Functional NanomaterialsARC Centre for Functional NanomaterialsThe University of Queensland, AustraliaThe University of Queensland, AustraliaThe University of Queensland, AustraliaThe University of Queensland, Australia
Http://Http://Http://Http://www.arccfn.org.auwww.arccfn.org.auwww.arccfn.org.auwww.arccfn.org.au
ARC Centre for
Functional
Nanomaterials
ARC Centre for
Functional
Nanomaterials
The University of Queensland (UQ)
• Founded in1910• 38,100 students
• 6,400 international students from130 countries
• 10,304 postgraduate students
• Comprehensive & research intensive
Australian Institute of Bioengineering and Nanotechnology (AIBN)
• The University of Queensland, Queensland Government, and a private benefactor (The Atlantic Philanthropies) have together provided over $72m to establish AIBN.
• It conducts multidisciplinary research at the interfaces between the physical and biological sciences, to develop new materials, devices and processes based on bioengineering and nanotechnology addressing key health, energy andenvironmental issues
Vision
To build a world-class institute of excellence, with collaborative links to leading research institutions and industries
AIBN Research Programs
1. Nanotechnology for Energy & the Environment
2. Cell & Tissue Engineering
3. Systems Biotechnology
4. Biomolecular Nanotechnology
$72m, 16 Groups/Centres, With 280 researchers
www.aibn.uq.edu.au
Nanoparticles
NanotubesThin films/membranes
Nanoporous/composite
products
techniques materialsNanoscale Sciences Nanoscale Sciences
Too
ls:
X-R
ays,
NM
R, M
icro
scop
y,
Spec
tros
copy,
Mol
ecula
r m
odel
ling A
pplication
s:
Clean
energy,en
vironm
ent
health
care•• 4 Universities4 Universities
((UQ,UNSW, ANU, UWS)UQ,UNSW, ANU, UWS)
•• over 100 researchersover 100 researchers
•• $12.5M $12.5M
Max Lu Group: >50Senior researchers:Joe da Costa
Jorge Beltramini
Lianzhou Wang
Mikel Duke
Gordon Xu
Denisa Jurakuva
Shizhang Qiao
Xiangdong Yao
Http://www.arccfn.org.au
ARC Centre for
Functional
Nanomaterials
ARC Centre for
Functional
Nanomaterials
Centre StructureCentre StructureInternational
Advisory Board
Management Committee Program leaders, nominated CIs
Director –
Prof Max Lu
Admin Assistant
Chief Op. Officer Steve Coombs
NSW/ACT Node
Director –R. Amal
Nano-Biomaterials(Matt Trau)
Films &Membranes(Ian Gentle)
Comput.Nanomaterials
Science(Sean Smith)
Nano-Particles
(Rose Amal)
Nanotubes (Ying Chen)
Functional NanomaterialsFunctional Nanomaterials
From Nanostructures to Nano-Products
Examples of nanostructures in nature and nanotechnology
Proof of Concept
ProductMarket
Productsdevelopment
Properties
Testing
Materials Discovery
Molecular understandingand design
Research and Innovation PipelineResearch and Innovation Pipeline
Computational
Nanotechnology
Experimental Research
Programs
SPRINT
Industrial Linkages
Astute Nanotechnology
First Best
Nanotechnology Applications
Hea
lth
Agricu
lture
Man
ufa
cturing
Ener
gy/
Envi
ronm
ent
Min
eral
Res
ourc
esICT
Tra
nsp
ort
Water and Energy
Applications of nanomaterials
• Water – Desalination (nanofilters), water
reuse and recycling (photocatalysis)
• Energy – Nanocatalysts for GTL, biofuels
– Hydrogen separation membranes
– H2 Storage and Electrodes for Fuel cells
Hydrogen Economy
Hydrogen EconomyGlobal Global
WarmingWarmingAir Air
PollutionPollution
Environment Environment DestructionDestruction
Economic Economic DependenceDependence
Fossil FuelEconomy
Solution
Hydrogen Separation MembranesHydrogen Separation Membranes
� Science: Carbonised template stabilizes pore structure by inhibiting silica migration, solving a major challenge in silicamembranes to maintain a robust pore structure in presence of steam (Duke, et al., Adv. Funct. Mater. 16, 1215–1220, 2006).
� Application: H2/CO2 separation for clean fuels, fuel cells feed purification.
