Nanomaterials

Advanced Catalytic Processes 2018

Doc. Mika Huuhtanen

Environmental and Chemical Engineering Research Unit
Definition of nanomaterials
“A natural, incidental or manufactured material containing particles, in an unbound state
or as an aggregate or as an agglomerate and where, for 50 % or more of the particles
in the number size distribution, one or more external dimensions is in the size range 1
nm - 100 nm.”*

“In specific cases and where warranted by concerns for the environment, health, safety
or competitiveness the number size distribution threshold of 50 % may be replaced by a
threshold between 1 and 50 %.”*

“By derogation from the above, fullerenes, graphene flakes and single wall carbon
nanotubes with one or more external dimensions below 1 nm should be considered as
nanomaterials.”*

*(Official Journal of the European Union L275/38, 20.10.2011)

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 What are nanomaterials, in general
‒ Nanoparticles are objects with all three external dimensions at the nanoscale.

‒ Nanoparticles which occur naturally (e.g., volcanic ash, soot from forest fires) or are by-
products of combustion processes (e.g., welding, diesel engines), are usually physically
and chemically heterogeneous and often called ultrafine particles.

‒ Engineered nanoparticles are intentionally produced and designed with very specific
properties related to shape, size, surface properties, and chemistry. These
properties are reflected in aerosols, colloids, or powders.

‒ Often, the behavior of nanomaterials may depend more on surface area than particle
composition itself. Relative-surface area is one of the principal factors that enhance the
reactivity, strength, and electrical properties of nanomaterials
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 oxides sulfides semiconductors
and compound
semiconductors
cationic dopants
co-catalyst metals
anionic dopants

http://wallboom.com/wp-content/uploads/2013/05/periodic-table-with-names.jpg University of Oulu

 What are nanomaterials, in general
‒ Engineered nanomaterials include e.g. carbon buckeyballs or fullerenes; carbon
nanotubes; metal or metal oxide nanoparticles and nanowires (e.g., gold, titanium dioxide);
various quantum dots, nanostars, etc...
‒ Engineered nanoparticles can be purchased from commercial vendors or generated via
experimental procedures by researchers in the laboratories.
‒ For example, carbon nanotubes (CNT) can be produced by laser ablation, HiPCO (high-
pressure carbon monoxide), arc discharge, and chemical vapor deposition (CVD).

Fulleren Carbon nanotubes Quantum dots Nanostars

Metal nanoparticles
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 Most common types
‒ Carbon based nanomaterials
- Nanotubes (CNT), fullerenes
‒ Metal based nanomaterials
- Quantum dots, nanogold, nanosilver,
stars, rods, wires and oxides with metal
bases
‒ Dendrimers
- Branched components that form
polymers and whose surface exhibit
chain ends suited for chemical
manipulation as tools
‒ Composites
- Combination of nanoparticles or
nanoparticles and other materials to
form unique nanomaterials (e.g.
catalysts)
Panikkanvalappil et al., Nano Rev. Exp., 2 (2011) University of Oulu
Various shapes and size

Govindaraju S. et al. (2018) 3 Biotech 8:113 Vasudevan D. et al. (2015) J. Alloys and Compouds 636: 395
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Nanoparticles form a dynamic system

Pt on polystyrene surface in HR-TEM

http://www.youtube.com/watch?feature=player_detailpage&v=ulrjiWrHLwo
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Carbon nanotube growth in situ...

© Wagner, Hansen & Dunin-

Borkowski

https://www.youtube.com/watch?v=B099DRAX_X4
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 Why nanomaterials...
‒ Not only chemical composition of the
nanomaterials but also their morphological
properties like size, shape and surface
properties determine their characteristics.
‒ Chemical properties, such as reactivity,
(photo)catalytic activities of a substance, and
energetic properties and their confinement
will and many times are different compared
to bulk materials.
‒ The properties of nanomaterials do NOT only
differ from their bulk counterpart but also
between different nanoforms of the same
material  changes in effects and behaviour.
http://www.petrosains.com.my/pusat2008/nanotech.html
‒ NOTE! Do not rely on the properties found
for bulk material!

(http://www.petrosains.com.my/pusat2008/nanotech.html)
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Properties of nanostructures
The shape and size affect how the functioning of the
nanostructures will change.

