高等学校化学学报 ›› 2026, Vol. 47 ›› Issue (8): 20250377.doi: 10.7503/cjcu20250377
黄诗雨1, 姜宏斌1,3(
), 刘贺然1,2, 代文臣1,3, 徐晓晨3, 陈捷3, 杨光1, 杨凤林3
收稿日期:2025-12-15
出版日期:2026-08-10
发布日期:2026-04-03
通讯作者:
姜宏斌
E-mail:jianghb@sylu.edu.cn
基金资助:
HUANG Shiyu1, JIANG Hongbin1,3(
), LIU Heran1,2, DAI Wenchen1,3, XU Xiaochen3, CHEN Jie3, YANG Guang1, YANG Fenglin3
Received:2025-12-15
Online:2026-08-10
Published:2026-04-03
Contact:
JIANG Hongbin
E-mail:jianghb@sylu.edu.cn
Supported by:摘要:
活化过氧乙酸(PAA)高级氧化技术是一种高效、 清洁的水污染处理方法, 有望成为解决水体中亚甲基蓝污染的合理方案. 然而, 现有研究主要围绕活化PAA机理开展, 对如何提高催化材料的实际应用性缺乏深入讨论, 制约了活化PAA技术的工程化应用. 本文报道了一类新型钴基非均相催化剂Co(x)/γ-Al2O3, 在最佳浸渍时间(12 h)可实现PAA的高效活化, 对10 mg/L亚甲基蓝废水的去除率可达99.6%. 与均相的钴离子(Co2+)活化体系相比, Co(x)/γ-Al2O3活化体系可节省约25%的PAA投加量. 同时, 该催化剂还具有较宽的pH适应范围、 较强的HCO3-耐受能力以及低于10 μg/L的超低金属溶出浓度, 其性能、 稳定性以及使用寿命均优于传统的PAA活化材料. 表面化学表征与理论计算结合表明, Co(x)/γ-Al2O3的催化活性源于催化剂表面Co2+/Co3+循环, 该过程中所产生的乙酰基(过)氧基自由基[CH3C(O)O·和CH3C(O)OO·]是攻击亚甲基蓝的主要反应物种. PAA活化主要发生在Co位点上, 其在Co3O4(311)平面具有较高的吸附能(1.00 eV)和d-带中心(1.55 eV), 可以增加PAA在反应平面上的吸附, 促进电荷转移, 从而增强Co(x)/γ-Al2O3对PAA的活化能力. 综上所述, Co(x)/γ-Al2O3催化剂为活化PAA工艺在亚甲基蓝废水处理领域的实际应用提供了一种可持续且高效的解决方案.
中图分类号:
TrendMD:
黄诗雨, 姜宏斌, 刘贺然, 代文臣, 徐晓晨, 陈捷, 杨光, 杨凤林. Co(x)/γ-Al2O3非均相催化剂活化过氧乙酸处理亚甲基蓝废水的研究. 高等学校化学学报, 2026, 47(8): 20250377.
HUANG Shiyu, JIANG Hongbin, LIU Heran, DAI Wenchen, XU Xiaochen, CHEN Jie, YANG Guang, YANG Fenglin. Study on Co(x)/ γ⁃Al2O3 Heterogeneous Catalyst Activation of Peracetic Acid for Treating Methylene Blue Wastewater. Chem. J. Chinese Universities, 2026, 47(8): 20250377.
| Sample | SBET/(m2∙g-1) | Pore volume/(cm3∙g-1) | Average pore size/nm |
|---|---|---|---|
| γ⁃Al2O3 | 226.531 | 0.416 | 3.753 |
| Co(6)⁃Al2O3 | 259.932 | 0.484 | 6.268 |
| Co(12)⁃Al2O3 | 253.194 | 0.482 | 6.281 |
| Co(18)⁃Al2O3 | 256.040 | 0.497 | 6.290 |
Table 1 Comparison of BET specific surface area and pore structure between γ -Al2O3 and Co(x)/ γ -Al2O3 series catalysts
| Sample | SBET/(m2∙g-1) | Pore volume/(cm3∙g-1) | Average pore size/nm |
|---|---|---|---|
| γ⁃Al2O3 | 226.531 | 0.416 | 3.753 |
| Co(6)⁃Al2O3 | 259.932 | 0.484 | 6.268 |
| Co(12)⁃Al2O3 | 253.194 | 0.482 | 6.281 |
| Co(18)⁃Al2O3 | 256.040 | 0.497 | 6.290 |
Fig.4 Comparison of degradation efficiency of methylene blue in different systems(A) PAA, Co2+, H2O2 system alone; (B) separate γ-Al2O3 and Co(x)/γ-Al2O3 systems; (C) Co2+, γ-Al2O3, and Co(x)/γ-Al2O3 activated H2O2 system;(D) Co2+, γ-Al2O3 and Co(x)/γ-Al2O3 activated PAA system.
Fig.5 Effect of PAA dosage on the degradation efficiency of methylene blue in Co2+/PAA system(A) and Co(12)/γ⁃Al2O3/PAA system(B), as well as the effect of catalyst dosage on the degradation efficiency of methylene blue in Co2+/PAA system(C) and Co(12)/γ⁃Al2O3/PAA system(D)
Fig.7 Effect of HCO3- concentration on Co2+/PAA(A) and Co(12)/γ⁃Al2O3/PAA systems(B), as well as the effect of Cl- concentration on Co2+/PAA(C) and Co(12)/γ⁃Al2O3/PAA systems(D)
| Repeated experiment stage | Total cobalt ion concentration/(μg∙L-1) | Repeated experiment stage | Total cobalt ion concentration/(μg∙L-1) |
|---|---|---|---|
| 1 | 5 | 4 | 2 |
| 2 | 3 | 5 | 3 |
| 3 | 4 |
Table 2 Test results of cobalt ion concentration in repetitive experiments
| Repeated experiment stage | Total cobalt ion concentration/(μg∙L-1) | Repeated experiment stage | Total cobalt ion concentration/(μg∙L-1) |
|---|---|---|---|
| 1 | 5 | 4 | 2 |
| 2 | 3 | 5 | 3 |
| 3 | 4 |
| Material | Percentage(%) | |||
|---|---|---|---|---|
| Co2+ | Co3+ | Olat | Oads | |
| Co(12)/γ-Al2O3 | 46.8 | 53.2 | 78.8 | 21.2 |
| Co(6)/γ-Al2O3 | 37.6 | 62.4 | 67.4 | 32.6 |
Table 3 XPS results of Co(12)/γ-Al2O3 catalyst
| Material | Percentage(%) | |||
|---|---|---|---|---|
| Co2+ | Co3+ | Olat | Oads | |
| Co(12)/γ-Al2O3 | 46.8 | 53.2 | 78.8 | 21.2 |
| Co(6)/γ-Al2O3 | 37.6 | 62.4 | 67.4 | 32.6 |
Fig.10 Effect of different quenchers on the Co(12)/γ⁃Al2O3/PAA system(A), ESR spectra of free radical DMPO adducts in different systems(B), free radical DMPO adducts in different systems under the influence of quenchers(C), and R—O· and DIPPMPO adducts in different systems(D)
Fig.11 PAA molecular structure(A), calculation result model of PAA molecule adsorption on γ⁃Al2O3(111)(B), calculation result model of PAA molecule adsorption on Co3O4(311)(C), adsorption energy of PAA molecules on γ⁃Al2O3(111) and Co3O4(311)(D), d⁃band center energy diagram of γ⁃Al2O3(111)(E) and Co3O4(F)
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