Enhanced U(VI) bioreduction by alginate-immobilized uranium-reducing bacteria in the presence of carbon nanotubes and anthraquinone-2,6-disulfonate

Uranium-reducing bacteria were immobilized with sodium alginate, anthraquinone-2, 6-disulfonate (AQDS), and carbon nanotubes (CNTs). The effects of different AQDS-CNTs contents, U(IV) concentrations, and metal ions on U(IV) reduction by immobilized beads were examined. Over 97.5% U(VI) (20 mg/L) was removed in 8 hr when the beads were added to 0.7% AQDS-CNTs, which was higher than that without AQDS-CNTs. This result may be attributed to the enhanced electron transfer by AQDS and CNTs. The reduction of U(VI) occurred at initial U(VI) concentrations of 10 to 100 mg/L and increased with increasing AQDS-CNT content from 0.1% to 1%. The presence of Fe(III), Cu(II) and Mn(II) slightly increased U(VI) reduction, whereas Cr(VI), Ni(II), Pb(II), and Zn(II) significantly inhibited U(VI) reduction. After eight successive incubation-washing cycles or 8 hr of retention time (HRT) for 48 hr of continuous operation, the removal efficiency of uranium was above 90% and 92%, respectively. The results indicate that the AQDS-CNT/AL/cell beads are suitable for the treatment of uranium-containing wastewaters.     

Carbon nanotubes-incorporated MIL-88B-Fe as highly efficient Fenton-like catalyst for degradation of organic pollutants

CNTs were incorporated into MIL-88B-Fe to get a new Fenton-like catalyst (C@M). Fe(II) was introduced in C@M to get a fast initiation of Fenton-like reaction. Fe(II) content in C@M was related with oxygen-containing functional groups on CNTs. C@M shows efficient catalytic degradation of pollutants over a wide pH range. Iron-based metal organic frameworks have been verified to be efficient heterogeneous Fenton catalysts due to their open pore channels and highly uniform distribution of metallic centers. In these catalysts, however, the iron element is mainly in the form of Fe(III), which results in a process required to reduce Fe(III) to Fe(II) to initiate Fenton reaction. To address this problem, carbon nanotubes (CNTs) with electron-rich oxygen-functional groups on the surface were incorporated into the metal organic frameworks (MIL-88B-Fe) to improve Fe(II) content for an enhanced Fenton-like performance. The prepared CNT@MIL-88B-Fe (C@M) showed much stronger catalytic ability toward H₂O₂ than MIL-88B-Fe. The pseudo-first-order kinetic constant for phenol degradation by C@M (0.32 min^–1) was about 7 times that of MIL-88B-Fe, and even higher than or comparable to the values of reported heterogeneous Fenton-like catalysts. Moreover, the Fenton-like system could effectively degrade various kinds of refractory organic pollutants and exhibited excellent catalytic activity over a wide pH range (4–9). XPS analysis confirmed that Fe(II) content of the catalyst gradually increased with CNT loadings. Electron spin resonance analysis showed that the signal intensity (•OH) of C@M was much higher than MIL-88B-Fe, which was consistent with the degradation efficiency of pollutants. Furthermore, the Fe(II) content of the catalyst gradually increased along with the oxygen-functional group content of CNTs. The result demonstrated that oxygen-containing functional groups of CNTs have a significant impact on the enhanced catalytic performance of C@M. This study provides a new insight to enhance Fenton reaction by using nanocarbon materials.     