E.g. Au and Ag has certain colour in bulk mode, but when they
occur as nanostuctures the colour changed.

Motl et al. Chem. Soc.

Rev., 2014, 43, 3823-3834
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 Optical
properties
in surface
plasmon
resonance

From: Amendola V. et al
2017 J. Phys.: Condens.
Matter 29 203002
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http://www.nanowerk.com/nanotech
nology-applications.php

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Synthesis and characterization of
nanomaterials

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Task. Find out…
the main principles of the synthesis methods for
inorganic nanomaterials by

‒ Group 1: Laser ablation method (LA)

‒ Group 2: Chemical vapor deposition method (CVD)
‒ Group 3: Atomic layer deposition (ALD)
‒ Group 4: Arc discharge

Time for the task 10 minutes + 1-2 min unwrapping.

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 Titanium dioxide nanofiber based catalysts
Motivation
 Photoelectrochemical water splitting by Fujishima, A. and Honda, K. (Nature 1972,
238, 37, cited ~4200 times)
 Titania is the most studied material for photocatalytic processes (~19.000 scores on
Web of Science)
 Cheap, abundant, non-toxic, stable (anatase and rutile)
 Versatility: Antimicrobial/self-cleaning surfaces, energy applications (water splitting, H2
from alcohols, CO2 reduction), air/water purification
 Degussa P25 is probably the most known commercial photocatalyst

The recent results of UOulu groups

 Synthesis and optimization of TiO2 nanofibre catalysts and their decoration with
metals (e.g. Pt, Pd, Au, Cu)
 Doping the lattice with N
 Applications with suspended and supported photocatalysts
 Enhanced photocatalytic activity (degradation of organics, hydrogen production)
 NFs offer an easy film casting and composites with polymers and other nanofibers

/ 16 Huuhtanen, Radiation interaction with material and its use in technologies 2012, Kaunas, Lithuania University of Oulu
 Example: TiO2 nanofiber synthesis
TiO2 Na-titanate Hydrogen or sodium Pristine or N-doped
nanoparticles nanofibers hydrogen titanate TiO2 nanofibers
nanofibers
• Alkaline • Ion • Calcination in • Metal
hydrothermal exchange air and/or nanoparticle
processing (Na+ → ammonia deposition
H+)

Nano Res. 2011, 4, 360.

/ 17 Huuhtanen, Radiation interaction with material and its use in technologies 2012, Kaunas, Lithuania University of Oulu
 N-doped TiO2 nanowires: Synthesis and optical properties
(A) (B)

𝟐% 𝐍𝐇𝟑 𝐢𝐧 𝐍𝟐 ,𝟔𝟎𝟎°𝐂,𝟏𝟓 𝐡
𝐇𝟐−𝐱 𝐍𝐚𝐱 𝐓𝐢𝐲 𝐎𝟐𝐲+𝟏 𝐍𝐅𝐬 𝐍 − 𝐓𝐢𝐎𝟐 𝐀 𝐍𝐅𝐬

𝐚𝐢𝐫,𝟔𝟎𝟎°𝐂,𝟏𝟐 𝐡 𝐚𝐧𝐝
𝟐% 𝐍𝐇𝟑 𝐢𝐧 𝐍𝟐 ,𝟔𝟎𝟎°𝐂,𝟐 𝐡 ACS Nano 5 (2011) 5025.
𝐇𝟐−𝐱 𝐍𝐚𝐱 𝐓𝐢𝐲 𝐎𝟐𝐲+𝟏 𝐍𝐅𝐬 𝐍 − 𝐓𝐢𝐎𝟐 𝐁 𝐍𝐅𝐬
Patent, FI20106086

Interstitial N Substitutional N Decomposition products, surface contamination

/ 18 Huuhtanen, Radiation interaction with material and its use in technologies 2012, Kaunas, Lithuania University of Oulu
 Metal decorated N-doped TiO2 nanofibers
pristine TiO2 NF N-TiO2(A) NF N-TiO2(B) NF

ACS Nano 5 (2011) 5025 & Patent application FI20106086

/ 19 University of Oulu
 Metal decorated TiO2 nanowires, surface cleaning

Wu et al. (2011) Nano Res. 4: 360

Wu et al. (2012) J. Nanosci. Nanotechnol. 12: 1421
/ 20 University of Oulu
 Experimental apparatus for
photocatalytic activity measurements

