Soft Template Synthesis of Porous Platinum Nanoballs

Michael Gaultois A presentation on the findings of G. Surendran et al.

Surendran, Geetarani; Ramos, Laurence; Pansu, Brigitte; Prouzet, Eric; Beaunier, Patricia; Audonnet, Fabrice; Remita, Hynd. Chemistry of Materials. 2007, 19 (21), 5045-5048.

November 21, 2007

Outline
Background on nanocatalysis Template synthesis Current work : Pt nanowires
Characterization
TEM - structure SAXS - crystallinity of template BET - pore size distribution, total surface area

Future studies
Catalytic activity In situ EXAFS study

Background

Results

Nanoparticle Catalysis
Pt known for catalytic applications Catalytic activity depends on morphology of nanoparticles Pt $$$$ High catalytic activity of Pt nanowires toward water-gas shift reactions.
Primary method of H2 production today.

Future

Fukuoka, A.; Higashimoto, N.; Sakamoto, Y.; Sasaki, M.; Sugimoto, N.; Inagaki, S.; Fukushima, Y.; Ichikawa, M. Catal. Today 2001, 66, 23.

Background

Results

Template synthesis

Future

Background

Results

Hard Templates

Future

Silica templates can be used as molds to obtain nanomaterials with high aspect ratio (Pt nanowires mentioned earlier)

Removal of silica requires harsh treatment (hydrofluoric acid) Nanoparticles must be resistant to any removal treatment

Fukuoka, A.; Higashimoto, N.; Sakamoto, Y.; Sasaki, M.; Sugimoto, N.; Inagaki, S.; Fukushima, Y.; Ichikawa, M. Catal. Today 2001, 66, 23.

Background

Results

Soft Templates
Mesophase: intermediate phase between crystalline and liquid. Some mesophases are liquid crystalline, which have partial orientational ordering.

Future

First shown by Attard et al. that binary liquid crystals (high viscosity) provide a strong confinement of metals in the aqueous phase Can be dissolved after synthesis of nanoparticles
No harsh chemical removal

Surfactant self-assembly can be tailored by changing system

Attard, G. S.; Gltner, C. G.; Corker, J. M.; Henke, S.; Templer, R. H. Angew. Chem., Int. Ed. Engl. 1997, 36, 1315. Attard, G. S.; Barlett, P. N.; Colemen, N. R. B.; Elliott, J. M.; Owen, J. R.; Wang, J. H. Science 1997, 278, 838.

Background

Results

Quaternary Mesophases
4 components
Water Oil Surfactant Cosurfactant Micelle Packing

Future

Forms hexagonally packed oil-filled cylinders in water Controlled cylinder size

Change ionic strength of aqueous phase

Can be used to synthesis structured nanomaterials in aqueous and oil phases

Pena dos Santos, E.; Tokumoto, M. S.; Surendran, G.; Remita, H.; Bourgaux, C.; Dieudonne, P.; Prouzet, E.; Ramos, L. Langmuir 2005, 21, 4362. Surendran, G.; Pena dos Santos, E.; Tokumoto, M. S.; Remita, H.; Ramos, L.; Kooyman, P. J.; Santilly, C. S.; Bourgaux, C.; Dieudonne, P.; Prouzet, E. Chem. Mater. 2005, 17, 1505. Surendran, G.; Apostelescu, G.; Tokumoto, M.; Prouzet, E.; Ramos, L.; Beaunier, P.; Kooyman, P. J.; Etcheberry, A.; Remita, H. Small 2005, 1, 964.

Background

Results

Current work
4 components
Water, 2mL Oil: cyclohexane, 2.98mL Surfactant: cetyltrimethylammonium bromide (CTAB), 1.03g Cosurfactant: 1-pentanol, 600L

Future
CTAB

Pt(NH3)4Cl2 , 0.1M Vortex together several minutes

Yields stable transparent gel (hexagonal mesophase)

Reduce: Irradiate 16h-rays, 60Co source (dose rate of 3.0 kGh-1) Add isopropanol (destabilize mesophase), centrifuge, collect nanoparticles

Take home message: you mix it, put it in front of -rays, then rinse and collect. Simple synthesis

Background

Nanorods (2.8nm average diameter) Ball-like aggregates (60-80nm diameter)

Resulting structures after collection - TEM

Results
Future

Background

Results

Growth mechanism

Future

The nanowires seem to result from the coalescence of spherical seeds (~2nm diameter) confined between cylinders This growth process has been proposed for nanowire growth of Ag in DMF and CdTe in aqueous solution. Confinement also drives the nanowire connection, which leads to 3D nanostructures (balls).

Krishnaswamy, R.; Remita, H.; Imperor-Clerc, M.; Even, C.; Davidson, P.; Pansu, B. ChemPhysChem 2006, 7, 1510.

Background

Results

After 6h irradiation
Fractal aggregates and nanorods seen.

