Preparation and antibacterial properties of GO@P-g-C3N4 composite photocatalytic material
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摘要: 通过静电自组装法制备了质子化石墨相氮化碳(P-g-C3N4)涂层的氧化石墨烯(GO)复合材料(GO@P-g-C3N4)，探究其在光催化抗菌方面的应用。通过SEM、TEM、XRD、XPS、Raman、UV-Vis DRS、稳态／瞬态荧光光谱(PL)等对GO@P-g-C3N4复合材料的微观形貌、晶态结构及光电性能进行表征，并通过调控P-g-C3N4的含量对GO@P-g-C3N4复合材料进行了结构优化。在模拟太阳光照射条件下，以大肠杆菌(E. coli)和金黄色葡萄球菌(S. aureus)为实验对象，研究了不同P-g-C3N4含量的GO@P-g-C3N4复合材料的光催化抗菌性能，以及光照时间对抗菌性能的影响。结果表明：GO与P-g-C3N4以质量比为1∶4合成的GO@P-g-C3N4-80%复合材料，光照100 min后，对E. coli和S. aureus的抑菌率分别为98.80%和95.99%；光照150 min后，对E. coli和S. aureus的抑菌率均达到99%以上，抗菌性能显著优于GO与P-g-C3N4。Abstract: A protonated graphite carbon nitride (P-g-C3N4) coated graphene oxide (GO) composite material (GO@P-g-C3N4) was prepared via electrostatic self-assembly method, and its application in photocatalytic antibacterial activities was investigated. The micro morphologyies, crystalline structures, and photoelectric properties of the GO@P-g-C3N4 composite material were characterized by SEM, TEM, XRD, XPS, Raman, UV-Vis DRS and steady-state/transient fluorescence spectroscopy (PL), etc. The structure of GO@P-g-C3N4 composite material was optimized by adjusting the content of P-g-C3N4. Under simulated solar light irradiation conditions, E. coli and S. aureus were used as experimental targets to study the photocatalytic antibacterial performance of GO@P-g-C3N4 composites with different P-g-C3N4 contents and the influence of irradiation times on antibacterial performance. It was found that GO@P-g-C3N4-80% composite material synthesized with a mass ratio of 1∶4 between GO and P-g-C3N4 exhibited antibacterial rates against E. coli and S. aureus of 98.80% and 95.99%, respectively after 100 minutes of illumination; after 150 minutes of illumination, antibacterial rates against both E.coli and S.aureus exceeded 99%, demonstrating significantly better antibacterial performance compared to individual GO or P-g-C3N4.
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Key words:
- graphene oxide /
- P-g-C3N4 /
- composite /
- photocatalysis /
- antibacterial performance
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图 1 (a) B-g-C3N4、(c) P-g-C3N4、(e) GO和(g) GO@P-g-C3N4的SEM图；(b) B-g-C3N4、(d) P-g-C3N4，(f) GO和(h) GO@P-g-C3N4的TEM图；(i) GO@P-g-C3N4的EDX元素分布图
Figure 1. SEM images of (a) B-g-C3N4, (c) P-g-C3N4, (e) GO and (g) GO@P-g-C3N4; TEM images of (b) B-g-C3N4, (d) P-g-C3N4, (f) GO and (h) GO@P-g-C3N4; (i) EDX image of GO@P-g-C3N4
图 2 GO、B-g-C3N4、P-g-C3N4和GO@P-g-C3N4的XRD图
Figure 2. XRD patterns of GO, B-g-C3N4, P-g-C3N4 and GO@P-g-C3N4
图 3 (a) P-g-C3N4、GO和GO@P-g-C3N4的XPS全谱图；(b) GO和(c) P-g-C3N4的O 1s高分辨率XPS谱图；(d) GO、(e) P-g-C3N4和(f) GO@P-g-C3N4的C 1s高分辨率XPS谱图；(g) P-g-C3N4和(h) GO@P-g-C3N4的N 1s高分辨率XPS谱图；(i) B-g-C3N4、P-g-C3N4、GO和GO@P-g-C3N4的Raman谱图
