苯胺聚合炭化制备Co-NC活化单过硫酸盐降解对乙酰氨基酚

doi:10.15541/jim20260383

摘要/Abstract

摘要： 非均相金属/碳材料催化剂在活化单过硫酸盐(PMS)用于高级废水处理方面展现出巨大前景, 然而改性碳材料中高分散金属活性中心的可控制备路径和活化PMS机理研究仍面临挑战。本研究首先利用钴离子诱导苯胺单体聚合过程, 形成高分散的Co–N配位键; 随后通过热解炭化制备钴改性氮掺杂多孔碳材料(Co-NC), 显著提高Co活性中心在碳材料表面的分散程度, 进而有效增强PMS活化降解对乙酰氨基酚(ACP)性能。在最佳Co添加量(2 mmol)条件下制备的Co-NC-2.0样品, 在5 min内可以有效活化PMS, 使ACP的去除效率达到99.6%; 30 min时对化学需氧量(COD)去除率达到69%, 且循环5次后降解性能基本保持不变。通过自由基捕获实验和电子顺磁共振谱证实了Co-NC活化PMS过程中主要生成了超氧自由基·O₂^–和单态氧¹O₂。机理研究表明, Co-NC材料是通过非自由基路径, 在Co活性中心有效吸附并活化断裂PMS分子中的O–O键, 分别合成·O₂^–和¹O₂, 进而有效降解矿化ACP。

关键词: 金属单分散, 聚苯胺, 多孔碳, 单过硫酸盐, 对乙酰氨基酚

Abstract: Heterogeneous metal/carbon material catalysts show great promise in activating peroxymonosulfate (PMS) for advanced wastewater treatment. However, the controllable preparation pathways for highly dispersed metal active centers in modified carbon materials and the mechanistic understanding of PMS activation remain challenging. To address this, this study first utilized cobalt ions to induce the polymerization of aniline monomers, forming highly dispersed Co–N coordination bonds. Subsequently, cobalt-modified nitrogen-doped porous carbon materials (Co-NC) were prepared through pyrolysis carbonization, significantly improving the dispersion of Co active centers on the carbon material surface, thereby effectively enhancing the performance of PMS activation for the degradation of acetaminophen (ACP). Under the optimal Co addition (2 mmol), the prepared Co-NC-2.0 sample could effectively activate PMS, achieving a degradation rate of 99.6% for ACP within 5 min and a chemical oxygen demand (COD) removal rate of 69% within 30 min, and the degradation performance remained unchanged after 5 cycles. Radical trapping experiments and electron paramagnetic resonance spectroscopy confirmed that superoxide radicals (·O₂^–) and singlet oxygen (¹O₂) were mainly generated during the Co-NC-activated PMS process. The mechanistic analysis indicated that the Co-NC material operates through non-radical pathways at the Co active centers, PMS molecules are effectively adsorbed and their O–O bonds are activated and cleaved, generating ·O₂^– and ¹O₂, which subsequently achieve efficient degradation and mineralization of acetaminophen.

Key words: metal monodisperse, polyaniline, porous carbon, peroxymonosulfate, acetaminophen

中图分类号:

TQ15

张斌, 柯军, 周元, 刘洁. 苯胺聚合炭化制备Co-NC活化单过硫酸盐降解对乙酰氨基酚[J]. 无机材料学报, DOI: 10.15541/jim20260383.

ZHANG Bin, KE Jun, ZHOU Yuan, LIU Jie. Co-modified Porous Carbon Induced by Carbonization of Aniline Polymerization for Persulfate Activation to Degrade Acetaminophen[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20260383.

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