Preparation and photocatalytic performance of polyvinyl alcohol /oxygen-doped carbon nitride composite nanofiber films
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摘要: 大量有机污染物对水循环造成严重污染，同时耐药细菌对人类健康构成严重威胁。光催化纳米材料已成为抗菌领域的研究热点。本文通过尿素和甲酸热聚合法烧制成氧掺杂氮化碳(O-CN)，优选比例的O-CN与聚乙烯醇(PVA)溶液混合，通过静电纺丝技术成功制备了聚乙烯醇/氧掺杂氮化碳(PVA/O-CN)复合纳米纤维膜。对O-CN和PVA/O-CN复合膜进行形貌和结构表征以及光催化抑菌和有机污染物去除性能的分析。结果表明，O原子部分代替CN中三-三嗪环结构中N的位置，O-CN的可见光吸收能力和电子-空穴对分离率较CN有所提高， PVA/O-CN-0.6复合纳米纤维膜对大肠杆菌和金黄色葡萄球菌有较好的抑制作用，抑菌率可达96%和93.7%。另外，PVA/O-CN-0.6复合纳米纤维膜对染料具有良好的去除性能，PVA/O-CN-0.6在4 h内对亚甲基蓝(MB)的去除率达到了97.7%。此外，该膜具有良好的热稳定性和优异的力学性能，在水净化及抑菌领域具有很大的应用潜力。Abstract: A large number of organic pollutants caused serious pollution to the water cycle, and drug-resistant bacteria posed a serious threat to human health. Photocatalytic nanomaterials have become a research hotspot in the field of antibacteria. In this paper, oxygen-doped carbon nitride (O-CN) was prepared by hot polymerization with Urea and formic acid. The optimal proportion of O-CN was mixed with polyvinyl alcohol (PVA) solution, and the polyvinyl alcohol/oxygen-doped carbon nitride (PVA/O-CN) composite nanofiber film was successfully prepared by electrospinning technology. The micro-morphology, structure, photocatalytic bacteriostatic properties and organic pollutant removal properties of O-CN and PVA/O-CN composite films were studied. The results showed that O atom could replace the N position in the triazine ring structure of CN, and the light absorption capacity and the separation rate of electron-hole improved compared with that of CN. PVA/O-CN-0.6 composite nanofiber membrane had the best inhibition effect on E.coli and S.aureus, and the inhibition rates were 96% and 93.7%, respectively. In addition, PVA/O-CN-0.6 composite nanofiber membrane had a good performance in dye removal, and the removal rate of methylene blue (MB) by PVA/O-CN-0.6 reached 97.7% within 4 h. Moreover, the film with excellent mechanical properties, has great application potential in many fields.
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图 1 氧掺杂氮化碳(O-CN)和聚乙烯醇/氧掺杂氮化碳(PVA/O-CN)的制备流程图
Figure 1. Preparation Processing diagram of oxygen-doped carbon nitride (O-CN) and polyvinyl alcohol/oxygen-doped carbon nitride (PVA/O-CN)
图 2 O-CN-0.6的(A)SEM和(a)TEM图像；O-CN-8的(B)SEM和(b)TEM图像；O-CN-16的(C)SEM和(c)TEM图像
Figure 2. SEM(A) and TEM(a) images of O-CN-0.6; SEM(B) and TEM(b) images of O-CN-8; SEM(C) and TEM(c) images of O-CN-16
图 3 CN和O-CN的(a)XRD和(b)FT-IR图谱
Figure 3. (a) XRD patterns and (b) FT-IR spectra of the prepared CN and O-CN
图 4 O-CN-0.6的(a)XPS全光谱和(b-d)高分辨率光谱
Figure 4. (a) XPS full spectrum and high-resolution spectrum(b-d) of O-CN-0.6
图 5 CN和O-CN的(a)荧光光谱；(b)紫外可见光谱；(c)Tauc绘制曲线
Figure 5. CN and O-CN of (a) Fluorescence spectra; (b)UV-vis spectra; (c) Tauc plots
图 6 复合纳米纤维膜的SEM图像和直径分布((a/f)PVA，(b/g)PVA/O-CN-0.6，(c/h)PVA/O-CN-4，(d/i)PVA/O-CN-8，(e/j)PVA/O-CN-16)
Figure 6. SEM images and diameter distributions ((a/f)PVA、(b/g)PVA/O-CN-0.6、(c/h) PVA/O-CN-4、(d/i)PVA/O-CN-8、(e/j)PVA/O-CN-16) of composite nanofiber membrane
图 8 (a)CN和O-CN去除MB效率图；(b)PVA和PVA/O-CN去除MB效率图；(c)O-CN-0.6和PVA/O-CN-0.6去除MB的循环使用效果
Figure 8. (a) MB removal rate diagram of CN and O-CN; (b) MB removal rate diagram of PVA and PVA/O-CN; (c) reusability study results of O-CN-16 and PVA/O-CN-0.6
图 9 光照下CN(A/F)、O-CN(B~E/G~J)、PVA/CN(A/G)、PVA/O-CN(B~E/h~k)和PVA(F/l)对大肠杆菌和金黄色葡萄球菌的抑菌圈结果
Figure 9. Inhibitory zone results CN(A/F)、O-CN(B~E/G~J)、PVA/CN (a/g)、PVA/O-CN(b~e/h~k) and PVA(f/l) under illumination against E.coli and S.aureus
图 10 光照下CN(A/F)、O-CN(B~E/G~J)、PVA/CN(A/G)、PVA/O-CN(B~E/h~k)和PVA(F/l)对大肠杆菌和金黄色葡萄球菌的平板计数结果
Figure 10. Plate count results of CN(A/F)、O-CN(B~E/G~J)、PVA/CN (a/g)、PVA/O-CN(b~e/h~k) and PVA(f/l) under illumination against E.coli and S.aureus
图 11 不同纳米片和纳米纤维对大肠杆菌和金黄色葡萄球菌的抑菌性能
Figure 11. Antibacterial properties of different nanosheets and nanofibers against E.coli and S.aureus
图 12 在黑暗和可见光(λ≥420 nm)照射下O-CN-0.6和PVA/O-CN-0.6中(a)DMPO捕获$ \text{·}\text{OH} $，(b)TEMP捕获$ \text{1}\text{O}\text{2} $和(c)DMPO捕获$ {\text{·O}}_{\text{2}}^{{-}} $的ESR光谱
Figure 12. ESR spectra of (a) $ \text{·}\text{OH} $ trapping by DMPO, (b) $ \text{1}\text{O}\text{2} $ trapping by TEMP and (c) $ {\text{·O}}_{\text{2}}^{{-}} $ trapping by DMPO for O-CN-0.6 and PVA/O-CN-0.6 in the dark and under visible-light (λ≥420 nm) irradiation
表 1 CN和O-CN-0.6的原子百分比
Table 1. Atomic percentage of CN and O-CN-0.6
Element CN O-CN-0.6 C 1s 42.13% 42.77% N 1s 55.13% 53.55% O 1s 2.74% 3.69% 
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