state-of-the-art flame synthesis of nanoparticles · state-of-the-art flame synthesis of...
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![Page 1: State-of-the-art Flame Synthesis of Nanoparticles · State-of-the-art Flame Synthesis of Nanoparticles Dr. Frank Ernst ernst@ptl.mavt.ethz.ch Particle Technology Laboratory, Department](https://reader034.vdocument.in/reader034/viewer/2022042312/5eda8b44ca56d138585eb2ed/html5/thumbnails/1.jpg)
State-of-the-art Flame Synthesis of Nanoparticles
Dr. Frank Ernst
Particle Technology Laboratory,
Department of Mechanical and Process Engineering
ETH Zurich, www.ptl.ethz.ch 200 nm
Verbrennung und chemisch reaktive Prozesse in der Energie- und Materialtechnik
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1 - 100 nm (at least into two dimensions)
The thickness (diameter) of a
human hair is 50,000 - 100,000 nm!
Nanoparticles
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Melt
ing
Po
int,
K
Particle diameter, Å
Au
Buffat and Borel, Phys. Rev. A 13, 2287 (1976)
The Melting Point Decreases
with Decreasing Nanoparticle Size
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Large surface area per gram
(adsorbents, membranes)
Stepped surface at the atomic level (catalysts)
Easily mix in gases and liquids (reinforcers)
Superfine particle chains (recording media)
Easily carried in an organism
(new medicines)
Cosmetics that last way into the night ...
Some people believe that nanoparticles are
a new state of matter!
10 mm
10 nm
SSA = 0.2 m2/g
SSA = 200 m2/g
Applications of Nanoparticles
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How are they made?
Many processes & synthesis conditions…
Plasma-arc
Laser ablation
Chemical Vapor Deposition
Wet-phase chemistry
etc.
Need synthesis technique that is:
Rapid, continuous & scaleable
Flame synthesis…
carbon black
TiO2
SiO2
C60/C70
Scale-up
limitations
106 t/year
103 t/year
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TiCl4
TiCl4
TiCl4 H2
H2 H2 O2
O2 O2
TiO2
TiO2
TiO2 TiO2
H2O
H2O H2O
HCl
HCl
Particle formation & growth – flames
Chemical reaction
Nucleation
Aggregation
Coagulation
25
00
20
00
15
00
10
00
50
0
T (K)
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H He
Li Be B C N O F Ne
Na Mg Al Si P S Cl Ar
K Ca Sc Ti V Cr Mn Fw Co Ni Cu Zn Ga Ge As Se Br Kr
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
Fr Ra Ac
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
Vapor flames
Can make many interesting materials:
Fillers for composites, catalysts etc.
However, limited compositions
C, TiO2, SiO2, Al2O3
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TiCl4
TiCl4
TiCl4 H2
H2 H2 O2
O2 O2
TiO2
TiO2
TiO2 TiO2
H2O
H2O H2O
HCl
HCl
Vapor flames
Chemical reaction
Nucleation
Aggregation
Coagulation
25
00
20
00
15
00
10
00
50
0
T (K)
Reactants in vapor phase
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Spray flames
Reactants in LIQUID phase
Keep aerosol processes
Dispersed
Product-
Molecules
& Cluster
Droplets contain:
- Organic solvent (comb. energy)
- Reactant precursor compound
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Spray flames
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Flame synthesis
Dispersed
Product-
Molecules
& Cluster
30
mm
300 nm
Vapor Flame Spray Flame
200 nm
Mädler, L., Kammler, H.K., Mueller, R., and Pratsinis, S.E., J. Aerosol Sci. 33 (2) 369-389 (2002).
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H He
Li Be B C N O F Ne
Na Mg Al Si P S Cl Ar
K Ca Sc Ti V Cr Mn Fw Co Ni Cu Zn Ga Ge As Se Br Kr
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
Fr Ra Ac
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
Spray Flame Pyrolysis (FSP)
Liquid enables composition flexibility
Opens up many possibilities…
H He
Li Be B C N O F Ne
Na Mg Al Si P S Cl Ar
K Ca Sc Ti V Cr Mn Fw Co Ni Cu Zn Ga Ge As Se Br Kr
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
Fr Ra Ac
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
Spray flames
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Single-phase particles & aggregates
Mixed-phase & composition
Embedded, surface clusters & shells
Surface functionalization
Formulations
Immobilization, films & 2D coatings
Devices
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Tailor-made particle structures
(size, morphology, crystallinity etc.)
with a large variety chemical compositions
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Flame Spray Pyrolysis
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Au on TiO2
15 nm
Mädler, L., Stark, W.J., Pratsinis. S.E., J. Mater. Res., 18 (1), 115-120 (2003).
