HIGH PRESSURE CONVERSION

OF CARBON MONOXIDE
(HIPCO)
 FABRICATION (GROWTH)
TECHNIQUES
1) Direct current arc-discharge
between carbon electrodes in an
inert-gas environment
2) Laser Ablation or Pulsed Laser
Vaporization (PLV)
3) Plasma Enhanced CVD
4) Catalytic Chemical Vapor
Deposition (CVD)
CCVD
High-pressure CO conversion
(HiPCO)
 HIGH-PRESSURE CO
CONVERSION (HIPCO)
 HIGH-PRESSURE CO CONVERSION
(HIPCO)

• New method of growing SWNT

• Primary carbon source is carbon monoxide

• Catalytic particles are generated by in-situ thermal
decomposition of iron penta-carbonyl in a reactor heated to 800 -
1200°C

• Process is done at a high pressure to speed up the growth (~10 atm)

• Promising method for mass production of SWNTs

• Carbon nanotubes are generally produced by three main techniques,
arc discharge, laser ablation and chemical vapour deposition.

• Though scientists are researching more economic ways to produce

these structures.

• In arc discharge, a vapour is created by an arc discharge between

two carbon electrodes with or without catalyst. Nanotubes self-
assemble from the resulting carbon vapour.
• In the laser ablation technique, a high-power laser beam impinges on
a volume of carbon containing feedstock gas (methane or carbon
monoxide). At the moment, laser ablation produces a small amount of
clean nanotubes, whereas arc discharge methods generally produce
large quantities of impure material.
• In general, chemical vapour deposition (CVD) results in MWNTs or
poor quality SWNTs. The SWNTs produced with CVD have a large
diameter range, which can be poorly controlled. But on the other hand,
this method is very easy to scale up, what favours commercial
production.
 Carbon nano tubes

Arc Discharge Laser Ablation technique Chemical Vapour Deposition

Synthesis of SWNT  Plasma enhanced CVD

SWNT versus MWNT
Thermal CVD
Synthesis of MWNT
Large scale synthesis of
Alcohol catalytic CVD
SWNT

Ultra fast Pulses from a  Vapour phase growth

free electron laser (FEL)
method Aero gel-supported
CVD

Continuous wave laser-powder Laser-assisted thermal CVD

method
CoMoCat process

High pressure CO
Disproportionation process
 HiPCO

Definition: A synthesis method for carbon nanotubes

that involves mixing high pressure (e.g. 30atmospheres) CO
that has been preheated (1000 deg. C) and a catalyst
precursor gas (metal carbonyl or metallocene).

Under these conditions the precursor decomposes forming

metal particle clusters on which carbon nanotubes nucleate
and grow. The carbon nanotubes are 99% single-walled
carbon nanotubes with small diameters (e.g., (5,5) tubes).
•The high-pressure carbon monoxide (HiPCO) process (603
Kb) was developed at Rice University, United State to
create single-walled carbon nanotubes (SWCNT) from the
gas-phase reaction of iron carbonyl with high-pressure
carbon monoxide gas.

• Iron penta carbonyl(Fe(CO)5) is used to produce iron

nanoparticles that provide a nucleation surface for
the transformation of carbon monoxide into carbon during
the growth of the nanotubes.

•Experiments use in the range of milligrams to grams of

material. Waste material is regularly picked up by a
professional waste disposal company, and the waste
material is incinerated, avoiding environmental release.
Fig 1.HiPco reactor, with the mixing/reaction zone
shown enlarged
•The high-pressure carbon monoxide (HiPCO) reactor
has catalytic particles formed in situ by thermal
decomposition of iron carbonyl(Fe(CO)5).

•Mixtures of Fe(CO)5 and CO are injected into the

reactor through an insulated, air or water-cooled
stainless-steel injector tipped with a Copper nozzle in a
quartz tube.

•The rapid heating of the CO + Fe(CO)5 mixture can

enhance the formation of nanotubes.

•The process can be operated continuously by using

continuous filtration to separate the carbon nanotubes
containing the iron catalyst from the unreacted carbon
monoxide.
•Carbon nanotubes contain iron particles (~5–6 at.%)
that are formed from the decomposition of the iron
carbonyl which act as the growth nucleation sites.

•The iron nanoparticles are not enclosed in heavy

graphitic shells as in the arc or laser vaporization
processes and are relatively easier to remove.