1. reactor 6. ice trap

2. irradiation source 7. liquid nitrogen trap
3. circulation pump 8. molecular sieve
4. cooler 9. hydrogen analyzer
5. mass flow controller 10. gas flow meter

21 University of Oulu
 Nanoparticles on diesel oxidation catalyst (DOC)

TEM images of the fresh catalyst, (a) the cross-sectional TEM images of the TA + SW-treated catalyst, (a) the cross-
sample, the inset with higher magnification and (b)–(d) the sectional sample, (b), (c), and (d) the powdered sample with
powdered sample with different magnifications different magnifications

Honkanen et al., Appl. Catal B. 182 (2016) 439.

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 Nanoparticles on DOC catalyst

(a) The microstructure of the fresh Pt/Al2O3 catalyst and (b) the SCa-treated Pt/Al2O3 catalyst as well as (c) Pt-
particles presented with arrow and circle in the SCa-treated Pt/Al2O3 catalyst.

Kolli et al., Catalysis Today 154 (2010) 303–307

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Thermal management with aligned CNT forests

Appl. Phys. Lett. 90 (2007) 123105. University of Oulu

 Multifunctional carbon foam

Pham et al., Sci. Rep. 4 (2014)

6933

Tuning hydrophilicity/hydrofobicity by manufacturing conditions:

http://www.nature.com/article-assets/npg/srep/2014/141106/srep06933/extref/srep06933-s3.avi
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 Multifunctional carbon foam

Pham et al., Sci. Rep. 4 (2014) 6933 University of Oulu

 Particle filters with CNT scaffolds

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ACS Nano 4 (2010) 2003.
 Catalyst membranes with CNT scaffolds

e)

Hydrogenation of unsaturated hydrocarbons

a) Schematic view of the gas flow trough catalyst scaffold.
b) Turnover rates of propene hydrogenation to propane
from 27 to 160 °C.
c) Corresponding Arrhenius plot shows the three different
catalytic reaction regimes typical for porous solid catalysts.
d) Aging test of catalyst shows no deactivation after a 2 h
time on stream.
e) Catalyst size determined from TEM analysis.
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ACS Nano 4 (2010) 2003.
 Supercapacitor electrodes

Bulk electrodes
9.8 ± 3.3 F/g
5.7 ± 0.8 mF/cm2
5.1 kW/kg

Patterned electrodes
29.2 ± 6.1 F/g
9.1 ± 0.7 mF/cm2
16.3 kW/kg

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Chem. Phys. Lett. 583 (2013) 87..
 Entirely inkjet printed CNT field effect transistors (FETs)

Entirely inkjet printed FET with PEG-functionalized SWCNT thin film as channel, COOH-functionalized SWCNT film electrodes (source, drain
and gate) and PEG film as gate dielectric on a flexible transparency foil. (a) optical micrograph and (b) schematic drawing of the device. (c)
IDS-VDS at VGS= 0 V and IDS-VGS at VDS= -1 V plots of a transistor showing p-channel behavior. (d)-(g) IDS-VGS plots of a device measured using
different gate bias sweeps. The applied external electrical field results in gradual n-doping of the p-type channel: (d) p-FET at -2 V <VGS< 2 V,
(e) p-FET with slightly ambipolar behavior at -5 V <VGS< 5 V, (f) ambipolar operation at -25 V <VGS< 25 V and (g) n-type FET device operation
after lowering the gate voltage sweep again to -2 V <VGS< 2 V
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ACS Nano, 4 (2010) 3318.
Hybrid carbon nanostructures for electrochemical sensing

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Sensors and Actuators B 211 (2015) 177.
Printed transparent conductive coatings

Mohl et al., Sci. Rep. 5 (2015) 13710

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Inkjet printed WO3 based gas sensors

J. Mater. Chem.
22 (2012) 17878.

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Some advantages and disadvantages
Advantages Disadvantages
- Micro fabrication - Health issues
- Production in large amounts - Difficult to analyze the properties
- Smaller structures - Cost (equipments)
- Cheap unit price - Too short experience
- Homogeneous composition - May be dangerous for
- Controlled shape and size environment

- Various applications
- Usable in visible light range

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