UiO-66/壳聚糖的制备及其对U(VI)的吸附机制

铀矿开采和冶炼等工艺产生大量低浓度铀废水,危害着生态环境和人类健康,从含铀废水中去除铀(VI)迫在眉睫。本文以UiO-66、壳聚糖(CS)为原料,采用交联法制备UiO-66/CS新型复合材料,通过静态吸附实验,考察不同pH值、吸附剂投加量、吸附时间及铀初始浓度等外部因素对U(VI)去除率的影响。通过SEM、FTIR、XPS等对UiO-66/CS材料进行表征分析,揭示吸附剂去除U(VI)的机制。结果表明：在铀初始浓度为5 mg/L,温度为298 K,p H为5,投加量为0.15 g/L,吸附时间120 min条件下,UiO-66/CS对U(VI)的去除率可达90.24%。吸附过程符合准二级动力学模型和Freundlich等温吸附模型。U(VI)吸附去除机制主要是-NH、-COOH、Zr-O、-OH等官能团与U(VI)发生络合作用。     

聚乙烯亚胺改性磁性酵母复合材料去除铀(VI)的性能

为了高效便捷地处理放射性废水,制备了聚乙烯亚胺(PEI)改性磁性酵母(MY)复合生物材料(MY@SiO₂-PEI),并将其用于铀(VI)的去除。采用SEM、FTIR、Zeta电位及XPS对材料进行表征,运用Visual MINTEQ模拟不同条件下U(VI)形态分布,通过研究不同溶液pH、温度、反应时间、离子强度,阴离子(CO₃2?、PO₄3?)及不同U(VI)初始质量浓度等方面,考察不同因素对MY@SiO₂-PEI吸附U(VI)的性能影响,并对MY@SiO₂-PEI的循环利用能力进行研究。结果表明,MY@SiO₂-PEI对U(VI)的吸附表现出强pH依赖性,离子强度对吸附效果无显著干扰,说明反应主要受表面络合作用控制。FTIR、XPS及Zeta电位分析发现促使U(VI)吸附的主要因素是材料表面不同官能团(N=C、NH(NH₂)、C—N=C)与U(VI)的络合作用及静电吸引作用。MY@SiO₂-PEI最大吸附量可达173.99 mg/g,且吸附在20 min就可达到吸附平衡。准二级动力学和Langmuir等温方程能很好的拟合此吸附过程,且热力学表明吸附过程是自发吸热过程。MY@SiO₂-PEI材料的合成方法简便,去除效果好,再生性佳,是一种很有前途的环境污染治理中放射性核素的吸附剂。      

硅藻土原位生长Nb2O5纳米棒及表面Cr(VI)吸附转化行为研究

以活化铌酸为铌源, 草酸铵为沉积剂, 十二烷基苯磺酸钠为模板剂, 采用水热法在硅藻土表面原位生长Nb₂O₅纳米棒。采用SEM、TEM、XRD、BET、FT-IR和XPS等分析方法对样品进行表征, 反应14 h后, Nb₂O₅纳米棒长度为500~700 nm, 直径为25~35 nm; 硅藻土原位生长Nb₂O₅纳米棒样品比表面积为157 m²/g。研究了样品对Cr(VI)的吸附与光还原行为, 可见光条件下对Cr(VI)吸附量可达220 mg/g; 紫外光条件下, 可将表面吸附的Cr(VI)转变为Cr(III), 样品经过5次循环使用后, 对Cr(VI)(100 mg/L)降解率仍能保持在93%左右。样品可对重金属污染废水中Cr(VI)进行吸附与毒性降解一体化去除。     

羟基磷灰石改性膨润土对铀的吸附效果及其机制

伴随我国核能的开发与高效利用，铀已成为我国地表水、地下水和土壤的常见污染物之一，从含铀废水中去除U(VI)已成为亟需解决的环境问题。本工作以膨润土(BTN)、磷酸氢二钠、硝酸钙为原料，采用简单易行的一步水热法成功制备出羟基磷灰石(HAP)改性膨润土复合材料(HAP/BTN)。考察了HAP/BTN对水溶液中铀的吸附性能，利用单因素试验和正交试验探讨了pH、转速、温度、投加量、时间对吸附性能的影响。试验结果表明，在p H=6.0、转速=100 r·min^-1、室温(298.15 K)、HAP/BTN投加量1 g·L^-1、吸附时间t=30 min时，该吸附材料对10 mg·L^-1含铀废水的去除率可达98%，最大吸附量为186.45 mg·g^-1。吸附过程更符合Langmuir模型和准二级动力学，热力学参数表明HAP/BTN对铀的吸附是自发吸热的过程，结合XPS及XRD的结果证实了HAP/BTN吸附铀主要归因于络合反应、化学吸附、静电吸附和离子交换作用。     

