Persulfate (PS)-based advanced oxidation process (AOP) has attracted wide attention in recent years, in which it is crucial to develop a cost-effective and environmentally friendly catalyst. Herein, a waste eggshell derived eggshell/CuS (ES-CuS) composite catalyst was successfully prepared in a simple way, and used in combination with PS to degrade tetracycline hydrochloride (TCH). Our results showed that the coated CuS had a sheet-like structure and was evenly distributed on the surface of the eggshell, which could effectively prevent agglomeration and enhance catalytic performance. Electron spin resonance (ESR) and free radical capturing experiments confirmed that a series of active species such as sulfate radicals (SO₄⁻), hydroxyl radicals (OH), as well as carbonate radicals (CO₃-) were produced during the catalysis process, which is the main reason for enhanced catalytic effect compared with that of the pure CuS. A possible degradation pathway was proposed. It can be expected that discarded eggshells can be used as a low-cost carrier for the synthesis of various composites to achieve its valorization, which have very broad development prospects in the field of environmental remediation or catalysis.

近年来，基于过硫酸盐（PS）的高级氧化工艺（AOP）受到了广泛的关注，在其中开发具有成本效益且对环境友好的催化剂至关重要。在此，以简单的方式成功地制备了废蛋壳衍生的蛋壳/ CuS（ES-CuS）复合催化剂，并与PS结合使用以降解四环素盐酸盐（TCH）。我们的结果表明，包被的CuS具有片状结构并均匀地分布在蛋壳表面，可以有效地防止团聚并增强催化性能。电子自旋共振（ESR）和自由基捕获实验证实了一系列的活性物质，如硫酸自由基（SO的₄ ^- ），羟基自由基（OH），以及碳酸酯基团（CO ₃-）是在催化过程中产生的，这是与纯CuS相比增强催化效果的主要原因。提出了一种可能的降解途径。可以预期，废弃的蛋壳可以用作合成各种复合材料以实现其增值的低成本载体，这在环境修复或催化领域具有非常广阔的发展前景。