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采用纳米吸附剂实现对有机染料的处理在污水净化领域具有很好的前景, 特别是拥有自沉积特性的纳米吸附剂可以更为有效地提高处理污水的效率. 本文利用液相结晶得到的二维纳米花瓣, 通过自组装制备的多孔花状硫化铜(CuS)级次纳米材料, 不仅实现了对污水中有机污染物的高效吸附处理, 而且拥有快速自沉积特性, 本文以甲基蓝等为吸附质对其吸附自沉积特性进行了研究. 结果表明: 使用10 mg多孔花状 CuS级次纳米结构材料在30 min内对0.8 mg甲基蓝分子的吸附效率可达100%, 在3 h内即可完成自沉积, 相比于CuS微米绒球的吸附效率提高了55%, 沉积效率提高了95%; 相比于CuS微米颗粒的吸附效率提高了26%, 沉积效率提高了3.17倍. 该优异的吸附自沉积性能归结于多孔级次纳米花比微米绒球和微米颗粒有更大的比表面积, 其表面具备更大的孔隙率, 且具备更强的静电吸附能力. 本研究结果为有效地处理污水中的有机染料提供了可能的新思路.In recent decades, growing population and industrial development have led to releasing huge amounts of highly toxic chemical pollutants into the environment globally. Several approaches to handling the removal of contaminants from wastewater for environmental remediation, including biological, chemical, physical, and advanced oxidation processes have been employed. Among them, using nano-adsorbents as a tool for effectively removing organic contaminants represents a promising strategy in sewage purification field. More importantly, the nano-adsorbents with auto-deposition property can greatly improve the efficiency of sewage treatment. Therefore, the developing of environment friendly nano-adsorbents is thus an important issue to remove organic contaminants in water via simply adsorbing. Here in this work, porous flower-like copper sulfide (CuS) grade sub-nanomaterials are successfully fabricated by simply mixing two inorganic salts. Furthermore, the as-prepared nano-adsorbents with auto-deposition property can create a super adsorption capability for organic contaminants in wastewater. We further study the adsorption/auto-deposition characteristics of porous flower-like CuS grade sub-nanomaterials systematically by using various organic dyes (methyl blue, crystal violet, lemon yellow, sunset yellow and amaranth) as target molecules. For instance, in a typical procedure, 0.8-mg methyl blue can be removed 100% via adding 10-mg porous flower-like CuS grade sub-nanomaterials sample in 30 min. Therefore, the adsorption efficiency can be enhanced by 55% and 26% in comparison with the adsorption efficiency of CuS micro pompons and micron particles, respectively. Additionally, the porous flower-like CuS grade sub-nanomaterials can self-deposite on the bottom of the solution within 3 h after adsorption has finished, and the deposition efficiency can be improved by 95% and 3.17 times in comparison with the deposition efficiency of CuS micro pompons and micron particles, respectively. Comparing with micron particles, the unique self-depositing characteristics of porous flower-like grade sub-nanomaterials are attributed to larger specific surface area, greater porosity and stronger electrostatic adsorption capacity. Remarkably, this work provides an effective method of effectively removing various organic dyes from wastewater.
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Keywords:
- self-deposition adsorption /
- porous sub-nanoflower /
- copper sulfide /
- self-assembly
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图 1 (a), (b)多孔级次纳米花; (c), (d)微米绒球; (e), (f)微米颗粒的SEM
Fig. 1. (a), (b) SEM image of porous grade sub-nanoflowers; (c), (d) SEM image of micron pompon; (e), (f) SEM image of micron particles.
图 2 (a) 多孔级次纳米花的S和Cu的能量散射谱; (b) mapping选区SEM图; (c), (d) 分别为S和Cu元素分布
Fig. 2. (a) Energy scattering spectra of S and Cu in porous grade sub-nanoflowers; (b) mapping selected SEM image; (c), (d) S and Cu elements mapping, respectively.
图 3 多孔级次纳米花CuS的TEM图 (a), (b), (c) 分辨率依次增大; (d) 选区电子衍图谱
Fig. 3. (a), (b), (c) The typical low and enlarged TEM image of porous grade sub-nanoflowers CuS; (d) the corresponding selected area electron diffraction (SAED) pattern.
图 4 CuS微米颗粒、微米绒球、多孔级次纳米花的XRD谱
Fig. 4. XRD spectra of CuS micron pompon、micron particles and porous grade sub-nanoflowers.
图 5 级次纳米花的XPS谱 (a) Cu; (b) S
Fig. 5. XPS spectra of grade sub-nanoflowers: (a) Cu; (b) S.
图 6 (a), (b), (c) 分别为多孔级次纳米花、微米颗粒、微米绒球的氮气吸脱附曲线; (d), (e), (f)为对应的孔径分布曲线
Fig. 6. (a), (b), (c) Nitrogen desorption curve of porous grade sub-nanoflowers, micron pompon and micron particles, respectively; (d), (e), (f) the corresponding aperture distribution curve.
