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Catalytic properties of nanomaterials

Suitability of catalysts
•Activity (How fast one or more reactions proceed in presence of catalyst)
•Selectivity
•Stability (deactivation behavior)
Performance of catalyst based on
•Conversion under constant reaction conditions
•Space velocity for a given conversion (Volume flow rate relative to catalyst mass = V0/mcat)
•Space time yield (STY, desired product quality/(catalyst volume . time)
•Temperature required for a given conversion
•Turnover frequency (TOF): Number of molecular reactions or catalytic cycles occurring at
the center per unit time. TOF = volumetric rate of reaction/(number of centers / unit time)
Selectivity of the catalyst

Priority:
Selectivity > Stability > Activity

Dr. S. Paria, NIT RKL Nanotechnology 1


CO oxidation by Fe2O3
NANOCAT can catalyze oxidation of almost 100%
of the carbon monoxide to carbon dioxide at 350
◦C in an inlet gas mixture of 3.44% carbon
monoxide and 20.6% oxygen at 1000 ml min−1.
Under identical conditions, the same amount of
the α-Fe2O3 powder with a particle size of 5 µm,
can only catalyze oxidation of less than 5% of the
carbon monoxide to carbon dioxide.
In addition to that, the initial light off
temperature for NANOCAT is more than 100 ◦C
lower than that of α -Fe2O3 powder.
In the second run, the whole conversion
curve shifted upward to a higher temperature
region by about 50 ◦C.
Comparison of the carbon monoxide conversion
efficiencies between NANOCAT and α-Fe2O3
powder.

Applied Catalysis B, 43, 2003, 151-162


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Reaction order

The linear relationship between the effluent carbon dioxide concentration and the inlet carbon
monoxide concentration indicated that the catalytic oxidation of carbon monoxide on NANOCAT
is first-order with respect to carbon monoxide.
NANOCAT is more active than other supported iron oxide catalysts in two ways. First, the onset
temperature is at least 100 ◦C lower (150 ◦C versus 250 ◦C). Secondly, the CO conversion
efficiency is higher. For example, 50 mg of NANOCAT can convert all of the CO gas (3.44% CO
in 1000 ml min−1 flow) to CO2 at 350 ◦C.

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Reason for oxidation at low temperature
High conversion efficiency: Its small particle size of 3 nm and high surface area of 250 m2 g−1.
However, the high surface area alone cannot explained why, for the first run, the onset
temperature of the NANOCAT is at least 100 ◦C lower than the onset temperatures of iron
oxide powder, supported or unsupported.

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Direct CO oxidant

Nanotechnology
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Limits of CO and Health effect
12,000 PPM* Death within 1 – 3 minutes
1600 PPM* Nausea within 20 minutes, death within 1 hour
800 PPM* Nausea and convulsions – death within 2 hours
400 PPM* Frontal headaches 1-2 hours life threatening within 3 hours
50 PPM* Maximum level for continuous exposure in an 8 hour workday
10–35 PPM* Marginal - Small children, elderly, and those suffering
respiratory or heart problems cautioned
9 PPM* The concentration often found on busy city streets
1–9 PPM* Any increase in indoor CO levels above outside measured
readings, warrants further investigation though may not be an immediate
health risk
Common symptoms associated with carbon monoxide poisoning:

loss of hearing
headaches
dizziness blurry vision
weakness vomiting
rapid heartbeat disorientation
loss of consciousness seizures
nausea coma
cardiac arrest respiratory failure

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Gold Catalyst
Since gold is the least reactive metal, it has been regarded as poorly active as a heterogeneous
catalyst.
When gold is deposited on select metal oxides as ultra-fine particles, we have found that its
chemistry dramatically changes. Highly dispersed gold catalysts are really very active in
many important reactions for chemical industry and environmental protection and have
already been used for commercial applications in offensive odor removal and gas sensors.
Noble metal catalysts are mostly prepared by impregnation methods, which, however, cannot
produce active gold catalysts. The impregnation methods can hardly lead to high dispersion of
gold except for a few cases of very low metal loadings because of the lower melting point of Au
(1063 °C) than those of Pd (1550 °C) and Pt (1769 °C) and partly because the catalyst
precursors are often calcined at low temperatures (be low 600 °C) where chlorine still remains
in the metal oxide supports.
The following four methods can deposit gold on a variety of metal oxides as small particles
with diameters below 5 nm.

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1. Coprecipitation: An aqueous solution of HAuC14 and a metal nitrate is poured into an
aqueous solution of Na2CO3 to obtain a hydroxide or carbonate coprecipitate. The precursor is
washed, dried, and finally calcined in air at a temperature above 250 °C.
2. Deposition-precipitation: After the pH of an aqueous solution of HAuC14 is adjusted to a
fixed point in the range of 6 to 10, a metal oxide support in any form, powder, bead, honeycomb, or
thin film is immersed in the solution. Aging for about 1 h results in the deposition of Au(OH)3
exclusively on the surface of metal oxide support if concentration and temperature is properly
chosen. The precursor is treated in a similar manner as in coprecipitation. The remarkable
influence of the pH on the particle size of Au is shown in Fig. for TiO2. Above pH 6 main species of
Au in solution is transformed from AuC14- to Au(OH)nCl4-n (n = 1-3) and the mean particle
diameters of Au in the calcined (400°C) catalysts become smaller than 4 nm.

