Effects of Hydration on the Adsorption of Benzohydroxamic Acid on the Lead-Ion-Activated Cassiterite Surface: A DFT Study.

The strategy of enhancing the surface activity by preadsorption of metal ions (surface activation) is an effective way to promote the adsorption of surfactant on surfaces, which is very important in surface process engineering. However, the adsorption mechanism of surfactant (collector) on the surface preadsorbed by metal ions in the explicit solution phase is still poorly understood. Herein, the effects of hydration on the adsorption of benzohydroxamic acid (BHA) onto the oxide mineral surface before and after lead-ion activation are investigated by first-principles calculations, owing to its importance in the field of flotation. The results show that the direct adsorption of BHA on the hydrated surface is not thermodynamically allowed in the absence of metal ions. However, the adsorption of BHA onto the lead-ion-activated surface possesses a very low barrier and a very negative reaction energy difference, indicating that the adsorption of BHA on hydrated Pb at cassiterite surface is very favorable in both thermodynamics and kinetics. In addition, the adsorption of BHA results in the dehydration of hydrated Pb. More interestingly, the surface hydroxyl groups could participate in and may promote the coordination adsorption through proton transfer. This work sheds some new lights on understanding the roles of interfacial water and the mechanisms of metal-ion surface activation.