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Uniform filling of the pores can be achieved using the incipient wetness technique, using concentrated solutions at pH
values that minimize adsorption. The pH is adjusted to take account of the isoelectric point of the support (Table 7). To
overcome the problem of aggregation during the drying step and nonuniformity of the adsorption using the incipient
wetness technique, greater quantities of liquid can be used and, in the extreme, this involves the use of a large excess of
dilute solution, which has been used by Wang and Hall (21) to prepare monolayer molybdenum/alumina catalysts.
Table 7. Isoelectric Points of Various Oxides
Oxide IEPS Adsorption
Sb2O5 <0.4 Cations
WO3 hydrous <0.5
SiO2 1.0¨C2.0
MnO2 3.9¨C4.5 Cations or anions
SnO2 ~5.5
TiO2 (anatase, rutile) ~6
-Fe2O3 6.5¨C6.9
ZrO2 hydrous ~6.7
CeO2 hydrous ~6.75
Cr2O3 hydrous 6.5¨C7.5
, -Al2O3 7.0¨C9.0
-Fe2O3 ~8.9 Anions
ZnO 8.4¨C9.0
La2O3 hydrous 8.7¨C9.7
MgO ~10.4
12.1¨C12.7
Controlled adsorption from solution uses highly diluted solutions of the additive and the pH is adjusted to control the
rate of adsorption. The method has been optimized for MoO3/ -Al2O3 and WO3/ -Al2O3 catalysts (20-22). The pH is
used to control two factors: (1) the surface charge of the support and (2) the size of oxyanions of molybdenum and
tungsten. It must be recognized that the surface of the oxide support changes its polarization according to the value of
the pH of the solution and the isoelectronic point, which is also known as the zero charge point (Table 7) (23). At a pH
below the isoelectronic point, the surface is positively charged and, therefore, attracts anions while, at a pH above the
isoelectronic point, the surface becomes negatively charged and, hence, attracts cations. An example of the control of
surface charge affecting adsorption is shown in Fig. 4 for the adsorption of cobalt and tungsten species onto -Al2O3.
The isoelectric point of alumina is ca pH 8¨C9 and the lack of adsorption of cobalt at pH <6 is due to the inability of the
positively charged cobalt cations to adsorb in the positively charged alumina surfaces. Additionally, at pH >8, cobalt
precipitates from the solution as hydroxides or basic carbonates. Hence, for alumina, there is a very narrow pH window
that can be used for the controlled adsorption of positively charged cations (22, 24). The reverse situation is observed
for the tungsten, and also molybdenum, species because of the negative charge of the tungstate and polytungstate
anions, which are readily adsorbed onto the positively charged alumina surface below pH 8.

[ Last edited by leeying on 2006-8-9 at 16:51 ]
3Â¥2006-08-09 16:50:25
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xibeilong

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