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原位构建绿色ZnFeO/亚5纳米氮、铜双掺杂SnO S型异质结构用于增强四环素去污的空间电荷分离:机理观点与水生危害评估

In situ construction of green ZnFeO/sub-5nm N, Cu dual-doped SnO S-scheme heterostructure with the boosted spatial charge separation towards decontamination of tetracycline: Mechanistic perspectives and aquatic hazard assessment.

作者信息

Nateq Kasra, Shohani Zadeh Mohammad, Amarzadeh Mohamadamin, Rostami Mohammad, Danaee Iman, Khosravi-Nikou Mohammad Reza

机构信息

Department of Chemical Engineering, Abadan Faculty of Petroleum Engineering, Petroleum University of Technology, Abadan, Iran.

Department of Safety, Health and Environmental Engineering, Abadan Faculty of Petroleum Engineering, Petroleum University of Technology, Abadan, Iran.

出版信息

J Environ Manage. 2025 Aug;389:126135. doi: 10.1016/j.jenvman.2025.126135. Epub 2025 Jun 12.

DOI:10.1016/j.jenvman.2025.126135
PMID:40505563
Abstract

The extensive consumption of pharmaceuticals has exacerbated environmental threats to living organisms globally. Herein, designing a green and magnetically separable S-scheme heterostructure with boosted visible light photocatalytic activity is imperative for the disintegration of these contaminants. In this study, ultra-fine (<5 nm) high surface area (118 m g) SnO nanoparticles (NPs) were constructed, exhibiting a remarkably reduced bandgap of 2.9 eV compared to the conventional value of 3.6 eV for SnO. Concurrently, N and Cu impurities were incorporated into the SnO lattice framework (denoted as NCS) to facilitate efficient charge carrier separation and augment visible light absorption capability through the introduction of acceptor and donor energy levels into the band structure. Furthermore, the magnetically separable ZnFeO/sub-5nm NCS (denoted as NCSZ) S-scheme heterostructure was constructed via an environmentally friendly and chemical free bio-hydrothermal approach. The incorporation of merely 4 % dopants and 10 % ZnFeO into SnO resulted in a superior rate constant of 7.9 min, which was 39.5 times higher than that of pristine SnO. Complete removal of tetracycline (TTC) was attained at a rate constant of 85.8 min within 60 min of visible light illumination. The mechanistic aspects of N and Cu doping, along with the S-scheme charge migration pathway, were scrutinized through trapping experiments and band structure analysis. A new approach was introduced to evaluate the photo-decomposition behavior of TTC across a broad pH range using density functional theory (DFT) calculations. Eventually, the aquatic hazards of both untreated and treated TTC solutions were assessed utilizing hazard quotient (HQ) method.

摘要

药品的大量消费加剧了全球对生物的环境威胁。在此,设计一种具有增强可见光光催化活性的绿色且可磁分离的S型异质结构对于分解这些污染物至关重要。在本研究中,构建了超精细(<5nm)高比表面积(118m²/g)的SnO纳米颗粒(NPs),与SnO的传统3.6eV带隙值相比,其带隙显著降低至2.9eV。同时,将N和Cu杂质掺入SnO晶格框架(记为NCS),通过在能带结构中引入受主和施主能级来促进有效的电荷载流子分离并增强可见光吸收能力。此外,通过环境友好且无化学试剂的生物水热法构建了可磁分离的ZnFe₂O₄/5nm NCS(记为NCSZ)S型异质结构。在SnO中仅掺入4%的掺杂剂和10%的ZnFe₂O₄就产生了7.9min⁻¹的优异速率常数,这比原始SnO的速率常数高39.5倍。在可见光照射60min内,以85.8min⁻¹的速率常数实现了四环素(TTC)的完全去除。通过捕获实验和能带结构分析研究了N和Cu掺杂的机理以及S型电荷迁移途径。引入了一种新方法,使用密度泛函理论(DFT)计算来评估TTC在广泛pH范围内的光分解行为。最终,利用危险商(HQ)方法评估了未处理和处理后的TTC溶液的水生危害。

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In situ construction of green ZnFeO/sub-5nm N, Cu dual-doped SnO S-scheme heterostructure with the boosted spatial charge separation towards decontamination of tetracycline: Mechanistic perspectives and aquatic hazard assessment.原位构建绿色ZnFeO/亚5纳米氮、铜双掺杂SnO S型异质结构用于增强四环素去污的空间电荷分离:机理观点与水生危害评估
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