Purification of carbon nanotubes

MTA SzFKI Carbon Nanotube Learning Seminar

Herndi Klra University of Szeged

April 18, 2005

What do we have to purify?

type of carbon nanotube SWNT MWNT synthesis method arc discharge/laser ablation/HiPCO Chemical Catalytic Vapor Deposition

The most common impurities

various types of carbon (any kind of synthesis) graphitic nanoparticles amorphous carbon fullerenes polyaromatic hydrocarbons, etc. catalyst material (SWNT; CVD) particles containing (transition) metal catalyst support (CVD)

How to remove contaminants?

Depending on the reactivity of impurities the stability of carbon nanotube samples

Chemical Physical Combined

method

How to start?
SWNT ropes Catalytic particles

as-prepared soot: arc-discharge, Fe-Ni catalyst, 500 Torr of He

S. Bandow et al., Appl. Phys. A 67 (1998) 23.

Purification of arc-discharge MWNT

suspension of 500 ml of distilled water, 2.5 g of SDS (sodium dodecyl sulfate) and 50 mg of MWNT arc powder was sonicated for 15 minutes sedimentation and centrifugation (at 5000 rpm for 10 minutes) removed all graphitic particles larger than 500 nm additional surfactant 12 CMC (critical micelle concentration) flocculation, formation of aggregates of large objects smaller objects remain dispersed, and sediment after a few days after decanting the suspension, procedure is repeated once or twice material remaining in suspension consisted nearly exclusively of nanoparticles the sediment contained nanotubes with a content of over 80 % in weight.
J-M. Bonard et al., Adv. Mater 9 (1997) 827.

Purification of arc-discharge MWNT

Purification of arc-discharge (laser) SWNT

a) SWNT soot (20 W/m2 laser) b) crude material after refluxing in 3 M HNO3 for 16 h (82%) c) purified sample after oxidation in air at 550C for 30 min (20%) d) after brief annealing at 1500C in vacuum

A.C. Dillon et al., Adv. Mater 11 (1999) 1354. A.G. Rinzler et al., Appl. Phys. A 67 (1998) 29.

Purification of arc-discharge (laser) SWNT

combustion of nonnanotube carbon

severe damage of nanotube carbon

~1593 cm-1 and ~1567 cm-1 (1.2 and 1.5 nm diameter SWNT)

Purification of arc-discharge (laser) SWNT

Why annealing can be necessary?

a) raw sample b-d) purified sample after mixed acid (sulfuric + nitric) treatment

Y. Zhang et al., Carbon 38 (2000) 2055.

Purification of HiPCO SWNT

pristine

purified

1st step: to remove carbon coating 100 mLmin-1 air flow at 623K for 30 min. 2nd step: to dissolve Fe nanoparticles treatment in 35% HCl at roomT for 48 h

C-M. Yang et al., Nano Letters 2 (2002) 385.

Purification of HiPCO SWNT

Wet oxidation technique 100 mg of raw HiPco SWNTs suspended in a mixture of 60 ml of 30% H2O2 and 110 ml of 22% HCl refluxed under continuous magnetic stirring at 70 C for 9 h cooling, filtration and washing with distilled water until pH 7 drying at 120 C for 30 min the yield of purified SWNTs was 90% the average diameter of the tubes is 1.5 nm
Cs. Mik, private communication

Mechanical purification of SWNT

Original sample 1. 2. 3. 4. 5. Suspension of raw material Addition of insoluble powder Strong sonication (Snooker effect) Collection of magnetic particles with a permanent magnet Separation of purified carbon nanotubes

L.Thin-Nga et al., Nano Letters 2 (2002) 1349 .

Mechanical purification of SWNT

empty shells 2-3 graphite layer

Final product:

Raw soot: strong ferromagnetic signal

H ig h p o w e r u ltra s o n ic fin g e r

M a g n e t (0 .1 T )

Purified soot
0 1000 20 00 3000 4000 50 00 6000

d e p o s it
N a n o tu b e so lu tio n

Ma gen ic Field [Gauss]

CVD: Silica supported catalysts

Removal of metallic particles (diluted mineral acid) Sonication Sedimentation Decantation non-destructive

XPS spectra before and after acidic treatment TEM images before and after mechanical purification low efficiency (~1%)

K. Hernadi, et al.: Synth. Metals 77 (1996) 31.

CVD: Zeolite supported catalysts

catalyst particle

amorphous carbon as-prepared sample after HF treatment

Purification: dissolving metallic and support particles in HF Problem: pore structure of zeolite liberating amorphous carbon Another purification step is necessary
K. Hernadi, et al.: Zeolites 17 (1996) 416.

CVD: Alumina supported catalysts

Purification: 1st step: dissolving alumina support in cc. NaOH at boiling point 2nd step: removal of metallic particles in acidic treatment

long bundle-like structure

Z. Knya, NATO-ASI Carbon Filaments and Nanotubes: (Eds.: Bir, L.P., Bernardo, C.A., Tibbetts, G.G., Lambin, Ph.): Carbon Filaments and Nanotubes: Common Origins, Differing Applications? Dordrecht, Kluwer Academic Publishers, 2000, Chapter VI, 85

Removal of amorphous carbon

Hydrogenation Oxidation!

Gaseous ozone at 200C, 90 min traces of Co, Zn, Cr

Ozone in acidic solution traces of Fe, Co

K. Hernadi et al.: Solid State Ionics 141-142 (2001) 205.

Removal of amorphous carbon

H2O2 almost no impur. HClO4

traces of Si, Cl, Cr, Zr

KMnO4 cc. HCl no impurities!!!

Result of oxidation

open end after oxidation

Reactivity of different kinds of carbon Competitive oxidation

Damage of carbon nanotubes (ends, defects, spirals)

Raman spectra

CVD: CaCO3 supported catalysts

Non-porous support

One-step purification: dissolving metallic particles + support in diluted mineral acid

E. Ljubovic et al.: Chem. Phys. Lett. 378, 9-17 (2003).

No amorphous carbon

Summary
Removal of impurities

carbon nanoparticles
oxidation, (dehydrogenation)

catalyst metal
acidic treatment

mechanical separation of different kind

catalyst support
suitable chemical

Thank you for your attention!