碳纳米管的特性及其在防腐涂层中的应用

综述了碳纳米管的结构、性能、制备方法和应用,并简要叙述了碳纳米管的发展历程。着重介绍了碳纳米管在防腐涂层中的研究和应用,其主要应用有化学复合镀、电镀和涂料。最后分析了碳纳米管在腐蚀领域的发展和应用前景。     

碳纳米管对亚甲基蓝的吸附性能研究

碳纳米管的一维管状中空结构,对有机物具有吸附能力,有望用于废水处理.本文通过理论分析和试验验证,探讨了采用碳纳米管时亚甲基蓝溶液浓度、溶液pH值、吸附时间和吸附温度等对吸附过程的影响,分析了碳纳米管对亚甲基蓝的吸附机理.结果表明,碳纳米管对亚甲基蓝的吸附在3 h达到平衡,吸附速率常数为384.49 h-1;吸附过程遵循Langmiur方程;碱性条件有利于吸附的进行;随着温度的升高,碳纳米管对亚甲基蓝的吸附量增加.吸附机理为,碳纳米管对亚甲基蓝的吸附是一个吸热过程,第一层吸附包含物理吸附和化学吸附,而多层吸附则是物理吸附.     

改性纳米碳管的理化性质、毒性及风险研究进展

随着纳米材料的广泛应用,在生产加工过程中,各种改性后的纳米碳管(CNTs)进入环境。充分认识改性后CNTs的理化性质是对其进行客观风险评价的重要前提。主要分析了几种常用方法改性后的CNTs的悬浮、吸附特征及其理化性质差异,综述了目前CNTs毒理学实验的研究进展,评价了其潜在风险,并提出了今后研究的方向。     

Enhanced U(Ⅵ) bioreduction by alginate-immobilized uranium-reducing bacteria in the presence of carbon nanotubes and anthraquinone-2,6-disulfonate

Uranium-reducing bacteria were immobilized with sodium alginate, anthraquinone-2,6-disulfonate(AQDS), and carbon nanotubes(CNTs). The effects of different AQDS-CNTs contents, U(Ⅳ) concentrations, and metal ions on U(Ⅳ) reduction by immobilized beads were examined. Over 97.5% U(Ⅵ)(20 mg/L) was removed in 8 hr when the beads were added to 0.7% AQDS-CNTs, which was higher than that without AQDS-CNTs. This result may be attributed to the enhanced electron transfer by AQDS and CNTs. The reduction of U(Ⅵ) occurred at initial U(Ⅵ) concentrations of 10 to 100 mg/L and increased with increasing AQDS-CNT content from 0.1% to 1%. The presence of Fe(Ⅲ), Cu(Ⅱ) and Mn(Ⅱ)slightly increased U(Ⅵ) reduction, whereas Cr(Ⅵ), Ni(Ⅱ), Pb(Ⅱ), and Zn(Ⅱ) significantly inhibited U(Ⅵ) reduction. After eight successive incubation-washing cycles or 8 hr of retention time(HRT) for 48 hr of continuous operation, the removal efficiency of uranium was above 90% and 92%, respectively. The results indicate that the AQDS-CNT/AL/cell beads are suitable for the treatment of uranium-containing wastewaters.     

碳纳米管基复合吸附剂的制备及其吸附性能

为了解决碳纳米管(CNTs)在吸附水中污染物时易聚集、难分离的问题,本文采用静电自组装技术将碳纳米管固定化在具有微米级粒径的碳酸钙颗粒表面,设计制备了壳-核结构的CNTs基复合吸附剂.实验考查了不同碳纳米管分散体系对复合吸附剂制备的影响,并采用Zeta电位、拉曼光谱、扫描电镜等手段对复合吸附剂的制备过程和结构进行表征,探讨了制备的碳纳米管基复合吸附剂对菲的吸附性能.结果发现,复合吸附剂对菲的吸附能力随CNTs载量的增加而增大,CNTs标化的吸附系数则随CNTs载量的增加而下降,碳纳米管是复合吸附剂的主要吸附位点.     