In-situ deposition of noble metals
For applications in
catalysts
sensors
optical devices, etc.
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Au wt%
4.02.01.0
Aver
age
cryst
al s
ize,
nm
0
5
10
15
20
Au / TiO2 (~ 100 m2/g)
Concentration vs. crystallite size
Mädler, L., Stark, W.J., Pratsinis. S.E., J. Mater. Res., 18 (1), 115-120 (2003).
Doubling gold concentration
doubles Au crystallite size
leaves support unchanged
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Au wt%
4.02.01.0
Aver
age
cryst
al s
ize,
nm
0
5
10
15
20
Au / TiO2 (~ 100 m2/g)
Au / SiO2 (~ 320 m2/g)
Concentration vs. crystallite size
Doubling gold concentration
doubles Au crystallite size
leaves support unchanged
Gold particle size is independent of ceramic supporting surface area
Mädler, L., Stark, W.J., Pratsinis. S.E., J. Mater. Res., 18 (1), 115-120 (2003).
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Flame Spray Pyrolysis
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Glucose sensor Proton Exchange
Membrane
Fuel Cell
detection of
• hydrogen peroxide
• biomolecules (glucose,
choline, ...)
• hydrogenation
• oxidation
• reforming
• electrodes for fuel cells
www.minimed.com www.gavial.com
Ernst et al., J. Mat.Chem., 20 (6), 2117-2123 (2008).
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time (min)
0 20 40 60 80 100
Cyclo
hexene c
onvers
ion (
%)
0
20
40
60
80supported(12 wt% Pt)
reference(5 wt% Pt)
supported(10 wt% Pt)
embedded(2.6 wt-%)
Hydrogenation of cyclohexene
Ernst et al., J. Mat.Chem., 20 (6), 2117-2123 (2008).
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Single-phase particles & aggregates
Mixed-phase & composition
Embedded, surface clusters & shells
Surface functionalization
Formulations
Immobilization, films & 2D coatings
Devices
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120°C
500°C Oxygen
Methane
Oxygen
Oxygen
Precursor liquid
Syringe pump
MFCs
Exhaust ventFilter housing
Spray flame
Support flame
Shield gas
PIPI
Water inWater out
Deposition
substrate
sensing area: 7 x 3.5 mm2
Mädler et al., European patent, Dec. 9th 2004.
Direct deposition on sensor substrate
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500 mm
SnO2
Deposition time: 180 s
Layer morphology – top view
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500 mm
SnO2
5 mm
Deposition time: 180 s
Layer morphology – top view
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Al2O3 5 mm
SnO2
Deposition time: 180 s
Layer morphology – cross section
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Single-phase particles & aggregates
Mixed-phase & composition
Embedded, surface clusters & shells
Surface functionalization
Formulations
Immobilization, films & 2D coatings
Devices
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Examples for FSP materials
50 nm
5 nm
Mädler, et al., J. Appl. Phys (2002).
Stark, W. J. et al., A., Chem. Commun. (2003).
Strobel, R. et al., J. Catal. (2003).
Metal oxides
SiO2, TiO2, Al2O3,
Bi2O3, CeO2, ZnO
Mixed metal oxides
SiO2/TiO2 ,V2O5/TiO2,
ZnO/SiO2, Zn2SiO4,
BaTiO3, CexZr(1-x)Oy
Noble metals
on oxides
Au, Pt, Pd on
TiO2, SiO2, Al2O3
200 nm Versatile Process
TiO2
Bi2O3
hollow
CexZr(1-x)Oy
ZnO/SiO2
Pt on
Al2O2
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Mueller et al., Chem. Eng. Sci., 58 (10), 1969 - 1976 (2003).
Scale-up
40 cm
HMDSO/EtOH spray flame
producing 300 g/h of silica.
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70
50
30
10
BE
T-e
qu
iva
len
t d
iam
ete
r, n
m
12009006003000
Production rate, g/h
1.26 M
3.0 M
4.7 M
Vapor Flames*
Oxygen12.5 l/min 50 l/min
SiO2 -
Scale-up
40 cm
HMDSO/EtOH spray flame
producing 300 g/h of silica. Mueller et al., Chem. Eng. Sci., 58 (10), 1969 - 1976 (2003).
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Nanoparticles for Materials
Flame Spray Pyrolysis & metal-oxide materials Vapor Spray flame: extend range of accessible
compositions
Flame Spry Pyrolysis (FSP)
Metal-oxide nanomaterials for many applications
Metal on metal-oxides
Sensors and emerging areas…
Nanoparticle Technology is a frontier for scientific
advances and business opportunities
Lecture summary