Nanomaterials Design: Challenges

and Opportunities
Professor G.Q. Max Lu Fed Fellow FTSE
ARC Centre for Functional Nanomaterials
The University of Queensland, Australia
Http://www.arccfn.org.au
Http://www.arccfn.org.au
ARC Centre for
Functional
Nanomaterials

The University of Queensland (UQ)

Founded in1910
38,100 students
6,400
international
students from130
countries
10,304 postgradu
ate 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 and
environmental 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

ARC Centre for

Functional
Nanomaterials

4 Universities

Max Lu Group: >50

Senior researchers:

Nanoparticles
Nanotubes
Thin films/membranes
Nanoporous/composite

techniques

Http://www.arccfn.org.au

Nanoscale Sciences

ent

Joe da Costa
Jorge Beltramini
Lianzhou Wang
Mikel Duke
Gordon Xu
Denisa Jurakuva
Shizhang Qiao
Xiangdong Yao

To
ol

over 100 researchers

$12.5M

m
ns: iron

XRa s:
Sp
ect ys, N
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cop , M
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ole osco
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(UQ,UNSW, ANU, UWS)

i o nv
cat y,e
pli erg
Ap an en are
Cle lth c
hea

elli
ng

products

materials

Centre Structure
International
Advisory Board
Admin Assistant
NSW/ACT Node
Director R. Amal

Director

Chief Op. Officer

Prof Max Lu

Steve Coombs

Management Committee
Program leaders, nominated CIs

NanoParticles
(Rose Amal)

Nanotubes
(Ying Chen)

Films &
Membranes
(Ian Gentle)

Comput.
NanoBiomaterials Nanomaterials
Science
(Matt Trau)
(Sean Smith)

Functional Nanomaterials

From Nanostructures to Nano-Products

Examples of nanostructures in nature and nanotechnology

Research and Innovation Pipeline

Molecular
understanding
and design

Materials
Discovery

Properties
Testing

Proof of
Concept
Product

Products
development

Market

Computational
Nanotechnology
Experimental Research
Programs
SPRINT
Industrial Linkages
Astute Nanotechnology

First

Best

rt

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ltu

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nm iro
en
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Re Mi
so ne
ur ral
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Nanotechnology Applications

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 Economy
Air
Pollution

Global
Warming

Fossil Fuel
Economy
Environment
Destruction

Solution

Economic
Dependence

Hydrogen Separation Membranes

Science: Carbonised template stabilizes pore structure by
inhibiting silica migration, solving a major challenge in silica
membranes to maintain a robust pore structure in presence
of steam (Duke, et al., Adv. Funct. Mater. 16, 12151220,
2006).

Application: H2/CO2 separation for clean fuels, fuel cells
feed purification.

IP and End Users: Worldwide patent
Johnson Matthey, Low Emissions
Technology, FZ Julich, Germany,
Stanwell

Mobility hindered and

permselective structure
maintained

Molecular Sieve Silica Membranes

(Effective pore diameter: 0.35-1nm)
uniform
solution

sol

xerogel
film

dense
film

a-Alumina, 500nm,0.3

Gelation &
evaporation

heat

Methyltriethoxysilane (MTES),
tetraethylorthosilicate (TEOS),
absolute ethanol (EtOH), nitric acid
(HNO3) and distilled water (H2O).

Da Costa, Lu and Rudolph

WO200193993; AU200173734; EP1299178EP1299178A1;JP2003534907A1;JP2003534907-W; US2004038044US2004038044-A1

J2 MSS membrane
1e-3
H2 (CO2)

100.0

H2/CH4
H2/CO2

H2 (CH4)

Flux (mol.m-2.s-1)

1e-4

10.0

i/j

CH4 (H2)

CO2/CH4

1.0
1e-5

pj/pi

CO2 (H2)

0.1

1e-6
50

100

150
o

20

40

60

80

100

Partial Feed Pressure of gas (i) (kPa)

Temperature ( C)

50/50 mixtures @ pi=50kPa

Permeation of gases in a mixture increases
with temperature.

Gas Separation Membranes

Molecular Sieve membrane

US DOE FutureGen

Hydrogen Economy

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
Transition Metals
Fe, V, Ti, Mn

Mg
Metal Oxides
Nb2O5 , TiO2, V2O5

Carbon Nanotubes
SWCNT/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. Zttel,
Nature, Vol. 414, 353-358,
2001

Ads-H2 (5-10wt%)

2000C/15min
1500C/60min

Mg-Cata1

Mg-Cata2

Mg-Cata3

Mg-Cata4

4.7%H

5.8%H

5.2%H

5.2%H

4.8%H

4.5%H

Developed a patented
new material with high
H2 storage capacity
and fast charging and
discharging kinetics

Multifunctional Nanoparticles

Salata, J Nanobiotechnology, 2004

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.

