两种抗生素对塔玛亚历山大藻生长和产毒的影响

论文以中国南海筛选的一株塔玛亚历山大藻Alexandrium tamarense C101为研究对象,研究了两种抗生素,氨苄青霉素(ampicillin,Amp)和新霉素(neomycin,Nm)对A.tamarense C101细胞生长、形态以及毒素含量的影响.结果表明:和空白对照组相比,经1 500μg/mL Nm...     

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.     

纳米Fe掺杂MIL-101(Cr)及其吸附放射性碘研究

目的改进并提高MIL-101(Cr)吸附气态碘单质的性能,以期用于核事故放射性碘富集吸收。方法通过水热法制备MIL-101(Cr)材料,并利用纳米Fe掺杂改性,运用SEM、XRD等对掺杂前后的材料进行表征。将材料在75℃条件下对气态碘单质进行吸附,并比较不同Fe掺杂量下材料对气态碘吸附性能的差异。结果纳米Fe成功掺杂于基体材料MIL-101中,并对基体材料晶体结构无破坏作用。吸附性能研究表明,掺杂纳米Fe质量分数为1%的Fe@MIL-101吸附性能最优,对气态碘的饱和吸附量可达3.42 g(I2)/g(MIL-101)。结论纳米Fe掺杂改性的MIL-101材料在高温条件下对气态碘单质具有良好的吸附效果,有望应用于核反应堆事故中对放射性碘的富集或捕集。     

新型MIL-100(Fe)基MOFs材料的制备及其对Sr2+的吸附

采用水热法和溶剂热法制备了金属有机骨架材料——MIL-100(Fe)和MIL-100(Fe)-DMA.利用FTIR、XRD、SEM、XPS和N₂吸附/脱附对材料结构进行了表征.通过静态吸附实验,探究了初始Sr²⁺浓度、吸附时间、溶液pH值和不同共存阳离子对材料吸附性能的影响,研究了两种材料对Sr²⁺吸附过程的吸附动力学和吸附等温线模型.表征结果表明:两种材料基本骨架一致,吸附Sr²⁺对材料骨架影响均可忽略;虽然MIL-100(Fe)-DMA比表面积小于MIL-100(Fe),但由于晶粒尺寸小,堆积形成的介孔结构更有利于Sr²⁺的扩散.吸附实验结果表明:随着反应时间和初始Sr²⁺浓度的增加,两种材料对Sr²⁺的吸附量先迅速增大再逐渐达到平衡;随着pH值的增大,两种材料对Sr²⁺的吸附量增大,且碱性条件下吸附效果好;两种材料吸附过程均符合准二级动力学模型、颗粒内扩散模型和Langmuir吸附等温模型;采用三价铁盐作为铁源以及DMA作为有机溶剂可提高MIL-100(Fe)材料对Sr²⁺的吸附效果.     

铁铜双金属有机骨架MIL-101(Fe,Cu)活化双氧水降解染料性能

针对非均相芬顿传质效率低和Fe（Ⅲ）Fe（Ⅱ）转化慢导致活性低等问题,采用溶剂热法制备铁铜双金属有机骨架材料[MIL-101（Fe,Cu）],并研究了材料界面性质、催化降解染料（亚甲基蓝）性能以及活化催化机制.结果表明,MIL-101（Fe,Cu）晶体结构完整且呈三维八面体形状;比表面积和平均孔径分别为667.2 m² ·g^-1和1.9 nm,可充分暴露反应活性位点.MIL-101（Fe,Cu）在广谱pH范围可活化H₂ O₂高效降解亚甲基蓝.当pH=5、反应20 min,MIL-101（Fe,Cu）/H₂ O₂对20 mg ·L^-1亚甲基蓝的去除率为100%,较MIL-101（Fe）/H₂O₂和单独H₂ O₂分别提高43.1%和88.9%.自由基猝灭实验与反应前后铁和铜价态变化结果表明,羟基自由基（·OH）是MIL-101（Fe,Cu）/H₂ O₂催化降解亚甲基蓝的主要活性物种;Cu（Ⅱ）掺杂引入新的活性位点,且Cu（Ⅱ）/Cu（Ⅰ）循环和Fe（Ⅲ）/Fe（Ⅱ）循环可协同产生·OH,进而提高催化效率.MIL-101（Fe,Cu）作为新型非均相类芬顿催化剂,无需复杂pH调节即可获得良好催化效果,在工业废水处理上具有较好地应用前景.     

Fast and efficient aqueous arsenic removal by functionalized MIL-100(Fe)/rGO/δ-MnO2 ternary composites: Adsorption performance and mechanism

Because of its significant toxicological effects on the environment and human health,arsenic(As) is a major global issue.In this study,an Fe-based metal-organic framework(MOF)(Materials of Institut Lavoisier:MIL-100(Fe)) which was impregnated with reduced graphene oxide(rGO) by using a simple hydrothermal method and coated with birnessitetype manganese oxide(δ-MnO_2) using the one-pot reaction process(MIL-100(Fe)/rGO/δ-MnO_2 nanocomposites) was synthesized and applied successfully in As removal.The removal efficiency was rapid,the equilibrium was achieved in 40 min and 120 min for As(Ⅲ) and As(Ⅴ),respectively,at a level of 5 mg/L.The maximum adsorption capacities of As(Ⅲ) and As(Ⅴ) at pH 2 were 192.67 mg/g and 162.07 mg/g,respectively.The adsorbent revealed high stability in pH range 2-9 and saturated adsorbent can be fully regenerated at least five runs.The adsorption process can be described by the pseudo-second-order kinetic model and Langmuir monolayer adsorption.The adsorption mechanisms consisted of electrostatic interaction,oxidation and inner sphere surface complexation.     