Fixed bed Honeycomb

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3. Co-sputtering: In an atmosphere containing oxygen, gold and metal oxide are
simultaneously sputter-deposited on a substrate to form thin film, which is finally annealed in
air.
4. Chemical vapor deposition: The vapor of an organic gold compound, typically dimethyl-
gold(III)-acetyl acetonate, is introduced onto an evacuated metal oxide support. The adsorbed
organic gold compound is pyrolyzed in air to decompose it into small gold particles. This
method can be applied to a wide variety of metal oxides, while the liquid-phase methods are
usually not valid to acidic metal oxides like SiO2.
Advantages: Nanoparticle Au catalysts are active under mild conditions, even at ambient
temperature or less, and this makes them unique. They will therefore be effective in reducing
running costs of chemical plants and could increase the selectivity of the reactions involved
where applicable. In pollution control applications, such as air cleaning, and purification of
hydrogen streams used for fuel cells, they have the characteristics to become the catalysts of
choice, especially now that their durability and resistance to poisons is being shown to be
better than had been anticipated. Use of mixed precious metal catalysts can produce even
higher activities than the use of Au alone.

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Yield of VAM (Vinyl acetate monomer)

Nanoparticulate Au on oxide can be used to catalyze the water gas shift to produce hydrogen
from CO and steam:
CO + H2O → H2 + CO2
For use in a fuel cell, the remaining CO in this reversible reaction must be removed to prevent it
poisoning the Pt catalyst in the fuel cell. Au catalysts have been found to be effective for this at
room temperature. The Au/TiO2 catalyst is very selective for CO oxidation and can remove high
levels from the hydrogen. The low (ambient) operating temperature gives high selectivity and no
additional energy is required to heat the reactor.

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Gold catalyzed oxidation of CO
• Unsupported gold in the form of sponge, wire, powder, etc, and large supported gold particles
are at best only weakly active for carbon monoxide oxidation.
• Much higher activities are shown by oxide supported small gold particles less than about 5 nm
in size, with the highest rates being shown at sizes of about 2 to 3 nm. This is true whatever the
method of preparation employed.
• Choice of support is very important: success depends on using an oxide of the first row of the
Transition Series elements. Of these, the oxides of titanium and iron have recently
commanded the most interest, although those of manganese, cobalt and nickel are also
effective.
• The method of preparation is critical. The traditional methods, such as ion exchange and
impregnation are not very successful although successive reduction and calcination can
generate activity in the impregnated material. Three methods in particular have been widely
used: (i) coprecipitation, in which the support and gold precursors are brought out of solution,
perhaps as hydroxides, by adding a base such as sodium carbonate; (ii) deposition-
precipitation, in which the gold precursor is precipitated onto a suspension of the pre-formed
support by raising the pH, and (iii) Iwasawa’s method in which a gold-phosphine complex (eg
[Au(PPh3)]NO3) is made to react with a freshly precipitated support precursor.
• The mode of pretreatment before use is also important: calcination is frequently used with
good results.

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Gold Bulletin 200, 33, 41-50
While catalytic activity of Pt/TiO2 is
independent of preparation methods, that of
Au/TiO2 changes dramatically. Au/TiO2 1% Au-IMP
catalysts prepared by DP are active even at 1% Pt-DP Au-DP
below 0 °C when Au loadings are above 1
wt% and have turnover frequency larger
than those of Pt/TiO2 by about 1 order of 1% Pt-IMP
magnitude.
Size effect can not explain fully this effect. Au
particle of 5 nm with TiO2 after calcination
air at different temperature from different
structure of gold nanoparticles (longest 0.9% Pt-FD
distance of perimeter interface). 1% Au-FD

200 K

Logarithmic reaction rate of CO oxidation over


Pt-TiO2 and Au-TiO2 catalysts as a function of
reciprocal temperature.

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Catalysis Today 36 (1997) 153-166
Effect of supporting material
The catalytic behavior of gold deposited on metal oxides
with different catalytic activities for CO oxidation, TiO2
(poorly active), α-Fe2O3 (active), and Co3O4 (very active)
can be summarized as follows.
1. The catalytic activity can be correlated with the contact
structure giving the longest perimeter distance of gold-
support interface
2. The turnover frequency increases with a decrease
in the mean diameter of gold particles
3. The reaction rate is 0 ~ 0.05 order with respect to CO and
0.05 ~ 0.24 with respect to O2.
4. Moisture enhances the catalytic activity
5. CO is adsorbed as a linearly bonded carbonyl on the surface and perimeter interface of gold
particles and the surface of metal oxide support as carbonate and carboxylate species. On
introduction of 18O2, oxygen-exchanged carbonyl Au-C ≡ 18O2 and oxygen-coadsorbed 18O2 = Au-
C ≡ O species appear on the surface of gold together with C16O2, C16O18O, and C18O2 in the gas
phase.
6. Even on unsupported fine gold powder O2 as well as CO can adsorb and the reaction between
them can also take place at 0°C, however, the catalytic activity per unit surface area of Au
particles is about 100 times smaller than that of Au/TiO2
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Comparison of different microscope

