Deactivation and Regeneration of Lewis Basic Sites Following Reversible Chemical Adsorption and Desorption of Hydroxyl Groups in Contaminant Degradation by Advanced Oxidation

The Lewis basic catalysts were susceptible to poisoning during the activation of peroxymonosulfate, resulting in their transformation into spent catalysts and subsequent secondary environmental contamination. In this work, the chemical constitution of the catalyst’s surface during both the deactivation and regeneration processes was intensively tracked. The mechanistic studies revealed that the reversible bonding of adsorbed hydroxyl groups generated from peroxymonosulfate activation with Lewis basic carbon atoms adjacent to pyridinic nitrogen was identified as the intrinsic mechanism responsible for the catalyst regeneration, accompanied by the reappearance of Lewis basic sites. Following high-temperature or sodium borohydride reduction, the activity of the catalysts was restored to over 90% of the initial activity, enabling the spent catalysts to be reused multiple times. Catalyst deactivation corresponded to an increase in the C–OH content from 24.3% to 35.2%, whereas regeneration reduced it to 25.16%. Furthermore, a strong inverse correlation was observed between the surface hydroxyl density and the catalytic activity. The study elucidates the deactivation and regeneration mechanisms of Lewis basic catalysts at the atomic scale, paving the way for durable applications in advanced oxidation processes.