Adsorption of Nickel Ions on the γ-Alumina Surface: Competitive Effect of Protons and Its Impact on Concentration Profiles.

Mesoporous γ-alumina is used as an adsorbent in the decontamination of water from heavy metals (e.g., nickel and cobalt) and as a support for heterogeneous catalysts prepared by impregnation. In these cases, alumina extrudates are in contact with aqueous solutions containing precursors of the active metal phase to be deposited. The proton concentration (or pH) in the metal solution in contact with alumina can impact the adsorption efficiency of decontamination processes and the activities of catalysts. Yet, it is difficult to quantify the effect of the pH inside the pores since protons are not detected by classical imaging techniques. In this article, the effect of protons on nickel adsorption on alumina is evaluated using a novel technique coupling liquid analysis (pH, conductivity, and UV/vis) and laser-induced breakdown spectroscopy (or LIBS) analysis of concentration gradients inside the solid. Both methods are in excellent agreement. The results show a slow diffusion of protons inside alumina pores (diffusion continues even after 940 min), yielding high proton concentration gradients. On the other hand, the nickel species penetrate the extrudates faster but are slowly displaced by protons under certain operating conditions. As a result, different metal concentration profiles are obtained, depending on the initial pH and contact time. These findings are interesting in catalysis since they prove the possibility of controlling the deposition of the active metal on catalysts by regulating the operating conditions of impregnation. For typical industrial impregnation times (a few minutes to 1 to 2 h), protons do not have enough time to deeply penetrate inside extrudates, so the initial pH of the metal solution will have nearly no effect on the metal distribution. Conversely, decontamination processes have much longer contact times; therefore, lower initial pH values should have negative impacts on the adsorption efficiency due to the protons displacing the adsorbed nickel.