Microscope (radiation/ interaction used) Magnification Resolution

Human eye (Visible light) - 100 µm


Optical Microscope (UV-vis-IR) 103 0.1 µm
Scanning Electron Microscope (electrons) 105-106 3 nm
Transmition Electron Microscope > 106 0.1 nm
(electrons)
Scanning Tunnelling Microscope (electron > 106 0.1 nm
current)
Atomic Force Microscope > 106 0.1 nm
Scanning Near-Field Optical Microscope > 105 20-30 nm
(Vis light)

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Scanning Probe Microscope (SPM)

• Family of microscope that forms images of surfaces using a physical probe that scans the
specimen.
• First SPM is known as Scanning Tunneling Microscope (STM) was developed in 1982 at
IBM by Gerd Binnig and Heinrich Rohrer, they got Nobel prize in 1996.
• Other SPMs are AFM, MFM (magnetic force microscopy).

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Scanning Tunneling Microscope (STM)
The governing principle of scanning tunneling microscopy (STM) is the quantum tunneling
of electrons through a thin potential barrier separating two electrodes. The instrument
basically consists of a very sharp tip which position is controlled by piezoelectric elements
(converting voltage in mechanical deformation). By applying a volatge (Vt) between the tip
and a metallic or semiconducting sample, a current can flow (It) between these electrodes
when their distance is reduced to a few atomic diameters. The amplitude of the current
strongly depends on the distance between the tip and the sample, and of course also on the
potential difference Vt.
The STM operates in the regime of extremely small
distances between the tip and the surface of only 0.5
to 1.0 nm, i.e. 2 to 4 atomic diameters. At these
distances, the electrons can ‘jump’ from the tip to the
surface or vice versa. This ‘jumping’ is a quantum
mechanical process, known as ‘tunneling’. Hence the
name of this microscope: tunneling microscope. The
tunneling process is very difficult, which implies that
the tunneling current is always very low. STMs
usually operate at tunneling currents between a few
picoAmperes (pA) and a few nanoAmperes (nA).
http://dpmc.unige.ch/gr_fischer/localprobe.html
http://www.physics.leidenuniv.nl/sections/cm/ip/group/Principle_of_SPM.htm

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• Tunneling distance very critically depends on the precise distance between the last
atom of the tip and the nearest atom of the surface. When this distance is increased
only a little bit, the tunneling current decrease strongly. As a rule of thumb, every
extra atom diameter that is added to the distance the current becomes factor of
1000 lower. This means that the tunneling current is highly sensitive of the distance
between the tip and the surface.

In a metal, the energy levels of the


electrons are filled up to a particular When the specimen and the tip are
energy, known as the ‘Fermi energy’ brought close to each other, there is
EF. In order for an electron to leave only a narrow region of empty space
the metal, it needs an additional left between them. On either side, the
amount of energy Φ, the so-called electrons are present up to the Fermi
‘work function’. energy. They need to overcome a
barrier Φ to travel from tip to
specimen or vice versa.
If the distance d between specimen and tip is small enough, electrons can ‘tunnel’
through the vacuum barrier. When a voltage V is applied between specimen and tip,
the tunneling effect results in a net electron current. In this example from specimen to
tip. This is the tunneling current.
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 2mΦ 

I (d ) = cons tan t × eV exp − 2 d 
 h 
This (approximate) equation shows that the tunneling
current obeys Ohm’s law, i.e. the current I is proportional
to the voltage V. It depends exponentially on the distance d.
The other quantities in the equation are the work function
Φ, the electron charge and mass e and m, and Planck’s
constant. For a typical value of the work function Φ of 4
electronVolt (eV), the tunneling current reduces by a factor
10 for every 0.1 nm increase in d. This means that over a Tip material: Si, Pt-Ir, Pt-Rh,
typical atomic diameter of e.g. 0.3 nm, the tunneling etc.
current changes by a factor 1000! This is what makes the Lead-Zirconium-Titanate
STM so sensitive. The tunneling current depends so (PZT) are known to be pizo
strongly on the distance that it is dominated by the crystal
contribution flowing between the last atom of the tip and
the nearest atom in the specimen.

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Transmission Electron Microscopy (TEM)
Similarity of Optical and Electron Microscope
Optical Electron
Electron gun
Anode
Essential difference:
Condenser lenses
wavelength of
Sample electrons: 3.7⋅10-3 nm
Objective lens
at 100 keV
wavelength of light:
400 - 700 nm
Intermediate image
Projector lens
Consequently:
resolution of electron
microscope higher
Final image

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Operating voltages : 20-200kv
TEM images are formed using transmitted eletrons (instead of the visible light) which
can produce magnificationdetails up to 10,00,000x with resolution better than 1 nm.
Furthermore, the analysis of the X-ray porduced by the interraction between the
acclerated eletrons with the sample allows detemining the elemental composistion of the
smaple with high spatial resolution.

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