图 7 (a), (b)分别为纳米枝晶正在生长为纳米花瓣时的TEM图和SEM图; (c)硫源释放S2– 速率过快导致CuS直接团聚而未能得到纳米花瓣; (d)自组装过程因能量不足导致大量纳米片散落
Fig. 7. (a), (b) TEM and SEM images when nanocrystals are growing into nanocrystals, respectively; (c) the S2– release rate of sulfur source is too fast, which leads to direct aggregation of CuS and fails to obtain nanopetals; (d) a large number of nanosheets were scattered due to lack of energy during the self-assembly process.
图 8 (a) CuS多孔级次纳米花, (b) CuS微米绒球, (c) CuS微米颗粒材料吸附MB溶液后上清液吸收谱随吸附时间的变化曲线; (d)表征三份材料对MB的吸附过程
Fig. 8. The varied absorption spectra of supernatant after adding (a) porous grade sub-nanoflowers, (b) micron pompon and (c) micron particle material to adsorb MB with changing adsorption time; (d) the adsorption process of MB by adding three materials, respectively.
图 9 溶液体系的吸收谱 (a)静置1 h, (b)静置3 h. 插图为吸附体系实物照片（批注：需要把曲线的文字注释和右上角插图中的文字注释中的“微米球”改为“微米绒球”，把“微米椭球”改为“微米颗粒”）
Fig. 9. The absorption spectra of the solution system after standing for (a)1 h and (b)3 h; The inset is a physical photo of the adsorption system.
图 10 (a)多孔级次纳米花, (b)微米绒球和(c)微米颗粒吸附MB染料分子后的SEM
Fig. 10. SEM images of (a) porous grade sub-nanoflowers, (b) micron pompon, and (c) micron particle material after adsorbing MB dye molecules.
图 11 (a)多孔级次纳米花对结晶紫, (b)柠檬黄, (c)日落黄, (d)苋菜红的吸附过程中测试离心液的吸收谱线
Fig. 11. The absorption spectra of (a) crystal violet, (b) lemon yellow, (c)sunset yellow and (d)amaranth by adding porous grade sub-nanoflowers as nano-adsorbents via centrifugal treatment.
图 12 (a)为苋菜红、日落黄、柠檬黄和结晶紫的原始吸收谱; (b), (c)分别为加入多孔级次纳米花材料静置30 min和3 h后溶液吸收谱
Fig. 12. (a) The original absorption spectra of amaranth, sunset yellow, lemon yellow and crystal violet; (b), (c) the absorption spectra of the solution after adding porous grade sub-nanoflowers materials for 30 min and 3 h, respectively.
表 1 三份样品的Zeta电势
Table 1. Zeta potential of three samples.
样品 Zeta电势/mV 级次纳米花 –13.3 微米绒球 –2.29 微米颗粒 –1.15 
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[1] Srivastava S, Sinha R, Roy D 2004 Aquat. Toxicol. 66 319
Google Scholar
[2] Wu Y, Su M, Chen J, Xu Z, Tang J, Chang X, Chen D 2019 Dyes Pigm. 170 107591
Google Scholar
[3] Zhang H, Chen M, Wang D M, Xu L L, Liu X D 2016 Opt. Mater. Express 6 2573
Google Scholar
[4] Miao X, Tang Y, Wong C W 2015 Nature 518 483
[5] Ghorai S, Sarkar A, Raoufi M, Panda A B, Schönherr H, Pal S 2014 ACS Appl. Mater. Interfaces 6 4766
Google Scholar
[6] Wu Z, Joo H, Lee K 2005 Chem. Eng. J. 112 227
Google Scholar
[7] Xie Y J, Yan B, Xu H L, Chen J, Liu Q X, Deng Y H, Zeng H B 2014 ACS Appl. Mater. Interfaces 6 8845
Google Scholar
[8] Feng M, You W, Wu Z S, Chen Q D, Zhan H B 2013 ACS Appl. Mater. Interfaces 5 12654
Google Scholar
[9] Yousefi M, Villar-Rodil S, Paredes J I, Moshfegh A Z 2019 J. Alloy. Compd. 809 151783
Google Scholar
[10] Zhan Y, Wan X, He S, Yang Q, He Y 2018 Chem. Eng. J. 333 132
Google Scholar
[11] Reddy P A K, Reddy P V L, Kwon E, Kim K, Akter T, Kalagara S 2016 Environ. Int. 91 94
Google Scholar
[12] Verdin A, Sahraoui A L H, Durand R 2004 Int. Biodeterior. Biodegrad. 53 65
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[13] Zhang X, Zhang P Y, Wu Z, Zhang L, Zeng G M, Zhou C J 2013 Colloids Surf., A 435 85
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Google Scholar
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