•CO + CO  C(s) + CO2(g).

when the metal clusters achieve a size near to that
of C60 they nucleate and grow SWNTs.
Fig 2.Layout of CO flow-tube reactor
•The above figure shows the layout of CO flow-tube
reactor.
•Size and diameter distribution of the nanotubes can be
roughly selected by controlling the pressure of CO.
•This process is promising for bulk production of carbon
nanotubes.
•Nanotubes as small as 0.7 nm in diameter, which are
expected to be the smallest achievable chemically stable
SWNTs , have been produced by this method.
•The average diameter of HiPCO SWNTs is approximately
1.1 nm.
•The yield that could be achieved is approximately 70%.
•The highest yields and narrowest tubes can be produced at
the highest accessible temperature and pressure. SWNT
material with 97% purity can be produced at rates of up to
450 mg/h .
• The method called high pressure conversion of
carbon monoxide (HiPco) is employed to
produce SWCNTs by continuously flowing CO
gas phase (i.e. the carbon feedstock) and
Fe(CO)5, the catalyst precursor [25], through a
heated reactor .
• The average diameter of HiPco SWCNTs is
approximately 1.1 nm and the yield reaches 70
% [12, 26]. CNTs made by this method
generally have an excellent structural integrity,
although the production rates are still relatively
low.
• A continuous-flow synthetic method, in whichSWNTs are
grown and separated. in a flowing gaseous feedstock
mixture, could produce SWNTs in large quantities. Such
schemes would involve introducing into the feedstock flow
stream nanometer-size catalyst particles on which the
individual tubes nucleate and grow. The catalyst particles
could be either pre-made or produced in situ by the
introduction of metal-containing species into the flow and
their subsequent condensation into appropriately sized
clusters. The latter technique is especially convenient,
because metal can be introduced in the form of volatile
organometallic molecules.
 here the catalytic production of SWNTs in a continuous-flow gas-
phase process using CO as the carbon feedstock and FeCO. as the
iron-con taining catalyst precursor. We find that both the yield of
SWNT material and the diameters of the nanotubes produced can
vary over a wide range, depending on the conditions and flow-cell
geometry used. In particular, we have succeeded in producing
SWNTs with diameters of 0.7 nm, which are expected to be the
smallest achievable chemically stable SWNTs w1x. This process or
variations of it. should be scalable for bulk SWNT production. The
products of FeCO. Thermal decomposition probably FeCO. , ns0–4.
react to n produce iron clusters in gas phase. These clusters act as
nuclei upon which SWNTs nucleate and grow solid carbon is
produced by CO disproportionation the Boudouard reaction
The flow cell apparatus consists of a 1Y 2.54 cm. OD thick-walled
quartz flow tube contained within a tube furnace, through which
reactant gases areflowed. The tube section inside the furnace was
maintained between 800 and 12008C, while the tube entrance and
exit were maintained at room temperature. We found that the rate
at which the reactant gases were heated had substantial effects on
the amount and quality of SWNTs produced. In some experiments
the CO and FeCO. were introduced through a water-cooled injector
positioned inside the quartz tube, which maintained the gases at low
temperature until they were injected into the furnace, resulting in
rapid heating. Around the exit of this injector could be positioned a
circle of narrow-gauge needles through which preheated CO was
passed at high flow rate to mix with the cool flow emerging from the
injector, further increasing the heating rate of the injected gas. The
CO sprayed from this ‘showerhead’ mixer was preheated by passing
through a spiral heatexchanger positioned within the furnace.
Our gas mixture consisted of CO 1–10 atm flowing at 1–2 standard liters per
minute. dosed with a small amount 0–25 mTorr. of gaseous FeCO 5. Dosing was
accomplished by passing a measured fraction of the CO stream through a
FeCO5. filled 5 bubbler maintained at 08C. This produced a partial pressure of
FeCO5. equal to its vapor pressure of 7 Torr, and the partial pressure of FeCO5.
was subsequently reduced by diluting with additional CO before its introduction
into the flow cell. Commercial
CO will always contain a few ppm of FeCO5. as a contaminant, which we filtered
out using an in-line catalytic purifier Oxyzorb, Matheson. prior to introduction
into our flow system. Alternately, this small ‘background’ concentration of
FeCO5. was used directly in experiments with high CO pressure andror low
FeCO5. concentration because the bubbler was found to be unreliable under
these conditions. The
concentration of background FeCO5. in the CO 5 stream, typically 2–10 ppm,
was determined by measuring the total amount of iron deposited in the
reactor. In control experiments using no FeCO5. with the catalytic purifier in
use., no iron or carbon reaction products were observed.
• Flow of COrFe CO. mixtures through the heated reactor
resulted in black deposits on the walls of the quartz tube
outside the furnace. These deposits consisted of SWNTs
and iron particles apparently overcoated with carbon.
THE DEPENDENCE OF SWNT PRODUCTION ON
TEMPERATURE, PRESSURE AND FE(CO)5
CONCENTRATION

