Degradation of bisphenol F by activated of peroxymonosulfate using sludge biochar loaded with cobalt iron bimetallic catalyst
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摘要: 近年来，污水处理厂的大规模建设导致污泥产量逐年增加，污泥的处理面临严峻挑战，双酚F (BPF)被广泛应用于工业中化学添加剂，在地表水，土壤和污泥中被频繁检出。本文利用市政污泥负载钴铁双金属制备了钴铁双金属@生物炭复合材料(CoFeO@SBC)，通过活化过一硫酸盐(PMS)降解BPF来探究其催化性能。采用扫描电子显微镜(SEM)、比表面积测定(BET)、红外光谱(IR)、X射线衍射(XRD)和X射线光电子能谱(XPS)等表征分析所制备材料的理化性质；并考察了材料投加量、PMS投加量、初始pH和无机阴离子对CoFeO@SBC/PMS体系降解BPF效果的影响。结果表明，CoFeO与SBC复合后孔隙结构显著优化，比表面积增加了6.0倍，且具备更丰富的氧空位和还原性—OH官能团，产生了更多的Fe(Ⅱ)和Co(Ⅱ)。因此，CoFeO@SBC具有优异的催化活性，投加量为0.04 g/L时可以在10 min内几乎完全降解BPF(5 mg/L)，降解速率与CoFeO相比提高了62%；Cl−和$\mathrm{NO}_3 ^{-} $对体系降解效果影响较小，而$\mathrm{HCO}_3 ^{-} $具有显著的抑制作用；通过EPR分析表明CoFeO@SBC/PMS体系存在羟基(·OH)和硫酸根($\mathrm{SO}_4 ^{\cdot-} $)自由基以及单线态氧(1O2)和超氧(${\mathrm{O}}_2^{ \cdot-} $)自由基，同时自由基淬灭实验证明，$\mathrm{SO}_4 ^{\cdot-} $是体系降解BPF的关键活性氧物种；最后通过液相色谱-质谱联用(LC-MS)对BPF的降解产物进行分析，揭示BPF在体系中的主要降解途径和机制。Abstract: In recent years, the large-scale construction of wastewater treatment plants has led to an increase in the production of sludge year after year, and the treatment of sludge is facing a serious challenge. Bisphenol F (BPF), which is widely used as a chemical additive in the industry, has been frequently detected in surface water, soil and sludge. By using municipal sludge loaded with cobalt-iron bimetal, cobalt-iron bimetallic@biochar composites (CoFeO@SBC) were prepared, and the catalytic performance was assessed by activating peroxymonosulfate (PMS) to degrade BPF. Scanning electron microscopy (SEM), specific surface area determination (BET), infrared spectroscopy (IR), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) were used to characterise and analyse the physicochemical properties of the prepared materials. The effects of the dosage of the materials, the dosage of the PMS, the initial pH, and the inorganic anions on the degradation of the BPF by the CoFeO@SBC/PMS system were investigated. The results showed that the pore structure of CoFeO was significantly improved after compounding with SBC, and the specific surface area was increased by 6.0 times. Moreover, CoFeO@SBC composites showed richer oxygen vacancies and —OH functional groups, which led to higher production of Fe(II) and Co(II). Therefore, CoFeO@SBC composites had excellent catalytic activity, which could almost completely degrade BPF (5 mg/L) within 10 min at the dosage of 0.04 g/L, and the degradation rate was 62% higher than that of CoFeO; Cl− and NO3− showed less influence on the degradation effect of the system, while HCO3− had a significant inhibitory effect; EPR analysis shows that there are hydroxyl (·OH) and sulfate ($\mathrm{SO}_4 ^{\cdot-} $) free radicals as well as singlet oxygen (1O2) and superoxide ($\mathrm{O}_2 ^{\cdot-} $) free radicals in the CoFeO@SBC/PMS system. At the same time, the free radical quenching experiment, it is proved that $\mathrm{SO}_4 ^{\cdot-} $ is the key reactive oxygen species for the degradation of BPF in the system. Finally, the degradation products of BPF were identified by liquid chromatography-mass spectrometry (LC-MS), which could elucidate the primary degradation pathways and mechanisms in CoFeO@SBC/PMS system.