Future

Past

Present

Exploring the aggregation

Binary CTAB micellar solution
2nm spherical particles (1)

Future

Lamellar mesophase (increase [cosurfactant])

fractal (random) aggregates or parallel nanowires (2, 3)

Electron beam reduction (>2000X dose rate)

6-8nm spherical nanoparticles (4)

Background

Small Angle X-ray Scattering (SAXS)

Results
Future

Elastically scattered x-rays (0.1-10 angles) Non-destructive Synchrotron and bench top Samples can be non-crystalline
Spatially averaged (due to random orientation)

Useful for studying structure of small particle systems (5-25nm)

Background

Results

SAXS Results
Before irradiation
See characteristic pattern of hexagonal phase
four peaks at position ratio

Future

1 : 31/2 : 2 : 71/2

After irradiation
Broad peak (*) overlaps preserved hexagonal phase

Background

Results

BET isotherms
Physical gas sorption isotherms
Fast, easy, reliable specific surface area (SBET)

Future

Modelling (BJH Pore Distribution Model)

pore volume average pore size pore size distribution (PSD)
Barrett, E. P.; Joyner, L. G.; Halenda, P. P. J. Am. Chem. Soc. 1951, 73, 373380. Brunauer, S.; Emmett, P.; Teller, E. J. Am. Chem. Soc. 1938, 60, 309-319.

Background

Results

Conclusions

Future

Nanowires (2.8nm average diameter) form, Aggregate into ball-like domains (60-80nm diameter) Acts as a porous material, 6.6-9.6nm pore size Specific surface area: 23 m2g-1 Nanowires seem to result from the coalescence of spherical seeds (~2nm diameter).

Background

Results

Future work
Insitu EXAFS studies to look at Pt during course of reaction.
Irradiate with synchrotron radiation and run spectra after every hour of -irradiation Examine Pt chemical environment changes, should be able to follow aggregation

Future

Examine catalytic activity of nanoballs.

Remerciments
Thank you: Etch-a-Sketch Lite-Brite Spirograph Skeletor

References
1. Attard, G. S.; Gltner, C. G.; Corker, J. M.; Henke, S.; Templer, R. H. Angew. Chem., Int. Ed. Engl. 1997, 36, 1315. 2. Attard, G. S.; Barlett, P. N.; Colemen, N. R. B.; Elliott, J. M.; Owen, J. R.; Wang, J. H. Science 1997, 278, 838. 3. Barrett, E. P.; Joyner, L. G.; Halenda, P. P. J. Am. Chem. Soc. 1951, 73, 373380. 4. Brunauer, S.; Emmett, P.; Teller, E. J. Am. Chem. Soc. 1938, 60, 309-319. 5. Groen, J. C.; Louk. A. A. P.; Perez-Ramirez, J. Microporous Mesoporous Mater. 2003, 60, 1. 6. Krishnaswamy, R.; Remita, H.; Imperor-Clerc, M.; Even, C.; Davidson, P.; Pansu, B. ChemPhysChem 2006, 7, 1510. 7. Fukuoka, A.; Higashimoto, N.; Sakamoto, Y.; Sasaki, M.; Sugimoto, N.; Inagaki, S.; Fukushima, Y.; Ichikawa, M. Catal. Today 2001, 66, 23. 8. Pena dos Santos, E.; Tokumoto, M. S.; Surendran, G.; Remita, H.; Bourgaux, C.; Dieudonne, P.; Prouzet, E.; Ramos, L. Langmuir 2005, 21, 4362. 9. Surendran, G.; Apostelescu, G.; Tokumoto, M.; Prouzet, E.; Ramos, L.; Beaunier, P.; Kooyman, P. J.; Etcheberry, A.; Remita, H. Small 2005, 1, 964. 10. Surendran, G.; Pena dos Santos, E.; Tokumoto, M. S.; Remita, H.; Ramos, L.; Kooyman, P. J.; Santilly, C. S.; Bourgaux, C.; Dieudonne, P.; Prouzet, E. Chem. Mater. 2005, 17, 1505. 11. Surendran, G.; Ramos, L.; Pansu, B.; Prouzet, E.; Beaunier, P.; Audonnet, F.; Remita, H. Chemistry of Materials. 2007, 19 (21), 5045-5048.

Brunauer-Emmett-Teller (BET)
BET equation for multilayer adsorption
P = adsorption pressure Po = saturation vapor pressure c = constant n = amount absorbed (moles per gram adsorbent) at P/Po nm = monolayer capacity (moles to make monolayer on 1g absorbent)

Plot P/[n(PO-P)] against (P/PO) to find nm S = NAnm

S = specific surface area (m2/g) NA = Avogadros number nm = monolayer capacity = area occupied by one molecule (from tables)

Brunauer, S.; Emmett, P.; Teller, E. J. Am. Chem. Soc. 1938, 60, 309-319.

BJH Pore Distribution Model

Barrett-Joyner-Halenda First published in 1951 Based on Kelvin equation, corrected for multilayer adsorption Fast, easy, reliable results. Surface area, pore volume, and pore size distribution (PSD)
Barrett, E. P.; Joyner, L. G.; Halenda, P. P. J. Am. Chem. Soc. 1951, 73, 373380.

Problems with BJH

More complex (and accurate) models using nonlocal density functional theory (NLDFT) have been investigated. BJH model underestimates real pore size (by ~1nm) Particularly problematic for pore sizes 2-10nm
Groen, J. C.; Louk. A. A. P.; Perez-Ramirez, J. Microporous Mesoporous Mater. 2003, 60, 1. - 82 citing publications.

BJH Errors
Particularly problematic for pore sizes 2-10nm, underestimation of ~1nm. Authors claim pore sizes are 6.6-9.6nm These errors were not taken into consideration by the authors, nor were they mentioned (and thus likely not known) Does not change impact of the paper (as the primary study is not on porosity), but it is nevertheless important!

SAXS - What does it tell you?

Particle shape Internal structure of particles Surface-to-volume ratio, porosity Molecular weight, aggregation number Degree of crystallinity Particle size distribution Surface sensitive, used for film characterization (small areas)