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第一作者：邓宇航
通讯作者：刘春波教授，姜维副教授，车广波教授
通讯单位：吉林师范大学，白城师范学院
DOI：10.1016/j.cej.2024.154580
理解活化过氧单硫酸盐(PMS)的催化机理对于设计高效的金属负载催化剂至关重要。本文构建了Co、S和O共掺杂氮化碳(CoCN-x)。DFT计算表明，掺杂多种元素的CN具有更好的PMS激活能力。优化后的CoCN-0.5在30 s内对磺胺甲噁唑(SMX)的去除率达到95%，降解速率常数为2.92 min-1，是CN的845.34倍。此外，对PMS的活化机制进行了深入的研究，揭示了•OH、SO4•-和O2•-等经典自由基以及涉及1O2、CoO2+和电子转移的非自由基的存在。利用DFT计算、HPLC-MS和3D EEMs也阐明了潜在的SMX降解途径。这项工作为开发通过自由基和非自由基机制有效激活PMS的催化剂提供了新的见解。
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Fig. 1. (a) Schematic diagram of the synthesis of CoCN-x. (b) SEM, (c) TEM, (d) HRTEM, and (e) EDS of CoCN-0.5.Fig. 2. (a) XRD, (b) FT-IR, (c) N2 adsorption-desorption isotherms and (d) pore size distributions of CN and CoCN-x. XPS spectra of CN and CoCN-x: (e) survey, (f) C 1s, (g) N 1s, (h) O 1s and, (i) Co 2p.Fig. 3. (a) SMX removal rate and (b) reaction rate constant of different reactions within 10 min. Influence of (c) catalyst dosage, (d) PMS dosage, (e) temperature on SMX removal in CoCN-0.5/PMS system. Effects of (f) Cl-, (g) H2PO4-, (h)HCO3- and (i)HA on SMX degradation.Experimental conditions: [SMX]=20 mg/L, [CoCN-0.5]=400 mg/L, [PMS]=0.4 mM, pH=7.00, T=25 ℃, stirring speed=600 rpm.Fig. 4. (a) Effects of different scavengers on SMX degradation. (b) The consumpstion of PMSO and the generation of PMSO2 in CoCN-0.5/PMS system. The EPR spectra of (c) TEMP-1O2 and (d)DMPO- O2•- in the CoCN-0.5/PMS system. (e) Degradation curves of SMX by CoCN/PMS in H2O and D2O. (f) SMX degradation after mixing PMS and CoCN-0.5. (g) LSV and (h) I-t spotting for CN and CoCN-0.5. (i) Degradation of SMX in CoCN-0.5/PMS system after metal shielding.Experimental conditions: [SMX]=20 mg/L, [CoCN-0.5]=400 mg/L, [PMS]=0.4 mM, pH=7.00, T=25 ℃, stirring speed=600 rpm.Fig. 5.(a) Differential charge density (yellow area indicates an increase in electron density, cyan area indicates a decrease in electron density [the isosurface value]=0.001 e/Bohr3) and (b) electrostatic potential of CN models doped with different elements (red is negative charge, blue is positive charge, [the isosurface value]=0.001 a.u). Electron Localization Function of (c) CN, (d) S, O-doped CN, (e) Co-doped CN and (f) Co, S, O-doped CN.Fig. 6.(a) The model of CoCN-0.5. (b) The adsorpion eneries of CoCN-0.5 rent sites of PMS. (c) Optimized structure after PMS adsorption. Planar-averaged charge density difference along z axis of (d) CN, (e) S, O doped CN, (f) Co doped CN and (g) Co, S, O doped CN. (The isosurface value=0.001 e/Bohr3)
Fig. 7. (a) The recycling performance of CoCN-0.5 for the SMX degradation. (b) Effect of different water bodies on the degradation efffciency of SMX in CoCN-0.5/PMS system. (c) XRD and (d) FT-IR of CoCN-0.5 before and after catalysis. XPS spectra after degradation reaction: (e) C 1s, (f) N 1s, (g) O 1s and (h) Co 2p. (i) Degradation of different pollutants by CoCN-0.5/PMS.本文成功合成了Co、S、O共掺杂氮化碳(CoCN-0.5)，表现出了良好的活化PMS降解SMX的能力。CoCN-0.5在30秒内达到95%的SMX去除率，降解速率常数为2.92 min-1。此外，系统考察了催化剂掺杂、PMS浓度、催化剂用量、反应pH、温度、无机阴离子和腐殖酸对SMX降解的影响。机理研究表明，CoCN-0.5对PMS的活化涉及到1O2、O2•-、高价钴氧化物(CoO2+)和电子转移，它们与•OH和SO4•-一起有效降解SMX。性能的增强主要是由于Co、S和O共掺杂的协同作用。Co、S和O的引入有效地调节了CN的电荷分布，提高了PMS的吸附能力。因此，CoCN-0.5/PMS系统是一种很有前途的修复含抗生素废水的方法。
Yuhang Deng, Simiao Wang, Tianyu Zhou, Bo Liu, Bo Hu, Liang Wang, Chunbo Liu, Wei Jiang, Guangbo Che. Highly-separated Co anchored on S, O-doped carbon nitride for enhanced peroxymonosulfate activation: Insights into radical and non-radical pathways, Chemical Engineering Journal 497 (2024) 154580. https://doi.org/10.1016/j.cej.2024.154580
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