Figure 3. (a) XPS survey spectra of P-g-C3N4, GO and GO@P-g-C3N4; High-resolution O 1s XPS spectra of (b) GO and (c) P-g-C3N4; High-resolution C 1s XPS spectra of (d) GO, (e) P-g-C3N4 and (f) GO@P-g-C3N4; High-resolution N 1s XPS spectra of (g) P-g-C3N4 and (h) GO@P-g-C3N4; (i) Raman spectra of B-g-C3N4, P-g-C3N4, GO and GO@P-g-C3N4
图 4 (a) P-g-C3N4和GO@P-g-C3N4的N2吸附-解吸等温线及(b)孔径分布图
Figure 4. (a) N2 adsorption/desorption isotherms and (b) pore size distributions of P-g-C3N4 and GO@P-g-C3N4
图 5 (a) P-g-C3N4和GO@P-g-C3N4的UV-Vis DRS及对应的(b) Kubelka-Munk曲线
Figure 5. (a) UV-Vis DRS of P-g-C3N4 and GO@P-g-C3N4 and (b) corresponding Kubelka-Munk curves
图 6 P-g-C3N4和GO@P-g-C3N4的光致发光谱图
Figure 6. Photoluminescence spectra of P-g-C3N4 and GO@P-g-C3N4
图 7 P-g-C3N4和GO@P-g-C3N4的光电流时间曲线
Figure 7. Photocurrent time curves of P-g-C3N4 and GO@P-g-C3N4
图 8 对照组和不同光催化剂对E. coli和S. aureus的光催化抑菌率
Figure 8. Photocatalytic inhibition rates of E. coli and S. aureus under control and different photocatalysts
图 9 不同光催化剂作用下的E. coli和S. aureus菌落琼脂平板照片
Figure 9. Images of the agar plates of bacterial colonies formed by E. coli and S. aureus under different photocatalys
图 10 不同质量比GO@P-g-C3N4对E. coli和S. aureus的光催化抑菌率
Figure 10. Photocatalytic inhibition rates of E. coli and S. aureus under different mass ratios
图 11 不同质量比GO@P-g-C3N4作用下E. coli和S. aureus菌落琼脂平板照片
Figure 11. Images of the agar plates of bacterial colonies formed by E. coli and S. aureus under different mass ratios
图 12 GO@P-g-C3N4-80%在不同光照时间下对E. coli和S. aureus的光催化抑菌率
Figure 12. Photocatalytic inhibition rates of E. coli and S. aureus by GO@P-g-C3N4-80% after different irradiation times
图 13 GO@P-g-C3N4-80%在不同光照时间下的E. coli和S. aureus菌落琼脂平板照片
Figure 13. Images of the agar plates of bacterial colonies formed by E. coli and S. aureus in the presence of GO@P-g-C3N4-80% after different irradiation times
图 14 GO@P-g-C3N4-80%在三次循环过程中对E. coli和S. aureus的光催化抑菌率
Figure 14. Photocatalytic inhibition rates of E. coli and S. aureus by GO@P-g-C3N4-80% during the three cycles
图 15 GO@P-g-C3N4-80%在三次循环过程中的E. coli和S. aureus菌落琼脂平板照片
Figure 15. Images of the agar plates of bacterial colonies formed by E. coli and S. aureus in the presence of GO@P-g-C3N4-80% during the three cycles
图 16 GO@P-g-C3N4-80%三次循环后的XRD谱图
Figure 16. XRD spectrum of GO@P-g-C3N4-80% after third cycles
图 17 (a-d) S. aureus和(a*-d*) E. coli在GO@P-g-C3N4-80%的催化下分别照射不同时间后的SEM图
Figure 17. SEM images of (a-d) S. aureus and (a*-d*) E. coli after irradiation for different times under the catalysis of GO@P-g-C3N4-80%
图 18 P-g-C3N4和GO@P-g-C3N4在(a)黑暗条件下和(b)光照5 min后的DMPO-·O2− ESR谱；GO@P-g-C3N4在黑暗条件下和光照5 min后的(c) DMPO-·OH ESR谱和(d) TEMPO-e− ESR谱
Figure 18. EPR spectra of DMPO−•O2− over P-g-C3N4 and GO@P-g-C3N4 under irradiation times of (a) 0 and (b) 5 min; EPR spectra of (c) DMPO−•OH and (d) TEMPO-e− with GO@P-g-C3N4 under irradiation times of 0 and 5 min
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