It is shown that, during the preparation of Cu/SiO 2 samples by selective adsorption of copper tetraammine complex [Cu(NH 3 ) 4 (H 2 O) 2 ] 2+ on silica, two types of supported Cu II species form: grafted Cu II ions and copper phyllosilicate. The formation of grafted Cu II ions results from electrostatic adsorption of Cu II ammine complex cations in solution onto the surface of silica particles negatively charged due to the high solution pH. Grafting of Cu II ions occurs during the subsequent drying step. The formation of copper phyllosilicate takes place in solution. It results from a reaction between silicic acid arising from silica dissolution and [Cu(OH) 2 (H 2 O) 4 ] 0 complex in solution. Both Cu II species lead to small metal particles after reduction. Several preparation parameters were investigated in this paper: the metal precursor concentration, the pH of the precursor solution, the solution/silica contact time, and the addition of ammonium nitrate to the precursor solution. The amount of copper phyllosilicate depends on the pH of the precursor solution; it is maximum at pH 9, that is, at the pH at which the concentration of [Cu(OH) 2 (H 2 O) 4 ] 0 complex is maximum according to calculation of Cu II speciation. The amount of copper phyllosilicate increases with the solution/silica contact time because its formation is a kinetically limited process. It was found that the addition of ammonium nitrate to the precursor solution prevents the formation of copper phyllosilicate. This can be explained by calculations of the Cu II speciation in solution. The formation of Cu II ammine complexes is favored in the presence of NH 4 + so that the concentration of [Cu(OH) 2 (H 2 O) 4 ] 0 complex strongly decreases and its maximum of concentration shifts to pH lower than the pH's of preparation.

The deposition of Mo on γ-alumina by the equilibrium adsorption method starting from ammonium heptamolybdate has been studied. Spectroscopic results converge to indicate that a previously unrecognized species, i.e., the Anderson-type heteropolymolybdate [Al(OH)6Mo6O18]3-, plays a major role in this type of synthesis as it is quantitatively formed in the solution within a few hours, by reaction of the heptamolybdate with dissolved aluminic species. This results in a considerable increase of alumina solubility in conditions generally thought to be nonaggressive. Furthermore, this species is also present in the solid catalyst after deposition, although it is harder to observe than in the liquid phase. A parallel is drawn with a well-known idea from the field of geochemistry, i.e., ligand-promoted oxide dissolution. The relevance of this phenomenon in catalyst preparation is evaluated in realistic conditions corresponding to published studies and/or industrial procedures. It is concluded that strong metal−support interaction in the deposition stage by surface dissolution followed by reaction in the liquid phase is most likely to be an important phenomenon, not only for cationic metal precursors as previously known but also for anionic precursors such as molybdates.