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Key words:
- bisphenol F /
- degradation /
- cobalt-iron bimetal /
- sludge biochar /
- peroxymonosulfate /
- radicals
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图 2 N2吸附-脱附等温线及孔径分布图: (a) CoFeO; (b) 钴铁双金属@生物炭复合材料(CoFeO@SBC); (c) SBC
Figure 2. N2 adsorption-desorption isotherm and pore size distribution of CoFeO (a), cobalt-iron bimetallic@biochar composites (CoFeO@SBC) (b) and (c) SBC
图 3 SEM表征: (a) SBC; (b) CoFeO; (c) CoFeO@SBC
Figure 3. Characterization of SBC (a)、CoFeO (b) and CoFeO@SBC (c) by SEM
图 4 (a) CoFeO和CoFeO@SBC的IR表征;(b) XPS全谱图; (c) C 1 s;(d) O 1 s;(e) Fe 2 p和(f) Co 2 p的XPS高分辨图
Figure 4. (a) Characterization of CoFeO and CoFeO@SBC by IR; (b) The XPS survey spectra of CoFeO and CoFeO@SBC; XPS high-resolution spectra of C ls spectra (c); 0 ls spectra(d); Fe 2 p spectra (e); Co 2 p spectra (f)
图 5 (a) 不同体系及CoFeO@SBC投加量对双酚F (BPF)去除效果的影响; (b) 不同体系及材料投加量的速率常数图
Figure 5. (a) Effect of different systems and CoFeO@SBC dosage on the removal of bisphenol F (BPF); (b)Rate constant diagram for different systems and material dosages
Ct/C0:The concentration of BPF after t min / The concentration of BPF before the reaction
图 6 (a) 过一硫酸盐(PMS)投加量对BPF去除效果的影响； (b) PMS投加量的速率常数图
Figure 6. (a) Effect of peroxymonosulfate (PMS) dosage on the removal of BPF；(b) Rate constant diagram of PMS dosage
图 7 (a) 不同初始pH对BPF去除效果的影响; (b) 不同初始pH的速率常数图
Figure 7. (a) Effect of different pH on the removal of BPF; (b) Rate constant plot for different initial pH
图 8 (a) 常见阴离子(Cl−、HCO3−和NO3−)对反应体系降解BPF的影响；(b) 常见阴离子的速率常数图
Figure 8. (a) Effect of anions (Cl−,HCO3− and NO3−)on BPF in reaction system; (b) Rate constant diagrams for common anions
图 9 (a) CoFeO@SBC/PMS体系自由基淬灭实验; (b) 自由基淬灭实验的速率常数图 不同ROS的鉴定; (c) MeOH (d) TBA (e) L-his (f) p-BQ
Figure 9. (a) Radical quenching experiment in CoFeO@SBC/PMS system; (b) Rate constant plot for free radical quenching experiment The identification of different ROS; (c) MeOH (d) TBA (e) L-his (f) p-BQ
图 10 CoFeO@SBC活化PMS降解BPF的机制示意图
Figure 10. Schematic diagram of the mechanism of CoFeO@SBC activation of PMS to degrade BPF
图 11 CoFeO@SBC/PMS体系中BPF降解路径
Figure 11. Possible degradation pathways of BPF in the CoFeO@SBC/PMS system
表 1 不同材料的表面结构特征
Table 1. The surface structure characterization of different material
Sample Surface area/(m²·g−1) Average pore diameter/nm Pore volume/(cm³·g−1) SBC 22.0203 15.88640 0.088944 CoFeO 5.2699 17.45430 0.023892 CoFeO@SBC 37.1189 9.48554 0.093656 
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表 2 CoFeO和CoFeO@SBC的XPS分析数据
Table 2. XPS analysis results of CoFeO and CoFeO@SBC
Sample Fe2+/Fe3+ Co2+/Co3+ C—O O2 CoFeO 1.3 0.7 22.59 % 32.90% CoFeO@SBC 1.5 0.98 30.99 % 36.31%
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