ZIF-8-SiO2的制备及其对U(VI)的吸附

以沸石咪唑酯骨架结构材料ZIF-8及硅酸四乙酯(TEOS)为原料制备ZIF-8-SiO₂复合材料,并采用XRD、SEM、EDS等方法对ZIF-8-SiO₂的结构及吸附U(VI)前后的形貌进行表征,结果表明ZIF-8-SiO₂成功制备且对U(VI)具有良好的吸附作用。以静态吸附实验,分别考察了pH值、时间、温度、溶液初始铀浓度、盐浓度及超高压环境等对ZIF-8-SiO₂吸附性能的影响。由实验结果可得,在初始浓度为80 mg·L?1时,25℃下ZIF-8-SiO₂对U(VI)的最大实际吸附量为498 mg·g?1,根据Langmuir模型拟合结果分析得出,ZIF-8-SiO₂对U(VI)的理论吸附量最高可达678.5 mg·g?1,且在200~500 MPa范围内,压强越高越有利于吸附。通过FTIR、XPS等方法对ZIF-8-SiO₂吸附铀酰离子前后的结构进行分析,探究该吸附过程中可能存在的吸附机制。      

ES@UiO-66-NH2复合材料对水溶液中Pd(Ⅱ)的有效吸附

采用简单的回流法合成了氨基功能化金属有机骨架(UiO-66-NH₂)和环氧基硅胶(ES)的复合材料(ES@UiO-66-NH₂),并将其用于Pd(Ⅱ)的吸附分离研究。通过傅里叶变换红外光谱(FT-IR)、N₂吸附-脱附以及扫描电子显微镜(SEM)等手段进行了表征并揭示其作用机理，表明ES@UiO-66-NH₂对Pd(Ⅱ)的吸附机理为Zr节点的不饱和配位和静电吸引共同作用。结果表明：在pH为3.0,温度为303K的条件下，ES@UiO-66-NH₂对Pd(Ⅱ)的最大吸附量为76.02mg/g,整个吸附过程符合Langmuir模型，而吸附动力学可用准二级动力学模型进行描述。此外，该复合材料具有较好的再生性与重复使用性能。研究结果为回收废水中的Pd(Ⅱ)提供了一种新选择，并在实际工业含Pd(Ⅱ)废水的回收中具有较大的应用潜力。     

三维大孔g-C3N4吸附和光催化还原U(VI)性能研究

将易溶的U(VI)还原为微溶的U(IV)是治理放射性铀污染的有效方法。本研究以SiO₂纳米球作为硬模板, 通过热聚合-刻蚀制备具有连续贯通的三维大孔g-C₃N₄光催化剂, 用于吸附-光催化还原U(VI)。材料表征结果显示: 三维大孔g-C₃N₄比表面积显著增加, 对可见光的吸收明显增强; 同时具有三维有序大孔结构, 并呈规则的紧密堆积结构, 孔壁完整多孔, 整个结构具有良好的三维连通性。吸附实验表明: 三维大孔g-C₃N₄对U(VI)最大吸附容量可达~30.5 mg/g, 该过程更符合Langmuir吸附模型, 与块体g-C₃N₄相比吸附容量提高了~1.83倍。光催化还原实验表明: 三维大孔g-C₃N₄具有高的光催化活性和良好的稳定性, 其还原反应速率常数为~0.0142 min ^-1, 是块体g-C₃N₄ (~0.0024 min ^-1)的~5.9倍。鉴于三维大孔g-C₃N₄具有较优异的吸附-催化还原性能, 该材料有望应用于放射性废水中U(VI)的快速高效清除。     

C@K2Ti6O13分级纳米材料对Cr(VI)的吸附去除

Cr(VI)具有非常大的生物毒性, 去除溶液中的Cr(VI)是当前的一个研究热点。本研究制备了C@K₂Ti₆O₁₃分级纳米材料, 并用不同表征手段对材料的物相和结构等进行表征, 进一步探究了初始pH、吸附时间、离子强度等对C@K₂Ti₆O₁₃复合纳米结构吸附Cr(VI)的影响。实验结果表明C@K₂Ti₆O₁₃复合纳米结构对Cr(VI)有较强的吸附能力, 1 h内去除率能够达到50%以上, 其吸附动力学符合准二级动力学模型, 吸附热力学符合Langmuir等温吸附模型, 表明这种分级纳米材料在环境治理方面应用潜力巨大。     