天然有机质模型化合物分子结构对碳纳米管分散性的影响

研究了不同分子结构的天然有机物质（NOM）模型化合物单宁酸（TA）、没食子酸（GA）和十二烷基苯磺酸钠（SDBS）对碳纳米管（CNTs）分散性的影响.通过计算得出,TA的临界胶束浓度（CMC）为1.12mmol/L,SDBS的CMC为0.24mmol/L,GA在所测试的浓度范围内没有形成胶束.比较NOM在CNTs表面的吸附过程和CNTs的分散过程,表明空间位阻和胶束包裹是2个促进CNTs分散的主要机理.借助透射电子显微镜（TEM）和测量悬浮的CNTs的平均流体动力学直径（DLS）结果表明,TA在较少的固相吸附量（S_e ≈ 0.01mmol/g）就能使CNTs分散,归因于其吸附后刚性芳香三维结构的TA能形成的较大空间位阻;同样具有芳香平面结构的GA分子在CNTs表面的吸附需要达到一定的厚度（S_e > 0.2mmol/g）,才能有效地分散CNTs;具有烷基脂肪链的SDBS,需要在形成半胶束或胶束后（S_e > 0.13mmol/g） CNTs才能有效地被分散.芳香族刚性结构和脂肪族柔性结构的模型化合物对CNTs的分散效果和机理存在较大的差别.     

碳纳米管预沉积改性膜的污染机理研究

为探究碳纳米管(Carbon Nanotubes,CNTs)预沉积改性膜的污染机理,本研究使用正压过滤法将CNTs预沉积在3种孔径的有机膜(20 kDa聚醚砜膜、0.01 μm和0.1 μm聚偏二氟乙烯膜)表面,研究了CNTs预沉积改性膜过滤3种典型污染物(牛血清蛋白、腐殖酸、海藻酸钠)过程中的膜污染情况.根据比通量、Hermia模型和传统滤饼过滤模型,对恒压死端过滤3种典型污染物过程中的污染机理进行了系统评价.结果表明,20 kDa PES膜和0.01 μm PVDF膜表面预沉积CNTs改性后,过滤3种典型膜污染物质时的膜污染情况都得到了一定程度的缓解.20 kDa PES膜表面预沉积CNTs后过滤HA初期为完全孔堵塞与滤饼过滤相结合的复合污染机理,最终转变为滤饼过滤;过滤SA的污染机理为完全孔堵塞与滤饼过滤相结合的复合污染机理.0.01 μm PVDF膜表面沉积CNTs改性后过滤HA初期的污染机理为膜孔堵塞与滤饼过滤相结合的复合污染机理,然后经过向滤饼过滤转变的过渡阶段,最终形成滤饼过滤,且随着CNTs沉积量的增加,过渡阶段持续时间延长.0.1 μm PVDF膜表面预沉积CNTs后过滤3种污染物,均未能缓解膜污染,膜污染机理不受CNTs沉积改性的影响,其过滤BSA和HA的污染机理为膜孔堵塞,过滤SA过程的污染机理符合滤饼过滤.     

Electro-assisted CNTs/ceramic flat sheet ultrafiltration membrane for enhanced antifouling and separation performance

• A stable and electroconductive CNTs/ceramic membrane was fabricated. • The membrane with the electro-assistance exhibited optimal fouling mitigation. • The removal efficiency was improved by the -2.0 V electro-assistance. • Electro-assisted filtration is energy-saving than that of commercial membrane. Ultrafiltration is employed as an important process for water treatment and reuse, which is of great significance to alleviate the shortage of water resources. However, it suffers from severe membrane fouling and the trade-off between selectivity and permeability. In this work, a CNTs/ceramic flat sheet ultrafiltration membrane coupled with electro-assistance was developed for improving the antifouling and separation performance. The CNTs/ceramic flat sheet membrane was fabricated by coating cross-linked CNTs on ceramic membrane, featuring a good electroconductivity of 764.75 S/m. In the filtration of natural water, the permeate flux of the membrane with the cell voltage of -2.0 V was 1.8 times higher than that of the membrane without electro-assistance and 5.7-fold greater than that of the PVDF commercial membrane. Benefiting from the electro-assistance, the removal efficiency of the typical antibiotics was improved by 50%. Furthermore, the electro-assisted membrane filtration process showed 70% reduction in energy consumption compared with the filtration process of the commercial membrane. This work offers a feasible approach for membrane fouling mitigation and effluent quality improvement and suggests that the electro-assisted CNTs/ceramic membrane filtration process has great potential in the application of water treatment.