Trigger efficient peroxydisulfate-assisted photocatalysis by S-scheme Co3O4/BiOCl heterojunctions: Vital roles of Co2+/Co3+ redox centers and oxygen vacancies

IF 7.2 2区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Environmental Chemical Engineering Pub Date : 2025-09-10 DOI:10.1016/j.jece.2025.119195

Chang-Bin Yu , Chong Xu , Lin He , Wei-Ya Huang , Kai Yang , Dan Li

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引用次数: 0

Abstract

Persulfate-assisted photocatalysis (PA-PC) has been considered as an efficient technique for wastewater treatment. However, regulating interfacial charge transfer and radical/non-radical active species in the reaction system is still a challenge. This study successfully decorated Co₃O₄ nanoparticles on BiOCl flower-like microspheres via a simple solution method, forming S-scheme Co₃O₄/BiOCl heterojunctions with enriched oxygen vacancies (OVs) for highly efficient PA-PC of tetracycline hydrochloride (TC). After exposure to 18-min visible light illumination in the presence of peroxydisulfate (PDS) (namely the BOC-5/PDS/Vis system), the optimized catalyst, BOC-5, reached a TC degradation of 92.3 % and a total organic carbon (TOC) removal of 66.2 %, outperforming many reported catalysts in the literature. Common anions (Cl⁻, CO₃²⁻, NO₃⁻) and cations (Zn²⁺) showed negligible interference on the performance of BOC-5/PDS/Vis system, demonstrating its excellent anti-interference capability. Such system was also proven with a broad pH adaptability in the range of 3.0 – 11.0. Cycling tests confirmed the outstanding stability of BOC-5, while toxicity assessments revealed significantly reduced ecological toxicity of intermediates in comparison with TC. The construction of S-scheme Co₃O₄/BiOCl heterojunctions with intimate 0D/2D interfacial contact markedly promoted charge carrier separation efficiency. The photogenerated electron (e^–) enabled the reduction of Co³⁺ to Co²⁺, accelerating the Co²⁺/Co³⁺ redox cycle to facilitate e^– transfer for PDS activation. The OVs improved light absorption and induced generation of more superoxide radicals (•O₂⁻) as the dominant active species. These along with singlet oxygen (¹O₂) boosted the degradation efficiency of TC. Our research presented efficient interfacial and defect engineering strategies for the design of heterojunctions aiming at antibiotic removal from wastewater through PA-PC.

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S-scheme Co3O4/BiOCl异质结触发高效过氧化二硫酸盐辅助光催化：Co2+/Co3+氧化还原中心和氧空位的重要作用

过硫酸盐辅助光催化（PA-PC）是一种高效的废水处理技术。然而，调节反应体系中的界面电荷转移和自由基/非自由基活性物质仍然是一个挑战。本研究通过简单溶液法将Co3O4纳米颗粒修饰在BiOCl花状微球上，形成具有富氧空位（OVs）的s型Co3O4/BiOCl异质结，用于高效的盐酸四环素（TC）的PA-PC。在过硫酸氢盐（PDS）（即BOC-5/PDS/Vis体系）存在的可见光照射下暴露18分钟后，优化后的催化剂BOC-5的TC降解率为92.3 %，总有机碳（TOC）去除率为66.2% %，优于文献中报道的许多催化剂。常见阴离子（Cl−、CO32−、NO3−）和阳离子（Zn 2 +）对BOC-5/PDS/Vis体系性能的干扰可以忽略不计，显示出优异的抗干扰能力。该体系还被证明具有3.0 - 11.0范围内的广泛pH适应性。循环试验证实了BOC-5出色的稳定性，而毒性评估显示，与TC相比，中间体的生态毒性显著降低。构建具有密切的0D/2D界面接触的S-scheme Co3O4/BiOCl异质结显著提高了载流子分离效率。光生电子（e -）使Co3+还原为Co2+，加速Co2+/Co3+氧化还原循环，促进PDS活化的e转移。OVs改善了光吸收，并诱导超氧自由基（•O2−）的产生，成为优势活性物质。这些与单线态氧（1O2）一起提高了TC的降解效率。我们的研究提出了高效的界面和缺陷工程策略来设计异质结，旨在通过PA-PC去除废水中的抗生素。

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来源期刊

Journal of Environmental Chemical Engineering Environmental Science-Pollution

CiteScore

11.40

自引率

6.50%

发文量

2017

审稿时长

27 days

期刊介绍： The Journal of Environmental Chemical Engineering (JECE) serves as a platform for the dissemination of original and innovative research focusing on the advancement of environmentally-friendly, sustainable technologies. JECE emphasizes the transition towards a carbon-neutral circular economy and a self-sufficient bio-based economy. Topics covered include soil, water, wastewater, and air decontamination; pollution monitoring, prevention, and control; advanced analytics, sensors, impact and risk assessment methodologies in environmental chemical engineering; resource recovery (water, nutrients, materials, energy); industrial ecology; valorization of waste streams; waste management (including e-waste); climate-water-energy-food nexus; novel materials for environmental, chemical, and energy applications; sustainability and environmental safety; water digitalization, water data science, and machine learning; process integration and intensification; recent developments in green chemistry for synthesis, catalysis, and energy; and original research on contaminants of emerging concern, persistent chemicals, and priority substances, including microplastics, nanoplastics, nanomaterials, micropollutants, antimicrobial resistance genes, and emerging pathogens (viruses, bacteria, parasites) of environmental significance.