氨化烟末生物碳吸附剂的制备及其对Cr(Ⅵ)的吸附行为

以卷烟废弃烟末为原材料,对其进行碳化处理后再引入氨基功能团制备氨化烟末生物碳吸附剂(NH₂/TPB),研究p H、投加量、温度、吸附时间对NH₂/TPB吸附Cr(Ⅵ)的影响。通过扫描电镜(SEM)、傅里叶红外光谱(FTIR)、X射线光电子能谱(XPS)等技术进行机制分析。结果表明:初始浓度为210 mg/L、pH=4、投加量为0.8 g/L、温度为45℃、吸附时间为120 min时,NH₂/TPB对Cr(Ⅵ)的最大吸附量为103.627 mg/g。吸附过程符合准二级动力学模型和Langmuir吸附等温模型。Cr(Ⅵ)吸附去除机制主要包括静电相互作用、还原反应以及与-NH₂、-OH、-COOH的配位络合,与Si-O-Si的"π-π"相互作用。通过5次吸附-解吸试验发现,Cr(Ⅵ)去除率在82.88%以上。研究表明氨化烟末生物碳具备处理与修复酸性含Cr(Ⅵ)废水污染的潜力。     

MOFs自牺牲模板法制备CoNx/g-C3N4纳米材料用作高效光催化还原U(VI)

近年来, 利用石墨氮化碳(g-C₃N₄)光催化法将易溶的U(VI)还原为难溶的U(IV)来清除铀, 已逐渐成为放射性核素研究的热点。本研究将一种含金属钴的金属有机框架材料(MOFs)作为自牺牲模板, 利用简单热共聚法成功合成了含有Co-N_x构型的CoN_x/g-C₃N₄催化剂。在固液比为1.0 g/L、pH 5.0、可见光照射45 min下, 制备的催化剂(w(Co-MOFs) : w(g-C₃N₄)=1 : 1)对50 mg/L的U(VI)标准溶液还原率达到100%。从形貌, 微观结构和光学性能等方面对催化剂进行了表征,结果显示, 引入Co有效拓宽了g-C₃N₄对可见光的吸收范围, 抑制了光生电子与空穴的复合, 从而促进了U(VI)的还原反应。此外, 基于捕获实验深入探究了U(VI)在CoN_x/g-C₃N₄材料表面催化可能的反应机理。研究表明, CoN_x/g-C₃N₄复合光催化剂光学性能优异, 制备方法简单且绿色环保, 对放射性废水中的U(VI)的光催化还原去除效果较好。本工作对后续石墨氮化碳类新型材料的设计、合成与实际应用具有一定的参考作用。     

Selective Supercritical Fluid Extraction of Uranium(VI) using N-Phenyl-(1,2-Methano-Fullerene C60)61-Formohydroxamic acid and Simultaneous On-line Determination by Inductively-Coupled Plasma-Mass Spectrometry (ICP-MS)

Uranium(VI) is extracted with N-phenyl-(1,2-methano-fullerene C₆₀)61-formohydroxamic acid, PMFFHA, in dichloromethane by supercritical carbon dioxide (SF-CO₂)-dichloromethane (modifier) medium. A 2.0 µL aqueous uranium is extracted accurately and also preconcentrated in an especially designed extraction vessel of 80 µL capacity. The extracted microdrop orange-red colored uranium(VI)-PMFFHA complex in dichloromethane was online measured by fiber optics spectrometry and ICP-MS. The distribution ratio (D_UO2²⁺) of U(VI) was determined. The slopes of log D_UO2²⁺ versus PMFFHA concentration plot, the extracted species both in SF-CO₂ extraction (SFE) and the solvent extraction (SE) were determined to be 2.0 as UO₂(PMFFHA)₂ complex. The uranium is determined as low as 0.10 ng mL^-1 in presence of several cations and anions. The effect of diluents, modifier concentration, temperature and pressure on the extraction and separation of uranium was studied. The uranium is determined in human blood serum, natural water, seawater, standard samples and also in monazite sand. The PMFFHA has been successfully used as carrier for the selective and efficient transport of uranium(VI). The feed comprised of a solution of uranium(VI) and aqueous solution of diverse cations and anions in pH 4.5, while 1M HNO₃ was used as a stripping agent in the receiving compartment of permeated cell. Maximum transportation was observed for 12 minutes with t_1/2 equal to 6.3 min. The uranium(VI) was determined in presence of uranium(IV).     

