Hydrothermal Synthesis of

Nanomaterials

Andrew van Bommel

January 18th, 2006
 Hydrothermal Synthesis
• The reactants are dissolved (or placed) in
water or another solvent (solvothermal) in
a closed vessel
• Bomb is heated above BP
• Conventional or MW oven
• Commercially:
– Tons of zeolites daily

Nazari, G.A., Pistoria, G. Lithium Batteries; Klumer Academic Pubs.: Boston, 2004.
 Conditions
• Solvent above boiling point (supercritical
water)
• Usually basic conditions
• Useful for Nano!
– Oxides (TiO2, VOx, MxMnO2)
– Layered oxides: nanowires/tubes
– C-nanotubes can be formed this way
– Some elemental nanostructures (eg: Bi)
 Mechanism for HT rxn
• Usually follows a liquid nucleation model
• Differs from solid-state- reaction
mechanism from diffusion of atoms or
ions between reactants
• Due to enhanced solubility:
– Solubility of water increases with
temperature, but alkaline solubility increases
dramatically with temperature

Barrer, R.M. Hydrothermal Chemistry of Zeolites; Academic Press: London, 1982

 Solubility
• Solubility of SiO2 (quartz)

T (°C) Sol (g/L) T (°C) NaOH wt% Sol (g/L)

100 - 300 1 20
5 135
150 0.0030 15 514

200 0.024 350 1 25

5 152
250 0.049 15 515

400 1 35
300 0.068
5 155
350 0.070 15 560

450 1 35
374 0.023
5 163
15 560

Barrer, R.M. Hydrothermal Chemistry of Zeolites; Academic Press: London, 1982

 Next Slides
• Examples:
– Nanoparticles
– Nanowires/tubes
– Nanoflowers
• Control of Shape
 BaTiO3 Nanoparticles
• Ba(OH)2 + TiO2  BaTiO3
nanoparticles
• 300 - 450°C, HT
• Two proposed mechanisms:
– Dissolution-recrystallization
– In situ crystallization

Hakuta, R., Ura, H. Hayashi, H, and Arai, K. Ind. Eng. Chem. Res. 2005, 44, 840-846
 Dissolution-Recrystallization
• BaTiO3 formation at 150°C
• Stated:
– “when varying the water/isopropanol ratio in synthesis at 150°C, the grain size of
barium titanate decreases when the amount of alcohol increases, i.e. when the
solubility of the precursors decreases”
– “TEM observations of incompletely reacted powders showed that the grains are
either amorphous or entirely crystalline BaTiO3, which means that
homogeneous nucleation and growth is occurring instead of heterogeneous
nucleation
– “high resolution TEM observations of fully reacted powders revealed the
presence of necks between particles. These three experimental observations in
the same reaction system provide strong evidence of dissolution-precipitation as
the primary reaction mechanism.”

Pinceloup, R., Courtoisa, C., Vicensb, J., Lerichea, A., and Thierry, B. J. Eur. Ceram.
Soc. Res. 1999, 19, 973-977.
 In-situ crystallization
• Non-dissolved TiO2 reacts with barium
and hydroxide ions

Eckert, J.O., Hung-Houston, C.C., Gersten, B.L., Lencka, M.M., Riman, R.E., J. Am.
Ceram. Soc. 1996, 79, 2939.
 Why Nano?
• For in-situ transformation, formation of a
porous product facilitates the transfer of
the reacting species, leading to a facile
reaction
• For dissolution-precipitation reaction,
dissolution (and subsequent precipitation)
must be fast to ensure a steady flow of
reactants

Eckert, J.O., Hung-Houston, C.C., Gersten, B.L., Lencka, M.M., Riman, R.E., J. Am.
Ceram. Soc. 1996, 79, 2939.
 Tube/wire Formation
• TiO2 +NaOHtitanate nanomaterial
• Crystal flakes rolled along [001] direction

Chen, Q., Du, G.H., Zhang, S., Peng, L.M. Acta Cryst. 2002, B58, 587-593.
 Why nanowires/tubes?
• Two-dimensional crystal flakes have low
resistance to bending: hydrothermal
energy curls these flakes
• Why tubes?
– When diameter grows, the strain in the tubes
is outweighed by the minimizing of energy
with nanotubes’ self-closed layers (no
dangling bonds)

Remskar, M. Adv. Mater. 2004, 16, 1497-1502.

 More Nano!
• Nanoflower ZnO- CTAB assisted
hydrothermal reaction of ZnO (in NaOH
solution)

Zhang, H., Yang, D., Ji, Y., Ma, X., Xu, J., Que, D. J. Phys. Chem. B. 2004, 108, 3955-
3958
 Hydrothermal Route
• Pros:
– New materials
– Easy, relatively cheap
• Cons:
– Difficult to control morphology, size
– Not for all materials
– May obtain variation in size
 Summary
• Hydrothermal synthesis involves the
chemical reaction of materials in aqueous
solution heated (usually above BP) in a
sealed vessel (bomb)
• Alkaline solution used to increase
solubility (for a dissolution-precipitation
reaction)
• It is difficult to predict the resultant
morphology of the product
 Summary
• Nanomaterials are apt to form in HT
synthesis as the formation of these
structures allows for facile diffusion of
reactants
• Hydrothermal synthesis is used for oxide
nanoparticle synthesis as the solubility is
high in the alkaline medium