• Table 1 lists the rate of SWNT production vs.

temperature at 10 atm
• The highest production rate is achieved at our
furnace’s highest available temperature, 1200oC
• SWNT production rate vs. pressure at 1200oC, where
the CO pressure is varied from 1 to 10 atm and the
relative concentration of Fe(CO)5 is maintained at
5ppm

• SWNT yield is increases as Fe(CO)5 concentration is

increased, but Fe(CO)5 concentration is increased
further, the rate of Fe accretion becomes large
enough, and the resultant shortening of a nanotube’s
growth and it slows down the rate of SWNT formation
 CHARACTERIZATION
METHODS
 SEM
 TEM
 Raman (interaction of incoming light with solid
vibrations)
 SPM (AFM , STM ,…)
 XRD (X-ray diffraction) similar to electron diffraction
 TPO, TGA (temperature programmed oxidation) and
(thermal gravimetric analysis)
 Electrical characterization
SEM IMAGES
 TEM
(LOW MAGNIFICATION)
CARBON NANOTUBES RAMAN
CHARACTERIZATION
TGA
UV-IR
 ADVANTAGES
With the HiPco method the thinnest single-walled carbon
nanotubes of very high quality, few structural defects
The smallest achievable chemically stable SWNT diameter
0.7nm
The average diameter of HiPco SWNTs is approximately 1.1 nm
the synthesis product yield is as high as 97%and the
purification yield is 90%
Narrow tubes were produced at the highest accessible
temperature and pressure, 1200oC and 10 atm,respectively
 high product yield and selectivity catalyst
 Purification steps are unnecessary due to use CO instead of
hydrocarbons
it is a continuous-flow process rather than a batch process
It produces continuously single-walled carbon nanotubes at a
rate of 0.45 g/h
 DISADVANTAGES
• The main limit on nanotube production appears to be
cessation of growth due to accretion of Fe atoms onto
growing nanotubes.
 One way to avoid this is operating at higher CO pressures,
which reduce the relative amount of catalyst present and
may increase the rate of reaction

• A major drawback of the HiPCO reactor is the low rate of

carbon monoxide conversion (~15–20% per cycle) even at
high pressure.

• CO disproportionation is much slower than hydrocarbon

thermal decomposition.
 To overcome this small amount of methane was added to
the CO flow to increase the amount of carbon available for
SWNT
 APPLICATIONS
Electronics
Hydrogen storage,
Chemical Sensors
Fuel Cells
Nano-transistors, nano-structures
Application in STM
Composite materials,
NANO-TRANSISTORS
 PHOTONIC CRYSTALS

• Similar to atomic periodicity, a structure with matter

periodicity is created to form a band-gap for optical
wavelengths.
• Only at certain wavelengths, standing waves can be created
and at some other wavelengths, transmission is prohibited
 FIELD EMISSION
• Each sharp tip of
nanotube acts as a field-
DEVICES
emitter device.
• The emitted electrons
hit the top electro-
luminescent material
(like ZnS).
• Pixels are clusters of
nanotubes
• Standard micro-meter
photo-lithography,
• Large area applications
• Stable structures are
needed for a reliable
application
 CONCLUSION
• We have seen a technique for catalyticproduction of single-walled
nanotubes in gas phase.
• Our flow reactor uses carbon monoxide as the carbonfeedstock and
gaseous iron pentacarbonyl as the metal-particle catalyst precursor.
Unlike methods involving hydrocarbon feedstocks, our method
results in no amorphous carbon overcoating on the product
nanotubes. Nanotubes as small as 0.7 nm in diameter have been
produced, and the size and diameter distribution of the nanotubes
produced can be roughly selected by controlling the pressure of CO
in which the reaction occurs. Highest yields and narrowest tubes.
were produced at the highest accessible temperature and pressure,
12008C and 10 atm,respectively.
• This process has advantages over other SWNT
• production methods: it is a continuous-flow process rather than a
batch process, and should be able to be scaled up to produce SWNTs
in much larger quantities.
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