无机阴离子对超声处理Fe81B10Si9非晶合金降解偶氮染料性能影响机制研究

Effect of Inorganic Anions on Degradation Performance of Azo Dyes by Ultrasonically-Treated Fe81B10Si9 Metallic Glass

摘要:

长期以来，以偶氮基染料为代表的各种工业染料废水造成了严重的环境问题。非晶合金凭借其独特的无序结构、较高的吉布斯自由能以及优异的耐腐蚀性，已成为一种极具前景、用于废水处理的催化剂。本研究采用超声预处理Fe₈₁B₁₀Si₉非晶合金，显著提升了其催化性能，经500 J超声处理的样品表现出最优表观反应速率常数（k_obs=1.66 min^-1），显著高于未处理样品。系统评估了典型无机阴离子（Cl^-、H₂PO₄^-、NO₂^-、SO₄^2-）在非均相类芬顿体系（Fe-MG/H₂O₂）中催化降解亚甲基蓝的影响机制。研究发现，随着阴离子浓度升高，Cl^-、H₂PO₄^-和NO₂^-均对降解产生不同程度抑制（k_obs<0.2 min^-1），而SO₄^2-对其降解过程影响较弱（k_obs=0.76 min^-1）。以Cl^-为代表对其协同作用过程进行了机理分析：淬灭结果表明，活性物种以?OH为主，并受溶液离子环境与表面通道协同调控。揭示了超声诱导的表面重构与价态调节对复杂阴离子环境下催化稳定性的促进作用，为复杂水体环境中高性能非晶合金催化剂的设计与应用提供了一定的理论支撑。

Abstract:

In recent years, industrial dye wastewater like azo dyes has caused severe environmental problems. Metallic glasses (MGs) are considered as promising catalysts for efficient water remediation due to their unique disordered structure, high Gibbs free energy, and excellent corrosion resistance. Ultrasonic pre-treatment was employed to enhance the catalytic performance of Fe₈₁B₁₀Si₉ MG. Results show that the sample treated with ultrasonic energy of 500 J exhibits the optimal reaction rate constant (k_obs) of 1.66 min^-1 compared with the untreated sample. The impact of typical anions (e.g., Cl^-, H₂PO₄^-, NO₂^-, and SO₄^2-) on the methylene blue solution degradation during the Fenton-like process (Fe-MG/H₂O₂) was investigated. With the increase in anion concentration, Cl^-, H₂PO₄?, and NO₂? all inhibit the degradation to varying degrees (k_obs< 0.2 min^-1), whereas SO₄^2- has a relatively weaker effect on the degradation process (k_obs=0.76 min^-1). Using Cl^- as a representative, the synergistic mechanism involved in the process was analyzed. Quenching experiment results indicate that ·OH are the dominant active species, which is synergistically regulated by solution chemistry and surface pathways. The ultrasonic-induced surface morphology reconstruction and valence state regulation enhance the catalytic stability in complex anionic environments. This work provides theoretical guidance for designing and developing high-performance MG catalysts in complex water environment.