N-doped graphene loaded with Ru sites as PMS activators for SMX degradation via non-radical pathway: efficiency, selectivity and mechanism

IF 13.3 1区工程技术 Q1 ENGINEERING, CHEMICAL

Chemical Engineering Journal Pub Date : 2025-04-04 DOI:10.1016/j.cej.2025.162230

Keke Zhi , Dong Liu , Jiajun Xu , Zhe Li , Shi Li , Lingjie Luo , Guifan Gong , Runyao Han , Aoxiang Yin , Lianghui Guo

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Abstract

The degradation of sulfamethoxazole (SMX) by advanced oxidation processes (AOPs) based on peroxomonosulfate (PMS) represents an effective and environmentally friendly approach to the elimination of sustainable pollution. In this study, an N-doped graphene activator loaded with Ru (N-rGO-Ru) active sites was synthesized by a onepot method. The Ru in N-rGO-Ru exists in the form of cluster bonds, and Ru-N bonds were formed. Under optimized conditions, (0.02 g·L⁻¹) N-rGO-Ru removed 92 % of SMX, rate constant (k = 0.0214 min⁻¹) in 120 min by a non-radical pathway mediated by singlet oxygen (¹O₂), as evidenced by quenching experiments and electron paramagnetic resonance (EPR) spectroscopy. The catalyst of N-rGO-Ru demonstrated exceptional tolerance to coexisting anions (e.g., Cl⁻, HCO₃⁻) and maintained 80 % efficiency after five cycles while minimizing metal leaching (<16 μg·L⁻¹), highlighting its robust stability and reusability. (Liquid Chromatograph Mass Spectrometer) LC–MS analysis identified four degradation pathways, including hydroxylation, sulphonamide bond cleavage, ring-opening, and coupling reactions, with ECOSAR modelling confirming significantly reduced acute and chronic toxicity of intermediates compared to SMX Theoretical calculations demonstrated that the Ru-N site enhanced the adsorption energy (−4.8 eV) and electron transfer efficiency of PMS, thereby facilitating efficient activation. The findings of this study indicate the capability of Ru-based materials to be utilized in the effective removal and detoxification of SMX in wastewater.

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负载钌位的n掺杂石墨烯作为非自由基途径SMX降解的PMS活化剂：效率、选择性和机制

基于过氧单硫酸盐（PMS）的高级氧化工艺（AOPs）降解磺胺甲恶唑（SMX）是消除可持续污染的有效和环保的方法。本研究采用一锅法合成了一种负载Ru （N-rGO-Ru）活性位点的n掺杂石墨烯活化剂。N-rGO-Ru中的Ru以簇键形式存在，形成了Ru- n键。在优化条件下，（0.02 g·L−1）N-rGO-Ru通过单线态氧（1O2）介导的非自由基途径，在120 min内脱除了92 %的SMX，速率常数（k = 0.0214 min−1），猝灭实验和电子顺磁共振（EPR）波谱证实了这一点。N-rGO-Ru催化剂对共存阴离子（如Cl−，HCO3−）表现出优异的耐受性，在五个循环后保持80 %的效率，同时最大限度地减少金属浸出（<16 μg·L−1），突出了其强大的稳定性和可重复使用性。LC-MS分析确定了四种降解途径，包括羟基化、磺胺键裂解、开环和偶联反应，ECOSAR模型证实与SMX相比，中间体的急性和慢性毒性显著降低。理论计算表明，Ru-N位点提高了PMS的吸附能（- 4.8 eV）和电子转移效率，从而促进了高效活化。本研究结果表明，钌基材料可用于废水中SMX的有效去除和解毒。

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来源期刊

Chemical Engineering Journal 工程技术-工程：化工

CiteScore

21.70

自引率

9.30%

发文量

6781

审稿时长

2.4 months

期刊介绍： The Chemical Engineering Journal is an international research journal that invites contributions of original and novel fundamental research. It aims to provide an international platform for presenting original fundamental research, interpretative reviews, and discussions on new developments in chemical engineering. The journal welcomes papers that describe novel theory and its practical application, as well as those that demonstrate the transfer of techniques from other disciplines. It also welcomes reports on carefully conducted experimental work that is soundly interpreted. The main focus of the journal is on original and rigorous research results that have broad significance. The Catalysis section within the Chemical Engineering Journal focuses specifically on Experimental and Theoretical studies in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. These studies have industrial impact on various sectors such as chemicals, energy, materials, foods, healthcare, and environmental protection.