MIL-101高效吸附测定土壤气中三氯乙烯及健康风险评估

为研究基于实测土壤气中ρ（三氯乙烯）计算风险值与Johnson-Ettinger联合Dual-Equilibrium Desorption（JE-DED）模型和J&E模型计算风险值的差异,在MIL-101、UIO-66、ZIF-8和MOF-801金属-有机骨架（MOFs）材料,球形活性炭、膨胀石墨碳吸附材料及HiSiv1000和HiSiv3000分子筛等3类8种吸附剂中筛选出吸附效率较高的MIL-101 MOF材料用以吸附并测定土壤气中ρ（三氯乙烯）,并将基于实测土壤气中ρ（三氯乙烯）计算的风险值与J&E模型和JE-DED模型计算的风险值进行比较.结果表明:①对于北京潮土和黑龙江黑土,J&E模型计算的风险值比基于实测土壤气中ρ（三氯乙烯）计算的风险值高2个数量级.②对于w（有机碳）较低的北京潮土,基于JE-DED模型计算的风险值比基于实测土壤气中ρ（三氯乙烯）计算的风险值高1个数量级,但比基于J&E模型计算的风险值低1个数量级,表明JE-DED模型预测结果更接近实际情况,但仍偏保守.③w（有机碳）较高的黑龙江黑土,JE-DED模型计算的风险值与基于实测土壤气中ρ（三氯乙烯）计算的风险值更接近,JE-DED模型可以比较准确地预测三氯乙烯的风险值.研究显示,采用土壤气中ρ（三氯乙烯）实测值和JE-DED模型进行风险评价在一定程度上可以避免J&E计算过于保守的问题,可以更加真实客观地反映场地污染程度而避免过度修复产生资源浪费.      

金属有机骨架MIL-68(Al)对水中典型荧光增白剂VBL的吸附去除

以金属有机骨架材料MIL-68(Al)为吸附剂,探究其对水中典型荧光增白剂VBL分子的吸附行为.采用粉末X射线衍射仪(XRD)、傅里叶变换红外光谱(FTIR)、场发射扫描电镜(SEM)及N_2吸附脱附对MIL-68(Al)的结构性质进行表征.探讨了p H值、离子强度、污染物初始浓度、反应温度及吸附时间对MIL-68(Al)吸附去除水中VBL的影响,并对吸附等温线、动力学、热力学及吸附机制进行了分析.实验结果表明,MIL-68(Al)对VBL的吸附能适应较宽的p H范围,吸附等温线符合Langmuir模型,最大吸附容量达到400.02 mg·g~(-1);吸附速率在前20 min很快,并且能在180 min达到吸附平衡,吸附动力学符合准二级动力学模型;吸附过程是吸热反应,吸附自发进行并且主要由熵驱动;静电作用和氢键作用对吸附均有贡献,静电作用是吸附发生的主要机制.由以上结果可知,MIL-68(Al)是一种潜在的高效吸附剂,在去除水中的VBL分子方面极具潜力.     

应用铁铜双金属有机骨架活化过硫酸盐催化剂去除水中有机污染物的研究

基于MIL-101(Fe)的合成方法,首次采用合成前金属掺杂法制备了双金属有机骨架MIL-101(Fe,Cu)催化剂,并利用X射线衍射仪(XRD)、傅里叶变换红外光谱仪(FTIR)、扫描电镜(SEM)和X射线能谱仪(EDS)对催化剂进行表征.同时,以罗丹明B(Rh B)为目标降解物,研究此催化剂催化过硫酸盐降解Rh B的性能,并初步尝试将催化剂应用于邻苯二甲酸二丁酯(DBP)的催化降解.XRD、FTIR、SEM和EDS等分析结果表明,铜离子的掺杂导致MIL-101(Fe)的结构与形貌发生了改变,提高了对污染物的吸附和催化降解作用.相比MIL-101(Fe),在90 min时MIL-101(Fe,Cu)对Rh B的去除率达到95%,在180 min时对DBP的去除率达到68%.此外,分析了催化剂催化性能提高的原因:配位竞争导致铁离子的不饱和趋向;形貌的变化加强了对污染物的吸附作用.     

铜改性MIL-101吸附溶液中碘离子研究

目的提升MIL-101对溶液中放射性碘离子的吸附性能。方法开展铜掺杂改性MIL-101研究。利用SEM,XRD和比表面与孔径分析仪等表征方法对改性前后的材料进行物理性能分析,并考察不同Cu掺杂量、吸附时间和初始碘离子浓度对吸附效果的影响。结果铜改性后吸附率明显增加,掺杂20%的铜时,材料的比表面积最大,吸附效果最佳;吸附速率随时间增大而降低,而吸附率随初始浓度减小而增大。结论铜改性后的MIL-101对溶液中碘离子有更好的吸附效果,其吸附速率和吸附量都有明显的优势。