Membrane

cytoplasm

MgAl-Cl-LDH
50-100 nm

LDH-FITC
NP
nucleus

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+xM3+(OH)2(1+x)An-1/nmH2O (x = 2-4, m = 2 )

Polymorphic stacking
patterns:
(a) hexagonal,
(b) rhomohedral.
Mg3Al(OH)8(CO3)1/2 2H2O

Synthesis: Co-precipitation and hydrothermal

refining
2Mg2+(aq) + Al3+(aq) + 6OH- + Cl- Mg2+2Al3+(OH)6Cl (s)

Mg2+ + Al3+
solution

NaOH solution

1-10
micrometers

18
100C 16 h

Intensity (%)

13

8
25C 20 m

-2
10

100

1000

Particle size (nm)

10000

Xu, Lu and Bartlett, JACS, 128, 36-37, 2006

Morphology
100 nm

5-500 nm
30-5000 nm

MgAl-Cl-LDH

50-100 nm

Nanoparticle Carriers for Drug and Gene Delivery

LDH particles carry positive charges overall, e.g. Mg2Al-CO3-LDH (100
nm) has zeta potential of +40-50 mV.
+ + + + +

+ + + + +

- - - - Exchange

+ + + + +

+ + + + +
LDH-DNA

LDH-NO3

+
+

+
+
+ + + + +
+ + + + +
+
+

+
+

- - -

Inside

LDH-FITC Transfection into Cell necleus

Membrane
cytoplasm

nucleus
nucleus
LDH-FITC NP

S
C
N

membrane
cytoplasm
O
O
C

FITC2-

Fluorescent Cells

Day 2, [DNA]=1.0 g/mL.

Day 3, [DNA]=1.0 g/mL.

Mag=20

Mag=10

Design of Nanocapsules for

Biomolecules

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

IP and End-Users
know-how
Novozyme, Denmark

VT

LCT

-N+ OSiFC4

Crystallization

Hybrid
Silica

CTAB+
Hybrid Silica

Extraction

Release of Ibuprofen from hollow

and solid PMO at pH = 7.4

(a & c) FC4/CTAB ratio = 0.6,

(b & d) FC4/CTAB ratio = 1.2

Djojoputro, et al. J Am Chem Soc, 128,

2006, 6321

Photocatalysis on Nanocrystalline TiO2

TiO2 Nanoparticles

Science: Developed a novel Fe-coated TiO2
nanoparticle by flame pyrolysis method
showing visible light photocatalysis (Teoh,
Amal, Mdler, 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 810nm Titania nanoparticles

TiO2 photocatalytic water purification

0s

15 s

1 min

Our catalyst

0s

15 min

1h

Degussa P25

Dramatically improved settling -recovery rate

a) Without templating, and b) with

PEO as template

Air Purification
Comparison of NQ titania
with Degussa P25

Normalised Formaldehyde reduction for Models 4 & 5, %

100
90
80
70
60
50
40
30
20
10
0

Model 4
Model 5

200

Photoclean filter apparatus

400

600
Time (mins)

800

1000

1200

destruction rates: NQ and P25

1

vehicles)

VOCs, Viruses, cigarette smoke etc.

Industrial air clean-up (organics)
Industrial emissions (styrene, paint
fumes, dioxins)
Ventilation tunnels

relative concentration (-)

Indoor (homes, buildings and

0.8

NQ (formaldehyde, normalized) 8W

0.6

0.4

P25 (acetone

0.2

measured) 60W

NQ (calculated) 60W
0
0

60

120

180

240

300

360

420

time (minutes)

480

540

600

660

720

Acknowledgements
Research associates and students: Dr. Gordon Xu, Dr
Shizhang Qiao, Dr X, Yao, Dr Denisa Jurcakova, Dr Joe da
Costa, Dr Z. Ding, Dr M. Duke, I. Kartini, Dr. S. Giessler, Dr. J.
Beltramini, Dr Z.H. Zhu, Dr B. Ladewig, Dr W. Hogarth, Katie
Porazik, Tom Rufford, Tom Cheng, Melvin Lim, Akshat
Tanksale, Yunyi Wong,
Collaborators: Perry Bartlett, HM Cheng, Peter Gray, Anton
Middleberg
Australia Research Council (ARC large, small and SPIRT grants;
QEII Fellowships, Fed Fellowship)
The University of Queensland (VCs Strategic Initiative Funds)
Queensland Sustainable Energy Award
Queensland Brian Institute
Australian Institute of Bioengineering and Nanotech.
Johnson Matthey, UK and Nanoquest Pty Ltd