Dye separation and self-cleaning performance of graphite carbon nitride-bismuth sulfide composite membrane
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摘要: 随着废水零排放的标准与要求不断深化，高效可持续的膜分离水处理技术成为研究热点，但面临着水通量低、易污染等问题。本研究通过石墨相氮化碳(g-C3N4)、细菌纤维素(BC)和硫化铋(Bi2S3)三者的有机结合，经真空辅助抽滤法制备得到光催化自清洁复合膜。通过一系列表征手段对粉末及膜材料进行物相结构与元素能态分析，研究了g-C3N4和Bi2S3不同添加量对复合膜染料分离性能的影响规律，探讨了两者在光催化下对染料的降解机制。结果表明，60wt%的g-C3N4、10wt%的BC、30wt%的Bi2S3与复合膜的综合性能最佳，水通量和截留率分别为23.48 L·m−2· h−1和100%，长时间过滤中依然保持16.65 L·m−2·h−1的水通量和90%左右的染料截留，在光照下浸泡3 h后通量恢复率达到96.5%，表明了该膜具有良好的光催化自清洁性能。该研究为高通量、可持续分离膜的设计提供了新的思路及基础探索。Abstract: With the deepening standards and requirements of zero wastewater discharge, efficient and sustainable membrane separation water treatment technology has become a research hotspot, but faces problems such as low water flux and easy pollution. In this work, photocatalytic self-cleaning composite membranes were prepared by the organic combination of graphitic carbon nitride (g-C3N4), bacterial cellulose (BC) and bismuth sulfide (Bi2S3) by vacuum-assisted filtration. The effects of different additions of g-C3N4 and Bi2S3 on the dye separation performance of the composite membranes were investigated through a series of characterization methods to analyze the physical structure and elemental energy states of the powders and membrane materials, and the degradation mechanism of the dyes under photocatalysis were explored. The results show that 60wt%g-C3N4, 10wt%BC, 30wt%Bi2S3 and the composite membrane have the best overall performance, with the water flux and rejection rate of 23.48 L·m−2·h−1 and 100%, respectively. The water flux of 16.65 L·m−2·h−1 and dye rejection rate of about 90% are still maintained in the long term filtration. The flux recovery rate reach 96.5% after soaking for 3 h under light, indicating that the membrane has good photocatalytic self-cleaning performance. This paper provides new ideas and basic exploration for the design of high-throughput and sustainable separation membranes.
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Key words:
- g-C3N4 /
- Bi2S3 /
- membrane separation /
- dye degradation /
- photocatalytic mechanism /
- bacterial cellulose
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图 2 g-C3N4-BC-30%Bi2S3的XPS图谱：(a) 总谱图；(b) C1s；(c) N1s；(d) S2p；(e) Bi4f
Figure 2. XPS spectra of g-C3N4-BC-30%Bi2S3: (a) Total spectrum; (b) C1; (c) N1s; (d) S2p; (e) Bi4f
图 3 CNB2、CNBB1、CNBB2、CNBB3不同倍率下截面的SEM图像((a1)~(d1), (a2)~(d2))；((a3)~(d3)) CNB2、CNBB1、CNBB2、CNBB3表面的SEM图像
Figure 3. SEM images of sections of CNB2, CNBB1, CNBB2 and CNBB3 at different magnification ((a1)-(d1), (a2)-(d2)); ((a3)-(d3)) SEM images of CNB2, CNBB1, CNBB2 and CNBB3 surfaces
图 4 (a) g-C3N4粉末；(b) CNB2；((c)~(d)) CNBB2不同倍率TEM图像
Figure 4. (a) g-C3N4 powder; (b) CNB2; ((c)-(d)) TEM images of CNBB2 at different magnification