锂离子筛前驱体Li4Mn5O12的制备及性能研究

吸附法是目前从低锂浓度的盐湖卤水中提取锂的最有前途的方法。采用EDTA-柠檬酸络合法制备了Li₄Mn₅O₁₂前驱体, 经酸浸脱锂后得到对Li⁺具有特殊选择性的锰氧化物锂离子筛。通过热重、XRD、SEM、FT-IR、化学组成、吸附动力学及共存金属离子的分配系数等手段对样品的晶相结构和Li⁺选择性吸附性能进行了研究。结果表明: 煅烧时间对Li₄Mn₅O₁₂前驱体生成有较大影响, 由400℃煅烧24 h所得的前驱体几乎为纯相的Li₄Mn₅O₁₂化合物, 经酸浸脱锂后的离子筛仍保持着与前驱体相同的尖晶石结构; 前驱体Li₄Mn₅O₁₂和离子筛MnO₂均为 200 nm左右的球状颗粒; 离子筛的最大吸附容量为43.1 mg/g, 并具有较好的Li⁺选择性。     

多技术联用鉴别含铅固体废物

采用X射线荧光光谱、X射线衍射等技术,结合超景深显微镜、扫描电镜等设备,对某含铅样品进行化学成分、物相组成和微观形貌分析,判断是否为固体废物.结果表明:样品主成分为Pb3(CO3)2(OH)2,PbSO4和Na2SO4等,并且含有大量玻璃态的钠钙铝硅酸盐和呈球状、椭球状、串珠状的金属铅和铅铁氧化物.样品中的硫酸铅呈疏松...     

Grape waste as a biosorbent for removing Cr(VI) from aqueous solution

Grape waste generated in wine production is a cellulosic material rich in polyphenolic compounds which exhibits a high affinity for heavy metal ions. An adsorption gel was prepared from grape waste by cross-linking with concentrated sulfuric acid. It was characterized and utilized for the removal of Cr(VI) from synthetic aqueous solution. Adsorption tests were conducted in batch mode to study the effects of pH, contact time and adsorption isotherm of Cr(VI), which followed the Langmuir type adsorption and exhibited a maximum loading capacity of 1.91 mol/kg at pH 4. The adsorption of different metal ions like Cr(VI), Cr(III), Fe(III), Zn(II), Cd(II) and Pb(II) from aqueous solution at different pH values 1-5 has also been investigated. The cross-linked grape waste gel was found to selectively adsorb Cr(VI) over other metal ions tested. The results suggest that cross-linked grape waste gel has high possibility to be used as effective adsorbent for Cr(VI) removal.     

SO2 SCRUBBING BY ULTRAFINE CA(OH)2 AEROSOL

The objective of the present study was to generate submicrometer calcium hydroxide aerosols and to investigate the effectiveness of such aerosols in sulfur capture. The effectiveness of SO₂ removal by Ca(OH)₂ aerosol has been investigated in an isothermal reactor. Ca(OH) ₂ aerosol was generated by a novel fluidizer system in which submicrometer-sized powders were entrained in gases. SO₂ was added to this aerosol to a concentration of 2000 ppm. The aerosol-SO₂ mixture was heated to 550°C-750°C in an isothermal tube reactor. The SO₂ removal efficiency, which varied from 20% to 70%, was determined to be a function of the aerosol concentration, reactor temperature and residence time. The fraction of aerosol reacted was not affected strongly by the aerosol concentration. The reaction kinetics were determined from the experimental data using a simple analytical model in which the rate is first order in both SO₂ and calcium hydroxide aerosol concentrations.     

粉煤灰活性炭处理含铬电镀废水

为了消除电镀废水中的金属离子等的污染,以粉煤灰活性炭为吸附剂、还原剂对含Cr(Ⅵ)的电镀废水进行了处理.考察了活性炭吸附废水中的Cr(Ⅵ)时,溶液的pH值、吸附时间、Cr(Ⅵ)浓度等因素对Cr(Ⅵ)的吸附量及废水中残余Cr(Ⅵ)浓度的影响;同时,还对活性炭的再生条件进行了研究.试验表明:溶液中Cr(Ⅵ)质量浓度为50 mg/L,pH=3,吸附时间1.5 h时,活性炭的吸附性能稳定,Cr(Ⅵ)离子的去除效果最好,经处理的废水Cr(Ⅵ)含量达到国家排放标准.     

Adsorption of Cr(VI) from aqueous solutions by spent activated clay

Adsorption of Cr(VI) onto spent activated clay (SAC), a waste produced from an edible oil refinery company, was investigated for its beneficial use in wastewater treatment. After pressure steam treatment, SAC was used as an adsorbent. The adsorption kinetic data were analyzed and fitted well in a pseudo-first-order equation and the rate of removal was found to speed up with decreasing pH and increasing temperature. Activation energy for the adsorption process was found to be 4.01–5.47 kcal/K mol. The Langmuir adsorption isotherm was used to fit the equilibrium data and the effect of pH, temperature and ionic strength were studied. The maximum adsorption capacities for Cr(VI) ranged from 0.743 to 1.422 mg/g for temperature between 4 and 40 °C under a condition of pH 2.0. The studies conducted show the process of Cr(VI) removal to be spontaneous at high temperature and endothermic in nature. From the waste utilization and environment point of view, the work carried out is important and useful. Results obtained can serve as baseline data for designing a treatment process using this low-cost adsorbent for the treatment of wastewater rich in Cr(VI).