Enhanced mineralization of oxalate by highly active and Stable Ce(III)-Doped g-C₃N₄ catalyzed ozonation

The degradation of carboxylic acid has been identified as one of the rate-determining steps in the mineralization of organic pollutants by ozonation. In this study, Ce(III)-doped graphitic carbon nitride (Ce-CN) composites with different Ce(III) contents were synthesized and used as catalysts for the ozonation of oxalate. The morphology and structure of the Ce-CN were comprehensively characterized using various techniques such as SEM, XRD, FTIR, and XPS. The results show that the structure of g-C₃N₄ provided an ideal site for the accommodation of Ce(III) and thus facilitated the formation of surface hydroxyl groups. With 2.5%Ce-CN as a catalyst, the degradation efficiency of oxalate was increased by 47.1% after reaction for 30 min. The decomposition of ozone was accelerated in the presence of Ce-CN. Hydroxyl radicals were recorded by electron spin resonance and identified as the major actives species. Under the catalysis of 2.5%Ce-CN, the production of hydroxyl radicals was increased by 40%. The Ce(III) and surface hydroxyl groups that distributed uniformly on the surface of Ce-CN were speculated as the dual catalytic sites for the complexation of oxalate and activation of ozone, respectively. Ce-CN had a high stability and reutilization capability. It is proposed that a complex was formed between surface Ce(III) and oxalate, and this complex could be more easily attacked by the surrounding ozone and hydroxyl radicals than free oxalate. As oxalate is a typical recalcitrant carboxylic acid, the findings from this study are expected to promote the application of ozonation in the removal of organic pollutants.