� IP and End Users: Worldwide patentJohnson Matthey, Low Emissions Technology, FZ Julich, Germany, Stanwell
Mobility hindered and Mobility hindered and
permselectivepermselective structure structure
maintainedmaintained
Molecular Sieve Silica MembranesMolecular Sieve Silica Membranes(Effective pore diameter: 0.35(Effective pore diameter: 0.35--1nm)1nm)
uniformsolution sol xerogel
filmdensefilm
Gelation &evaporation
heat
Methyltriethoxysilane (MTES),
tetraethylorthosilicate (TEOS),
absolute ethanol (EtOH), nitric acid
(HNO3) and distilled water (H2O).
a-Alumina, 500nm,0.3
DaDa Costa, Lu and RudolphCosta, Lu and RudolphWO200193993; AU200173734; EP1299178WO200193993; AU200173734; EP1299178--
A1;JP2003534907A1;JP2003534907--W; US2004038044W; US2004038044--A1A1
Temperature (oC)
50 100 150
Flu
x (
mo
l.m
-2.s
-1)
1e-6
1e-5
1e-4
1e-3
H2 (CH
4)
H2 (CO
2)
CO2 (H2)
CH4 (H
2)
• 50/50 mixtures @ pi=50kPa• Permeation of gases in a mixture increases with temperature.
Partial Feed Pressure of gas (i) (kPa)
0 20 40 60 80 100α
i/j
0.1
1.0
10.0
100.0 H2/CH4
H2/CO2
CO2/CH4
pj/pi
J2 MSS membrane
Gas Separation MembranesGas Separation Membranes
Molecular Sieve membraneMolecular Sieve membrane
Hydrogen EconomyHydrogen Economy
US DOE US DOE FutureGenFutureGen
Hydrogen Storage Targets
• US DOE benchmarks
– 4.5 wt%, 1.2 kWh/L, and $6/kWh, by 2005
– 6.0 wt%, 1.5 kWh/L, and $4/kWh, by 2010
– 9.0 wt%, 2.7 kWh/L, and $2/kWh, by 2015
• IEA benchmark
– 5.0 wt.% and 50 kg H2/m3
MgH2 nanocomposites
Mg
Transition MetalsFe, V, Ti, Mn
Metal OxidesNb2O5 , TiO2, V2O5
Carbon NanotubesSWCNT/MWCNT
Catalysts and CNT decrease the heat of formation of (Mg,X)H2 and weaken bonding Mg-H; rate limiting: disassociation and recombination of H2, thus beneficial to have nanophased catalysts, and MgH2
Nanomaterials for H2 Storage and Fuel Cells
L. Schlapbach and A. Züttel, Nature, Vol. 414, 353-358, 2001
Ads-H2 (5-10wt%)
Developed a patented
new material with high
H2 storage capacity
and fast charging and discharging kinetics
4.5%H4.8%H1500C/60min
5.2%H5.2%H5.8%H4.7%H2000C/15min
Mg-Cata4Mg-Cata3Mg-Cata2Mg-Cata1
Salata, J Nanobiotechnology, 2004
Multifunctional Nanoparticles
LDH Nanoparticles LDH Nanoparticles � Novel technique for layered double
hydroxide (LDH) nanoparticles with good particle size and stability control ( PCT patent filed) (Xu et al, J. Am. Chem. Soc.128, 36-37, 2006).
� A world first technique in tailoring these particular nanoparticles and holds promise for efficient cellular drug and DNA delivery.
MgAl-Cl-LDH
50-100 nm
Membrane
cytoplasm
nucleus
LDH-FITC NP
Layered Double Hydroxides (LDH)
•layered structure is related to brucite (Mg(OH)2). Mg2+ is partially substituted with Al3+, resulting in a positively charged layer. Anions in the interlayer keep the charge balanced.
• Hydrotalcite: Mg3Al(OH)8(CO3)1/2 2H2O
• LDH: M2+xM
3+(OH)2(1+x)An-
1/nmH2O (x = 2-4, m = ∼2 )
Polymorphic stackingpatterns:
(a) hexagonal,
(b) rhomohedral.Mg3Al(OH)8(CO3)1/2 2H2O
Synthesis: CoSynthesis: Co--precipitation and hydrothermal precipitation and hydrothermal
refiningrefining
2Mg2+(aq) + Al3+(aq) + 6OH- + Cl- → Mg2+2Al3+(OH)6Cl (s)
Mg2+ + Al3+
solution
NaOH solution
1-10 micrometers
-2
3
8
13
18
10 100 1000 10000
Particle size (nm)
Inte
ns
ity
(%
)
100C 16 h
25C 20 m
Xu, Lu and Bartlett, JACS, 128, 36-37, 2006
Morphology
5-500 nm
30-5000 nm
MgAl-Cl-LDH
50-100 nm
100 nm
Nanoparticle Carriers for Drug and Gene Delivery
+ + + + +
+ + + + +
+
+
+
++
+
+
+
---
----
--
--
- -
-
- -
Inside
LDH particles carry positive charges overall, e.g. Mg2Al-CO3-LDH (∼100 nm) has zeta potential of +40-50 mV.
+ + + + +
+ + + + +
- - - - -
LDH-NO3
Exchange
+ + + + +
+ + + + +
LDH-DNA
LDH-FITC Transfection into Cell necleus
Membrane
cytoplasm
nucleus
LDH-FITC NP
membrane
cytoplasm
nucleus
FITC2-
O-
COO-
NCS
OO
Fluorescent Cells
Day 2, [DNA]=1.0 µg/mL. Day 3, [DNA]=1.0 µg/mL.
