A simple electrostatic model of metal adsorption onto oxide surfaces has great utility
for the preparation of typical supported metal catalysts. Owing to the chemistry of
the surface hydroxide groups, the oxide surfaces become protonated and positively
charged at pH values below their PZC, and capable of strongly adsorbing metal
anions. Above the oxide PZC, the surface is deprotonated and negatively charged
and capable of strongly adsorbing cations. In either case, however, the oxide buffering
effect must be overcome. This is accomplished in practice by measuring and
controlling the final pH of the slurry solution. It is hypothesized that once the metal
precursor has been strongly adsorbed, it can be reduced to its active elemental state
at conditions that retain its high dispersion.
The strong electrostatic adsorption approach can be applied to a novel system
in three steps: (1) measure the PZC of the oxide (or carbon), and choose a metal
cation for low PZC materials and an anion for high PZC materials, (2) perform an
uptake-pH survey to determine the pH of strongest interaction in the appropriate pH
regime (high pH for low PZC and vice versa), and (3) tune the calcination/reduction
steps to maintain high dispersion. Highly dispersed Pt materials have been prepared
in this way over silica, alumina, and carbon. Other oxides can be employed similarly.
Bimetallics should be effectively synthesized by adsorbing a second metal complex
selectively onto a precursor oxide phase of the first metal and then reducing the
intimately contacted metals. Over promoter/support surfaces, pH can be used to
achieve selective adsorption of the metal complex onto the promoter and not the
support.