硝酸改性抑制颗粒活性炭活化PDS去除水中AO7的机理研究

doi:10.19965/j.cnki.iwt.2024-0419

摘要/Abstract

摘要：

利用硝酸对颗粒活性炭（GAC）进行改性，之后利用改性后的颗粒活性炭（NAC）活化过硫酸钠（PDS）降解水中酸性橙7（AO7）。结果显示，相较于GAC/PDS体系，NAC/PDS体系对AO7的降解表现出一定的抑制作用。为研究该抑制作用的机理，采用猝灭实验对NAC/PDS体系中的主要活性氧物种进行探究，在此基础上采用电子自旋共振（EPR）实验分析改性前后体系中活性氧物种的产生情况，同时对比分析改性前后GAC的形貌结构及活性位点。结果表明，NAC/PDS体系中的主要活性氧物种为表面结合态自由基（SO₄ ^·- _ads、·OH_ads），其含量低于GAC/PDS体系；相比于GAC，NAC比表面积与孔容减小，吸附能力下降，同时，其结构中—COOH及C $̿$ O含量增多，C—O及可供电子的π共轭结构（π*）有所减少。体系对AO7的降解机理表明，SO₄ ^·- _ads、·OH_ads作为主要活性氧物种对AO7进行降解，而电子转移作用可促进PDS活化生成更多活性物种，因此，改性后NAC活化PDS去除水中AO7的效果下降。

关键词: 硝酸, 活性炭, 过硫酸钠, 酸性橙7, 抑制机理

Abstract:

Granular activated carbon(GAC) was modified by nitric acid. The modified granular activated carbon(NAC) was used for activating sodium persulfate(PDS) to degrade acid orange 7(AO7) in water. The results showed that compared to the GAC/PDS system, the NAC/PDS system exhibited a certain inhibitory effect on the degradation of AO7. To investigate the mechanism of the inhibitory effect, quenching experiments were conducted to explore the main active oxygen species in the NAC/PDS system. Based on this, electron spin resonance(EPR) experiments were used to analyze the generation of active oxygen species in the modified and unmodified systems. Meanwhile, the morphology, structure, and active sites of GAC before and after modification were compared and analyzed. The results showed that the main active oxygen species in the NAC/PDS system were surface bound free radicals(SO₄ ^·- _ads and ·OH_ads), with lower content than those in the GAC/PDS system. Compared to GAC, NAC had reduced specific surface area and pore volume, resulting in a decrease of adsorption capacity. Meanwhile, the content of —COOH and C $̿$ O in the structure increased, while the content of C—O and electron donating π-conjugated structures (π*) decreased. The degradation mechanism of AO7 by the system indicated that SO₄ ^·- _ads, ·OH_ads, as the main active oxygen species participated in the degradation of AO7, and electron transfer could promote the activation of PDS to generate more active species. Therefore, the effectiveness of modified NAC activated PDS to remove AO7 in water was decreased.

Key words: nitric acid, activated carbon, sodium persulfate, acid orange 7, inhibition mechanism

中图分类号:

马梦杰, 谢鹏飞, 章慧娟. 硝酸改性抑制颗粒活性炭活化PDS去除水中AO7的机理研究[J]. 工业水处理, 2025, 45(6): 187-193.

Mengjie MA, Pengfei XIE, Huijuan ZHANG. Inhibition mechanism of AO7 removal by PDS activated by nitric acid-modified granular activated carbon[J]. Industrial Water Treatment, 2025, 45(6): 187-193.

https://www.iwt.cn/CN/Y2025/V45/I6/187

图/表 8

图1 不同体系对AO7的去除效能

Fig.1 Removal efficiency of AO7 by different systems

图2 猝灭剂对NAC/PDS体系去除AO7的影响

Fig.2 Effect of scavengers on the removal of AO7 by NAC/PDS system

图3 反应体系的EPR分析

Fig.3 EPR analysis of reaction systems

表1 改性前后活性炭表面各元素质量分数 (%)

Table 1 Mass fraction of each element on the surface of activated carbon before and after modification

样品	N	C	H	S	O
GAC	0.29	90.29	1.60	0.19	7.63
NAC	1.18	84.10	1.59	0.07	13.08

图4 改性前后活性炭的SEM

Fig.4 SEM of activated carbon before and after modification

图5 硝酸处理对活性炭表面性质的影响

Fig.5 Effect of nitric acid treatment on surface properties of activated carbon

图6 活性炭样品的XPS

Fig.6 XPS of activated carbon samples

图7 不同体系中PDS和TOC变化

Fig.7 Changes of PDS and TOC in different systems

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