Recently, activation of peracetic acid (PAA) with the copper-based heterogeneous catalysts has been applied for organic pollutant abatement, yet the efficiency is limited by the sluggish Cu(II)/Cu(I) redox cycling. Regarding that reductive W(IV) can continuously effectively promote the regeneration of Cu(I) via the redox-reversible W(IV)/W(VI) couple, the W(IV) component is introduced to copper sulfide for efficient activation of PAA (simplified as the W-CuS/PAA process). Morphological and structural characterizations validate the incorporation of W(IV) component into the CuS lattice structure. Under neutral conditions, tetracycline (TC) can be completely removed within 30 min with the apparent first-order rate constant 5 times higher than that of the CuS/PAA process. CH₃C(=O)OO is demonstrated as the main radical responsible for TC abatement by radical quenching experiment and electron paramagnetic resonance (EPR). The redox properties and electron transfer capacity of CuS are significantly improved by the W(IV) component. The reductive W(IV) and S(–II) components facilitate the Cu(II)/Cu(I) redox cycling with the concomitant generation of reactive radicals. In addition, the influence of various parameters and coexisting anions on TC abatement is systematically investigated. Four degradation pathways of TC are put forward and the toxicity of intermediates is evaluated. The W-CuS/PAA process shows superior reuse performance and excellent adaptability in different water matrices. This study highlights the capability of the W(IV) to modulate the Cu(II)/Cu(I) redox cycle and proposes a feasible activator amelioration strategy for the efficient activation of PAA.

最近，用铜基多相催化剂活化过乙酸 (PAA) 已应用于有机污染物的减少，但效率受到缓慢的 Cu(II)/Cu(I) 氧化还原循环的限制。关于还原性 W(IV) 可以通过氧化还原可逆的 W(IV)/W(VI) 对持续有效地促进 Cu(I) 的再生，将 W(IV) 组分引入硫化铜中以有效活化 PAA （简化为 W-CuS/PAA 工艺）。形态和结构表征验证了 W(IV) 组分并入 CuS 晶格结构中。在中性条件下，四环素 (TC) 可在 30 分钟内完全去除，表观一级速率常数比 CuS/PAA 工艺高 5 倍。CH ₃ C(=O)OO通过自由基淬灭实验和电子顺磁共振 (EPR) 证明是导致 TC 减少的主要自由基。W(IV) 组分显着提高了 CuS 的氧化还原特性和电子转移能力。还原性 W(IV) 和 S(–II) 成分促进 Cu(II)/Cu(I) 氧化还原循环，同时产生反应性自由基。此外，系统地研究了各种参数和共存阴离子对 TC 消减的影响。提出了原药的四种降解途径，并对中间体的毒性进行了评价。W-CuS/PAA 工艺在不同的水基质中显示出卓越的再利用性能和出色的适应性。