图 5 CNB2、CNBB2的氮气吸附-脱附等温线 (a) 和孔径分布 (b)
Figure 5. Nitrogen adsorption desorption isotherms (a) and pore size distribution (b) of CNB2 and CNBB2
dp—Pore size; V—Volume; STP—Standard temperature and pressure
图 6 不同膜材料的水接触角(a)和纯水通量(b)
Figure 6. Water contact angle (a) and pure water flux (b) of various membranes
图 7 (a) 复合膜CNB1~CNB3水通量和截留率；(b) 刚果红(CR)的截留率；(c) 考马斯亮蓝(CBB)的截留率；(d) CR的归一化水通量；(e) CBB的归一化水通量
Figure 7. (a) Water flux and rejection rate of composite membrane CNB1-CNB3; (b) Rejection rate of Congo red (CR); (c) Rejection rate of coomassie brilliant blue (CBB); (d) Normalized water flux of CR; (e) Normalized water flux of CBB
图 8 (a) CR和CBB的水通量和截留率； (b) CR的截留率；(c) CBB的截留率；(d) CR的归一化水通量；(e) CBB的归一化水通量
Figure 8. (a) Water flux and rejection rate of CR and CBB; (b) Rejection rate of CR; (c) Rejection rate of CBB; (d) Normalized water flux of CR; (e) Normalized water flux of CBB
图 9 本研究复合膜与其他纳滤膜截留率和水通量的比较
GO—Graphene oxide; MOF—Metal-organic frameworks; RO—Reverse osmosis; NF—Nanofiltration; AAO—Anodic aluminum oxide; PVDF—Polyvinylidene difluoride; CA—Cellulose acetate; PA—Polypiperazine-amide; BIPOL/PAN-5—Biphenol/polyacrylonitrile-5
Figure 9. Comparison of rejection rate and water flux between composite membrane and other nanofiltration membranes in this study
图 10 CNB2、CNBB2光催化降解性能与自支撑效果
Figure 10. Photocatalytic degradation performance of CNB2, CNBB2
C—Concentration of solution after photocatalysis; C0—Concentration of solution before photocatalysis; DOM—Ammonium oxalate monohydrate; IPA—Isopropanol; BQ—Benzoquinone
图 11 CNB2和CNBB2的通量恢复率
Figure 11. Flux recovery rate of CNB2 and CNBB2
DI—Deionized water
图 12 g-C3N4、CNB2、CNBB2的光学性能：(a) 紫外-可见漫反射光谱图；(b) 带隙能(αhv)1/2与光子能(hv)的关系图
Figure 12. Optical properties of g-C3N4, CNB2 and CNBB2: (a) Diffuse reflectance UV-vis spectra; (b) Plots of band gap energy (αhv)1/2 vs photon energy (hv)
Eg—Band gap
图 13 CNBB2在可见光照射下记录的5, 5-二甲基-1-吡咯啉-N-氧化物 (DMPO)-•OH (a)、DMPO-•O2−加合物(b)的ESR图谱
Figure 13. ESR spectra of the 5,5-dimethyl-1-pyrroline-N-oxide (DMPO)-•OH (a) and DMPO-•O2− adducts recorded with the CNBB2 under visible light irradiation
图 14 g-C3N4-BC-Bi2S3复合膜有机染料去除及光催化机制
Figure 14. Separation and photocatalytic mechanism of organic dyesin g-C3N4-BC-Bi2S3 composite membranes
表 1 不同膜的添加比例
Table 1. Addition ratio of different membrane
Membrane g-C3N4
/wt%BC
/wt%Bi2S3
/wt%Total
/mgCNB1 90 10 — 60 CNB2 90 10 — 90 CNB3 90 10 — 120 CNBB1 80 10 10 90 CNBB2 60 10 30 90 CNBB3 40 10 50 90 Notes: BC—Bacterial cellulose; g-C3N4—Graphitic carbon nitride; CNB—g-C3N4-BC; CNBB—g-C3N4-BC-Bi2S3. 
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表 2 不同膜的孔隙与比表面积
Table 2. Porosity and specific surface area of different membranes
Membrane Specific surface area/(m2·g−1) Pore diameter/nm Pore volume/
(cm3·g−1)CNB2 76.37 5.89 0.16 CNBB2 61.96 7.81 0.13
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