第一作者：Qiuyue Wan
通讯作者：孙治荣 教授
通讯单位：北京工业大学环境工程系
DOI:10.1016/j.apcatb.2025.125054
创新性地使用废锌锰电池电极材料（ZMB）作为前驱体。通过对 ZMB 进行简化的 “洗涤-球磨-煅烧 ”工艺，开发出一种新型活化剂（代号为 BWZMB492），用于过一硫酸盐（PMS）活化和去除新出现的污染物。BWZMB492/PMS 系统可在 6 分钟内完全去除 20 mg-L-1 对乙酰氨基酚（APAP）。通过淬灭、探测和预混合实验，排除了活性氧的贡献，证实了电子传递过程（ETP）的主导作用。实验结果表明，PMS 倾向于优先吸附并形成 BWZMB492/PMS⁎ 复合物。同时，APAP 可作为电子供体，促进 ETP 的发生。此外，还选择了九种亲电指数不同的污染物进行去除实验和电化学测试。这些亲电指数较低的污染物在 BWZMB492/PMS 系统中表现出较高的去除效率。结果表明，去除效果和机理与污染物的亲电指数相关。
Fig. 1. (a) Removal efficiency of APAP in different systems; (b) Pseudo-first-order reaction kinetics fitting diagram with different activators; Effect of (c) activator dosage and (d) PMS concentration on APAP removal. Reaction conditions: [APAP] = 20 mg·L-1, [volume] = 150 mL, [activator] = 0.5 g·L-1 (except for panel c), and [PMS] = 0.5 mmol·L-1 (except for panel d).
Fig. 2. SEM images of (a, e) ZMB, (b, f) WZMB, (c, g) BWZMB, and (d, h) BWZMB492; (i) EDS elemental mapping images, (j) TEM image, (k) high-resolution TEM image, and (l) SEAD pattern of BWZMB492; (m) Contact angle images of the prepared activators.
Fig. 3. The (a) XRD, (b) Raman, (c) FTIR, (d) Nitrogen adsorption-desorption isotherms, (e) the full XPS spectrum, and high-resolution XPS spectra of (f) C 1 s, (g) O 1 s, (h) Mn 2p of ZMB, WZMB, BWZMB, and BWZMB492.
Fig. 4. (a) Effect of various scavengers on APAP removal; (b) Premixing experiment (PMS and BWZMB492 were premixed for 3 and 6 min, then APAP was added into the system); (c) FTIR spectra of PMS, BWZMB492, PMS/BWZMB492 and PMS/BWZMB492/APAP; (d) The in-suit Raman spectra of different reaction systems； Electron density difference for (e) PMS and BWZMB492 and (f) APAP and BWZMB492/PMS⁎ complex. Reaction conditions: [APAP] = 20 mg·L-1, [volume] = 150 mL, [activator] = 0.2 g·L-1, and [PMS] = 0.3 mmol·L-1.
Fig. 5. (a) The open-circuit potential of ZMB, WZMB, BWZMB, and BWZMB492; (b) Removal efficiency of different pollutants in BWZMB492/PMS system; (c) Pseudo-first-order reaction kinetics fitting diagram with different pollutants; (d) HOMO and LUMO of different pollutants; (e) Open-circuit potential of BMZMB492 with the addition of PMS and different pollutants; (f) Different falling potentials after adding various pollutants; (g) Correlation between the lnkobs of different pollutants and their falling potentials obtained in BWZMB492/PMS systems. Reaction conditions: [Pollutants] = 20 mg·L-1, [volume] = 150 mL, [activator] = 0.2 g·L-1, and [PMS] = 0.3 mmol·L-1.
Fig. 6. (a) Effect of pH on APAP removal; (b) Real-time change of pH during the reaction; Effects of (c) co-existing ions, (d) humic acid, (e) different water matrices on APAP removal in the BWZMB492/PMS system; (f) Water quality index before and after APAP treatment in simulated sewage; (g) Cyclic experiment of BWZMB492/PMS/APAP system; (h) Metal leaching in the cyclic experiment; (i) XRD patterns of BWZMB492 before and after the cyclic experiment. Reaction conditions: [APAP] = 20 mg·L-1, [volume] = 150 mL, [activator] = 0.2 g·L-1, [PMS] = 0.3 mmol·L-1.
本研究采用简化的 “洗涤-球磨-煅烧 ”工艺，成功制备了具有优异催化活化性能的 BWZMB492 活化剂。该制备工艺操作简单，产品收率高，具有工业适用性。BWZMB492/PMS 系统可在 6 分钟内完全去除 20 mg-L-1 的 APAP。在 BWZMB492/PMS/APAP 系统中，PMS 倾向于吸附在 BWZMB492 表面，形成复合物 BWZMB492/PMS⁎。与此同时，污染物 APAP 作为电子供体，驱动 ETP 过程实现对 APAP 的去除。考虑到污染物的特点，本研究选取了9种亲电指数不同的PPCPs，通过BWZMB492/PMS体系对其机理进行了全面研究。结果表明，亲电指数较低的7种污染物（APAP、BPA、TC、CTC、CBZ、SMZ和SMX）能有效诱导ETP过程，且亲电指数越低越有利于ETP反应。结果表明，ETP中的降解效果和机理与污染物的亲电指数相关，这为理解活化剂的选择性氧化行为提供了一个重要的视角。本研究以 APAP 为例，系统评价了 BWZMB492/PMS/APAP 体系在不同环境条件下的适应性和稳定性。结果表明，该体系在酸性或中性条件、多类离子共存、复杂水环境和循环实验中均表现出优异的降解性能。通过结合 LC-QQQ-MS 和 DFT，揭示了 APAP 降解的三种可能途径。该研究为锌锰电池废液的高值化利用提供了一种创新方法，为制作有效的活化剂奠定了科学基础。此外，它还有效验证了 ETP 中污染物特性与活化剂的协同诱导效应。
Qiuyue Wan, Zhirong Sun, Mechanochemically synthesized peroxymonosulfate activators from spent zinc-manganese battery electrode material: correlation between pollutant electrophilicity index and electron transfer process, Applied Catalysis B: Environment and Energy, 2025, https://doi.org/10.1016/j.apcatb.2025.125054
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