与传统EAOP相比，该过程具有以下优势：1. 本研究涉及的HEF系统可在常压条件下运行，无需氧气通气，从而实现操作便捷和成本效益[27]；2.该工作系统可同时降解电子缺乏型和电子富集型污染物，展现出高效率且能耗低；3.密度泛函理论（DFT）计算表明，HMX和DNAN分子的活性位点更易受到活性氧（ROS）的攻击。CeO₂–MnO₂@CuO纳米线/碳纤维（CF）的p-n异质结增强了界面电荷转移，并在2e⁻氧还原反应（ORR）中展现出优异活性。总体而言，本研究通过巧妙利用质子交换膜（PEM），开发了一种结合HEF与EC-PMS的双重降解策略，实现了爆炸性污染物的同步去除，并展现出在废水处理中应用的巨大潜力。
Fig. 1. Morphological and structural characterization. (a-b) SEM images of Cu(OH)2 NWs/CF and CeO2-MnO2@CuO NWs/CF, (c) TEM/HRTEM images of CeO2-MnO2@CuO NWs/CF and its outer surface, interior layer and interface, (d) Scanning TEM and its corresponding EDS element color mapping for O, Cu, Mn and Ce, (e) XRD patterns of CeO2-MnO2 and CeO2-MnO2@CuO NWs/CF, (f) Raman spectra, (g-j) XPS spectra of O 1 s, Ce 3d, Mn 2p, Cu 2p for CeO2-MnO2@CuO NWs/CF before and after use, (k) LSV measurement of different electrocatalysts in 0.1 M KOH, (l) Nyquist plots, (m) CV curve and corresponding extracted peak current density as a function of the scan rate.
Fig. 2. Tests of p-n heterojunction. (a-b) UV–Vis diffuse reflectance spectra of samples, (c-d) The Mott-Schottky plots of CuO NWs/CF, CeO2-MnO2 and CeO2-MnO2@CuO NWs/CF, (e) Proposed photocatalytic reaction processes and charge transfer of CeO2-MnO2@CuO NWs/CF.
Fig. 3. The synthesis strategy and characterizations. (a) Synthetic process of CoS2@CC, (b) SEM images of CoS2@CC, (c) Particle size distribution, (d-f) Scanning TEM, SAED and its corresponding EDS element mapping for Co, S, O, (g) XRD patterns, (h) Raman spectra of CC and CoS2@CC, (j-l) XPS spectra of before and used CoS2@CC catalyst: high resolution of C 1 s, Co 2p, S 2p.
Fig. 4. Effects of experimental parameters. (a) Current intensity, (b-c) pH values, (d) Ions on HMX and DNAN degradation, condition: [HMX]0 = 10 mg/L, [DNAN]0 = 15 mg/L, [PMS] = 20 mmol/L, current density = 10 mA cm−2, electrolyte = 0.01 mol/L.
Fig. 5. Determination of free radicals and calculation of molecular active sites. (a) Quenching experiment, (b-d) EPR spectra of HMX degradation, (e) Quenching experiment, (f-g) EPR spectra of DNAN degradation, (h-i) DFT simulation and Fukui index of HMX and DNAN molecules, condition: [HMX]0 = 10 mg/L, [DNAN]0 = 15 mg/L, [PMS] = 20 mmol/L, current density = 10 mA cm−2, electrolyte = 0.01 mol/L.
Fig. 6. DFT calculations. (a) The structure model of CuO NWs/CF, MnO2@CuO NWs/CF, CeO2@CuO NWs/CF and CeO2-MnO2@CuO NWs/CF, (b) The thermodynamic activity of 2e− ORR over different electrocatalysts, (c) The Sabatier volcano plot of ΔGHOO⁎, (d) Free energy change of the atomic H* -initiated H2O2 in electrocatalytic process, (e) O-O bond (lO-O) of H2O2 and Cat. - H* - H2O2 adduct.综上所述，一种将HEF与EC-PMS相结合的双电化学系统被创新性地开发出来，用于同时去除电子缺乏型/电子富集型爆炸性污染物。CeO₂–MnO₂@CuO纳米线/碳纤维（NWs/CF）的p-n异质结被用作HEF系统的阴极材料。紫外-可见漫反射光谱表明，与CuO NWs/CF相比，CeO₂–MnO₂@CuO NWs/CF显著促进了界面电荷转移并提高了载流子迁移率。原位拉曼光谱和密度泛函理论（DFT）计算证实了 2e− 氧还原反应（ORR）的转化。在 EC-PMS 系统中，CoS₂@CC 被用作阳极材料，以实现 PMS 的快速活化，其中钴作为活性位点，而 S²⁻ 可参与 Co²⁺ 的再生。当阴极室初始 pH 值为 5，阳极室 pH 值为 9 时，HMX 和 DNAN 的同时降解效率最佳。自由基淬灭和电子顺磁共振（EPR）实验表明，在HEF系统中，H*和1O2是主要贡献者，而在EC-PMS系统中，•OH占主导地位。使用CeO2 -MnO₂@CuO纳米线/碳纤维（CF）的EEC为11.23 kWh·log⁻¹·m⁻³，而PMS活化的CoS₂@CC在10 mA cm⁻²的低电流密度下，每去除15 mg/L DNAN消耗0.29 kWh·log⁻¹·m³，实现HMX去除率高达90.2%的同时，DNAN去除率达100%。研究表明，HEF系统和EC-PMS系统适用于实际工业环境中HMX和DNAN废水的降解。工业HMX和DNAN废水的COD去除率分别达到56.7%和77.9%。通过模拟HMX暴露的鱼类毒理学实验及DNAN的QSAR预测毒性评估表明，降解产物通常转化为低毒性化合物。该双重降解系统在废水处理中展现出显著的实际应用潜力，并为高效同时降解具有电子缺乏和电子富集结构的污染物提供了新思路。
Lingzhen Miao, Siqi Luo, Shuaijie Jiang, Yuxin Guo, Chun Cai, Ming Lu, Yaqi Qin, Jie Zhu, Pengcheng Wang, A one-stone-two-birds strategy for electrochemical dual degradation of explosive wastewater, Chemical Engineering Journal, 2025, https://doi.org/10.1016/j.cej.2025.164476
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