Mag=20 Mag=10
Design of Design of NanocapsulesNanocapsules for for
BiomoleculesBiomolecules� Science: We discovered a
new synthesis route for hollow spheres of silica with tuneable wall thickness (Djojoputro et al., J. Am. Chem. Soc. 128, 6320-6321,
2006).
� Application: Remarkable capacity to store and release drugs and enzymes
Hybrid Silica
-N+ −−−−OSi-
FC4 CTAB+ Hybrid Silica
Crystallization Extraction
VT LCT
� IP and End-Usersknow-how Novozyme, Denmark
Release of Ibuprofen from hollow and solid PMO at pH = 7.4
(a & c) FC4/CTAB ratio = 0.6,
(b & d) FC4/CTAB ratio = 1.2Djojoputro, et al. J Am Chem Soc, 128,
2006, 6321
Photocatalysis on Nanocrystalline TiO2
TiOTiO22 NanoparticlesNanoparticles
� Science: Developed a novel Fe-coated TiO2
nanoparticle by flame pyrolysis method –showing visible light photocatalysis (Teoh, Amal, Mädler, Pratsinis, Catal. Today 2006)
� Application: Water purification, Anti-bacterial,
self-cleaning surfaces.
� IP and End-Users: Provisional Patent filed.
Industrial partners: Orange County Water District Authority, USA CH2M Hill, and G. James Pty Ltd.
20 nm
Uses of Nanoparticle TiO2
A mirror coated with 8A mirror coated with 8--
10nm 10nm TitaniaTitania nanoparticlesnanoparticles
a) Without templating, and b) with PEO as template
TiOTiO22 photocatalyticphotocatalytic water purificationwater purification
0 s 15 s 1 min 0 s 15 min 1 h
Our catalystOur catalyst Degussa P25Degussa P25
Dramatically improved settling -recovery rate
Photoclean filter apparatus
Air PurificationComparison of NQ titania with Degussa P25
time (minutes)
rela
tiv
e c
on
ce
ntr
ati
on
(-)
destruction rates: NQ and P25
0 60 120 180 240 300 360 420 480 540 600 660 7200
0.2
0.4
0.6
0.8
1
NQ (formaldehyde, normalized) 8W
P25 (acetone measured) 60W
NQ (calculated) 60W
Normalised Formaldehyde reduction for Models 4 & 5, %
0
10
20
30
40
50
60
70
80
90
100
0 200 400 600 800 1000 1200
Time (mins)
Model 4
Model 5
– Indoor (homes, buildings and
vehicles)
– VOCs, Viruses, cigarette smoke etc.
Industrial air clean-up (organics)
– Industrial emissions (styrene, paint
fumes, dioxins)
– Ventilation tunnels
AcknowledgementsAcknowledgements
•• Research associates and students:Research associates and students: Dr. Gordon Dr. Gordon XuXu, Dr , Dr ShizhangShizhang QiaoQiao, Dr X, Yao, Dr , Dr X, Yao, Dr DenisaDenisa JurcakovaJurcakova, Dr Joe , Dr Joe dadaCosta, Dr Z. Ding, Dr M. Duke, I. Costa, Dr Z. Ding, Dr M. Duke, I. KartiniKartini, Dr. S. , Dr. S. GiesslerGiessler, Dr. J. , Dr. J. BeltraminiBeltramini, Dr Z.H. Zhu, Dr B. , Dr Z.H. Zhu, Dr B. LadewigLadewig, Dr W. Hogarth, Katie , Dr W. Hogarth, Katie PorazikPorazik, Tom , Tom RuffordRufford, Tom Cheng, Melvin Lim, , Tom Cheng, Melvin Lim, AkshatAkshatTanksaleTanksale, , YunyiYunyi Wong, Wong,
•• Collaborators:Collaborators: Perry Bartlett, HM Cheng, Peter Gray, Anton Perry Bartlett, HM Cheng, Peter Gray, Anton MiddlebergMiddleberg
•• Australia Research Council (ARC large, small and SPIRT grants; Australia Research Council (ARC large, small and SPIRT grants; QEII Fellowships, Fed Fellowship)QEII Fellowships, Fed Fellowship)
•• The University of Queensland (VCThe University of Queensland (VC’’s Strategic Initiative Funds)s Strategic Initiative Funds)
•• Queensland Sustainable Energy AwardQueensland Sustainable Energy Award
•• Queensland Brian InstituteQueensland Brian Institute
•• Australian Institute of Bioengineering and Nanotech.Australian Institute of Bioengineering and Nanotech.
•• Johnson Matthey, UK and Nanoquest Pty LtdJohnson Matthey, UK and Nanoquest Pty Ltd