过渡金属磷化物活化过一硫酸盐降解水中有机污染物的研究进展

Recent Advances in Transition Metal Phosphides for Peroxymonosulfate Activation toward the Degradation of Organic Pollutants in Water

摘要: 过一硫酸盐(PMS)活化技术因可原位生成$S{O}_4^{•-}$ 、•OH、$O_{\text{2}}^{•-}$ 、¹O₂及高价金属氧物种，已成为难降解有机污染物去除的重要高级氧化路径。传统均相金属离子、金属氧化物和碳材料虽然能够活化PMS，但常受限于金属残留、低价金属再生缓慢、pH适应性不足、界面电子转移效率有限和实际水体干扰。过渡金属磷化物(TMPs)近年来进入PMS催化领域，核心原因在于其类金属性导电性、M-P键诱导的M^δ+/P^δ−协同位点、以及还原性P物种对金属价态循环的促进作用。现有研究已从早期CoP、Fe_xP和Ni₂P单金属磷化物，发展到Co₂P/C、CoP/NC、Fe₂P/biocarbon、CoP/CoO_x、CoFe₂P_x、FeNiP、NiFeP_x、FeP/NiP₂异质界面、固定化FeCoP@NF、光热耦合Co-Ni₂P和磷空位调控体系。总体上，TMPs/PMS体系在抗生素、染料和酚类污染物去除中表现出较高反应速率、宽pH适用范围和一定循环稳定性。然而，机理判定仍存在自由基猝灭过度依赖、¹O₂来源不清、电子转移路径与高价金属氧物种难以区分等问题。未来研究应从结构可控合成、原位谱学和同位素追踪、固定化反应器、实际废水基质及毒性削减评价几个方向推进，使TMPs从高效模型催化剂走向可验证的水处理材料。

Abstract: Peroxymonosulfate (PMS) activation has become an important advanced oxidation pathway for the removal of refractory organic pollutants because it can generate $S{O}_4^{•-}$ , •OH, $O_{\text{2}}^{•-}$ , ¹O₂, and high-valent metal-oxo species in situ. Although conventional homogeneous metal ions, metal oxides, and carbon materials can activate PMS, they are often limited by metal residues, slow regeneration of low-valent metal species, insufficient pH adaptability, restricted interfacial electron-transfer efficiency, and interference from real water matrices. Transition metal phosphides (TMPs) have recently attracted increasing attention in PMS catalysis, mainly because of their metallic-like conductivity, M^δ+/P^δ⁻ synergistic sites induced by M-P bonds, and the ability of reductive phosphorus species to promote metal valence cycling. Existing studies have evolved from early monometallic phosphides, such as CoP, Fe_xP, and Ni₂P, to Co₂P/C, CoP/NC, Fe₂P/biocarbon, CoP/CoO_x, CoFe₂P_x, FeNiP, NiFeP_x, FeP/NiP₂ heterointerfaces, immobilized FeCoP@NF, photothermal-coupled Co-Ni₂P, and phosphorus-vacancy-regulated systems. Overall, TMPs/PMS systems exhibit high reaction rates, broad pH applicability, and certain cycling stability in the degradation of antibiotics, dyes, and phenolic pollutants. However, mechanistic identification still suffers from excessive reliance on radical quenching tests, unclear sources of ¹O₂, and difficulty in distinguishing electron-transfer pathways from high-valent metal-oxo species. Future studies should focus on controllable structural synthesis, in situ spectroscopy and isotope tracing, immobilized reactors, real wastewater matrices, and toxicity reduction assessment, so that TMPs can move from efficient model catalysts toward verifiable water-treatment materials.