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Schematic diagram of solvothermal synthesis setup: (1) stainless steel autoclave (2)
precursor solution (3) Teflon liner (4) stainless steel lid (5) spring
The high photocatalytic capacity of TiO2 leads to the degradation of organic [6][7] and
biological molecules [8][9] into smaller and less harmful compounds. Because of their small
size, TiO2 nanostructures also provide increased surface area at which photocatalytic
reactions may occur, increasing their activity. This photocatalytic activity may be applied to
air purification,[10] self-sterilization,[11] water purification [12] and molecular hydrogen
production.[13] Thus the ability of solvothermal synthesis to precisely tailor TiO2
nanostructures has the potential to maximize the efficiency of those nanostructures in
applications.
References
1. ^ Oliveira, Marcela M.; Schnitzler, Danielle C.; Zarbin, Aldo J. G. (2003).
"(Ti,Sn)O2Mixed Oxides Nanoparticles Obtained by the SolGel Route".
Chemistry of Materials 15 (9): 1903. doi:10.1021/cm0210344.
2. ^ Andersson, Martin; sterlund, Lars; Ljungstrm, Sten; Palmqvist, Anders (2002).
"Preparation of Nanosize Anatase and Rutile TiO2by Hydrothermal Treatment of
Microemulsions and Their Activity for Photocatalytic Wet Oxidation of Phenol".
The Journal of Physical Chemistry B 106 (41): 10674. doi:10.1021/jp025715y.
3. ^ Xie, Rong-Cai; Shang, Jian Ku (2007). "Morphological control in solvothermal
synthesis of titanium oxide". Journal of Materials Science 42 (16): 6583. Bibcode
2007JMatS..42.6583X. doi:10.1007/s10853-007-1506-0.
4. ^ Choucair, Mohammad; Thordarson, Pall; Stride, John A. (2008). "Gram-scale
production of graphene based on solvothermal synthesis and sonication". Nature
Nanotechnology 4 (1): 303. Bibcode 2009NatNa...4...30C.
doi:10.1038/nnano.2008.365. PMID 19119279.
5. ^ Hu, Gang; Ma, Ding; Cheng, Mojie; Liu, Lin; Bao, Xinhe (2002). "Direct
synthesis of uniform hollow carbon spheres by a self-assembly template
approachElectronic supplementary information (ESI) available: SEM pictures of the
products from simple mixing. See http://www.rsc.org/suppdata/cc/b2/b205723a/".
Chemical Communications (17): 1948. doi:10.1039/B205723A.
6. ^ Kongsuebchart, W; Praserthdam, P; Panpranot, J; Sirisuk, A;
Supphasrirongjaroen, P; Satayaprasert, C (2006). "Effect of crystallite size on the
surface defect of nano-TiO2 prepared via solvothermal synthesis". Journal of
Crystal Growth 297: 234. Bibcode 2006JCrGr.297..234K.
doi:10.1016/j.jcrysgro.2006.09.018.
7. ^ Kus, Mahmut; Gernjak, Wolfgang; Ibez, Pilar FernNdez; Rodrguez, Sixto
Malato; Glvez, Julin Blanco; Icli, Siddik (2006). "A Comparative Study of
Supported TiO[sub 2] as Photocatalyst in Water Decontamination at Solar Pilot
Plant Scale". Journal of Solar Energy Engineering 128 (3): 331.
doi:10.1115/1.2210494.
8. ^ Cheng, Y.W.; Chan, Raphael C.Y.; Wong, P.K. (2007). "Disinfection of
Legionella pneumophila by photocatalytic oxidation". Water Research 41 (4): 842
52. doi:10.1016/j.watres.2006.11.033. PMID 17224169.
9. ^ Amezagamadrid, P; Silveyramorales, R; Cordobafierro, L; Nevarezmoorillon, G;
Mikiyoshida, M; Orrantiaborunda, E; Solis, F (2003). "TEM evidence of
ultrastructural alteration on Pseudomonas aeruginosa by photocatalytic TiO2 thin
films". Journal of Photochemistry and Photobiology B: Biology 70: 45.
doi:10.1016/S1011-1344(03)00054-X.
10. ^ Josset, S; Taranto, J; Keller, N; Keller, V; Lett, M; Ledoux, M; Bonnet, V;
Rougeau, S (2007). "UV-A photocatalytic treatment of high flow rate air
contaminated with Legionella pneumophila". Catalysis Today 129: 215.
doi:10.1016/j.cattod.2007.08.010.
11. ^ Mitoraj, Dariusz; Ja?czyk, Agnieszka; Strus, Magdalena; Kisch, Horst; Stochel,
Gra?yna; Heczko, Piotr B.; Macyk, Wojciech (2007). "Visible light inactivation of
bacteria and fungi by modified titanium dioxide". Photochemical & Photobiological
Sciences 6 (6): 6428. doi:10.1039/B617043A. PMID 17549266.
12. ^ Yurdakal, S; Loddo, V; Augugliaro, V; Berber, H; Palmisano, G; Palmisano, L
(2007). "Photodegradation of pharmaceutical drugs in aqueous TiO2 suspensions:
Mechanism and kinetics". Catalysis Today 129: 9.
doi:10.1016/j.cattod.2007.06.044.
13. ^ Park, H.; Vecitis, C.D.; Choi, W.; Weres, O.; Hoffmann, M.R. (2008). "Solar-
Powered Production of Molecular Hydrogen from Water". Journal of Physical
Chemistry C 112 (4): 885. doi:10.1021/jp710723p.
