Combining chemical oxidation and adsorption is highly desirable but challenging to remove organoarsenic compounds for water purification. Herein, we prepared a Zn-doped CuO (CuZnOx-2) catalyst by incorporating Zn atoms into the CuO lattice, which results in abundant surface oxygen vacancies (OVs) and modulates the electronic structure of Cu-OVs-Zn sites for PMS activation to degrade p-arsanilic acid (p-ASA) and adsorb the secondary arsenic species simultaneously. The elevated d-band centers for Cu upward to the Fermi level can significantly strengthen the adsorption of PMS, p-ASA, and the generated arsenic species. The OVs cause the charge redistribution to form electron-rich centers, which accelerate the electron transfer from Cu-OVs-Zn sites to adsorbed PMS, facilitating the cleavage of peroxide bond to produce SO4•−, •OH. Furthermore, the PMS adsorbed on the local environment of OVs with different configurations can directly decompose to produce 1O2 without undergoing PMS → O2•− → 1O2 or O2 → O2•− → 1O2 processes. The evolution process of the main arsenic species in solution and catalyst surface with oxidation was clarified. The ultimate removal of the total As involves 20 % As(III), 60 % As(V), and 20 % organic arsenic intermediates via forming inner-sphere complexes or electrostatic interaction. This contribution provides a brand-new perspective for the remediation of organoarsenic pollution over designing highly active catalysts.

中文翻译：

---

促进CuZnOx-2/过氧一硫酸盐体系中氧空位对砷酸降解和次生砷物种固定化的影响


化学氧化和吸附相结合是非常可取的，但去除有机砷化合物以净化水具有挑战性。在此，我们通过将 Zn 原子掺入 CuO 晶格中制备了一种 Zn 掺杂 CuO （CuZnOx-2） 催化剂，这导致丰富的表面氧空位 （OVs） 并调节 Cu-OVs-Zn 位点的电子结构以激活 PMS，以降解对砷酸 （p-ASA） 并同时吸附仲砷物种。Cu 的 d 带中心升高至费米能级可以显着加强对 PMS、p-ASA 和生成的砷种类的吸附。OV 导致电荷重新分布形成富电子中心，从而加速电子从 Cu-OVs-Zn 位点转移到吸附的 PMS，促进过氧化物键的裂解以产生 SO4•−， •OH。此外，吸附在不同构型的 OVs 局部环境中的 PMS 可以直接分解产生 1O2，而无需→ O2•− → 1O2 或 O2 → O2•− → 1O2 过程。阐明了主要砷种在溶液和催化剂表面的氧化演化过程。总砷的最终去除涉及 20% 的 As（III）、60% 的 As（V） 和 20% 的有机砷中间体，通过形成内球络合物或静电相互作用。这一贡献为有机砷污染的修复提供了全新的视角，而不是设计高活性催化剂。