Hydrothermal synthesis
From Wikipedia, the free encyclopedia
Jump to: navigation, search
Crystallization
Concepts
Crystallization Crystal growth
Recrystallization Seed crystal
Protocrystalline Single crystal
Fundamentals
Nucleation Crystal
Crystal structure Solid
Methods and technology
Boules BridgmanStockbarger
Czochralski process Fractional crystalliz.
Frac. freezing Hydrot. synthesis LHPG
v
t
e
A synthetic quartz crystal grown by the hydrothermal method
Possible advantages of the hydrothermal method over other types of crystal growth include
the ability to create crystalline phases which are not stable at the melting point. Also,
materials which have a high vapour pressure near their melting points can also be grown by
the hydrothermal method. The method is also particularly suitable for the growth of large
good-quality crystals while maintaining good control over their composition.
Disadvantages of the method include the need of expensive autoclaves, and the
impossibility of observing the crystal as it grows.[1]
Contents
1 History
2 Uses
3 Equipment for hydrothermal crystal growth
4 Methods
o 4.1 Temperature-difference method
o 4.2 Temperature-reduction technique
o 4.3 Metastable-phase technique
5 See also
6 References
7 External links
History
In 1839, the German chemist Robert Bunsen contained aqueous solutions in thick-walled
glass tubes at temperatures above 200 C and at pressures above 100 bars.[2] The crystals of
barium carbonate and strontium carbonate that he grew under these conditions mark the
first use of hydrothermal aqueous solvents as media. Other early reports of the
hydrothermal growth of crystals were by Schafhult in 1845 and by de Snarmont in 1851,
who produced only microscopic crystals.[3] Later G. Spezzia (1905) published reports on
the growth of macroscopic crystals.[4] He used solutions of sodium silicate, natural crystals
as seeds and supply, and a silver-lined vessel. By heating the supply end of his vessel to
320-350 C, and the other end to 165-180 C, he obtained about 15 mm of new growth over
a 200 day period. Unlike modern practice, the hotter part of the vessel was at the top. A
shortage in the electronics industry of natural quartz crystals from Brazil during World War
2 led to postwar development of a commercial-scale hydrothermal process for culturing
quartz crystals, by A. C. Walker and Ernie Buehler in 1950 at Bell Laboratories.[5] Other
notable contributions have been made by Nacken (1946), Hale (1948), Brown (1951), and
Kohman (1955).[6]
Uses
A large number of compounds belonging to practically all classes have been synthesized
under hydrothermal conditions: elements, simple and complex oxides, tungstates,
molybdates, carbonates, silicates, germanates etc. Hydrothermal synthesis is commonly
used to grow synthetic quartz, gems and other single crystals with commercial value. Some
of the crystals that have been efficiently grown are emeralds, rubies, quartz, alexandrite and
others. The method has proved to be extremely efficient both in the search for new
compounds with specific physical properties and in the systematic physicochemical
investigation of intricate multicomponent systems at elevated temperatures and pressures.
Methods
Temperature-difference method
The most extensively used method in hydrothermal synthesis and crystal growing. The
supersaturation is achieved by reducing the temperature in the crystal growth zone. The
nutrient is placed in the lower part of the autoclave filled with a specific amount of solvent.
The autoclave is heated in order to create two temperature zones. The nutrient dissolves in
the hotter zone and the saturated aqueous solution in the lower part is transported to the
upper part by convective motion of the solution. The cooler and denser solution in the
upper part of the autoclave descends while the counterflow of solution ascends. The
solution becomes supersaturated in the upper part as the result of the reduction in
temperature and crystallization sets in.
Temperature-reduction technique
In this technique crystallization takes place without a temperature gradient between the
growth and dissolution zones. The supersaturation is achieved by a gradual reduction in
temperature of the solution in the autoclave. The disadvantage of this technique is the
difficulty in controlling the growth process and introducing seed crystals. For these reasons,
this technique is very seldom used.
Metastable-phase technique
This technique is based on the difference in solubility between the phase to be grown and
that serving as the starting material. The nutrient consists of compounds that are
thermodynamically unstable under the growth conditions. The solubility of the metastable
phase exceeds that of the stable phase, and the latter crystallize due to the dissolution of the
metastable phase. This technique is usually combined with one of the other two techniques
above.
See also
Crystallography
Verneuil Process
Czochralski
Epitaxy
Crystal growth
Chemical vapor deposition
Flux method
References
1. ^ O'Donoghue, M. (1983). A guide to Man-made Gemstones. Great Britain: Van
Nostrand Reinhold Company. pp. 4044. ISBN 0-442-27253-7.
2. ^ Laudise, R.A. (1986). "Hydrothermal Synthesis of Crystals". C&EN. September
28: 3043.
3. ^ "Hydrothermal Crystal Growth - Quartz". Roditi International. Retrieved 2006-
11-17.
4. ^ Spezzia, G. (1905). Accad. Sci. Torino Atti 40: 254.
5. ^ McWhan, Denis McWhan (2012). Sand and Silicon: Science That Changed the
World. Oxford Univ. Press. pp. 11. ISBN 0199640270.
6. ^ Laudise, R.A. (1958). R.H. Doremus, B.W. Roberts and D. Turnbull. ed. Growth
and perfection of crystals. Prroceedings of an International Conference on Crystal
Growth held at Cooperstown, New York on August 2729, 1958.. Wiley, New York.
pp. 458463.
Autoclave Engineers was founded by Fred Gasche in 1945 to fill a gap in the
world of high pressure and high temperature technology. Autoclave has created
and produced many novel pressure vessel designs as well as made significant
break throughs in high pressure technology such as the MagneDrive
magnetically coupled agitator. We have made these developments through
commitments to constant innovation and hiring the best technical personnel
available. This commitment is supported and encouraged by our parent company
Snap-tite, Inc.
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