甲醛分子在羟基化TiO2-B(100)面吸附的第一性原理研究

利用第一性原理研究TiO₂-B表面上甲醛分子（HCHO）与氧桥位羟基（BH）、钛顶位羟基（TH）共吸附时羟基基团对HCHO分子吸附的影响.结果表明：这两种羟基的存在对HCHO在清洁和羟化表面形成多种化学吸附构型产生不同影响.与HCHO分子共吸附时，氧桥位羟基弱化HCHO的吸附；而钛顶位羟基强化HCHO的吸附，且在不同面积超胞上均能显著强化其吸附.利用电子结构分析不同吸附的内在机制，为理解HCHO分子与TiO₂基材料表面的相互作用提供新的视角.     

巯基化、钠化和酸化膨润土对Cu2+，Pb2+和Zn2+的吸附性能研究

基于改性膨润土可能存在的优异吸附能力,利用傅里叶变换红外光谱仪和场发射扫描电镜研究分析了巯基化、钠化及酸化三种改性膨润土对Cu2+,Pb2+和Zn2+的等温吸附与竞争吸附实验结果。研究结果表明,在单一重金属离子的等温吸附环境下,巯基化膨润土对Cu2+,Pb2+和Zn2+的吸附能力明显优于其他两种材料,且对Pb2+具有一定的吸附选择性,吸附率达到近100%;在竞争吸附环境下,三种改性膨润土对Cu2+,Pb2+和Zn2+的吸附率都有所下降,但巯基化膨润土仍旧能够保持较好的吸附能力,较其他膨润土的吸附率大约高出10%～40%;三种重金属离子的吸附量均表现为Cu2+＞Pb2+＞Zn2+,这与三种重金属离子的竞争能力、化学亲和力等大小有关;膨润土的巯基改性,步骤简单且吸附重金属的效果好,对膨润土改性及其应用具有重要意义。     

不同形貌锰氧化物对重金属离子吸附的AAS和AFS分析

通过简单的水热法控制性合成了两种不同形貌的锰氧化物(层状OL和隧道状OMS),并考察了这两种材料对几种重金属离子Pb2+,Cu2+,Ni2+,Hg2+的吸附。通过原子吸收光谱(AAS)和原子荧光光谱(AFS)测定吸附前后离子浓度,比较两种材料的吸附性能,以及对不同离子的选择性吸附。实验表明OMS形貌的锰氧化物是一种良好吸附剂,对铅离子具有很好的选择性吸附,两分钟内吸附率达98%。由此可建立一种简单、绿色、高效地去除污水中重金属离子的方法。     

磁性Pb(Ⅱ)表面印迹聚合物(Fe_3O_4/GO-IIP)的制备及谱学表征

吸附法处理含铅废水因其经济性备受关注。开发可回收的专一性Pb(Ⅱ)吸附材料是高效处理含铅废水和实现铅回收的关键。结合氧化石墨烯(GO)的强吸附性、Fe_3O_4的磁性和表面印迹技术,以氧化石墨烯负载四氧化三铁(Fe_3O_4/GO)为载体,硝酸铅为模板离子,甲基丙烯酸(MAA)及水杨醛肟(SALO)为功能单体,乙二醇二甲基丙烯酸酯(EGDMA)为交联剂制备了磁性Pb(Ⅱ)表面印迹材料(Fe_3O_4/GO-IIP),并探讨其重复利用性和对Pb(Ⅱ)的专一性吸附性。结合XRD,SEM,FTIR等谱学方法,对Fe_3O_4/GO-IIP进行表征,并分析其对Pb(Ⅱ)的吸附机理。以Fe_3O_4/GO-IIP作为吸附剂选择性去除水溶液中的Pb(Ⅱ),结果表明,Fe_3O_4/GO-IIP对Pb(Ⅱ)具有很好的亲和性,反应在5min内,对初始浓度10mg·L-1的Pb(NO3)2的去除率达到70%,反应在20min左右达到吸附平衡。准二级吸附动力学和Langmuir吸附等温线能较好的表达其吸附过程。TEM和SEM图谱证明了Fe_3O_4均匀地分散在GO表面,粒径为10~20nm,Fe_3O_4/GO-IIP表面存在Pb(Ⅱ)印迹孔穴,增强其对Pb(Ⅱ)的选择吸附性;在竞争离子[Cd(Ⅱ),Zn(Ⅱ),Cu(Ⅱ)]存在条件下,Fe_3O_4/GO-IIP对目标污染物Pb(Ⅱ)的选择性系数比非印迹吸附材料(NIP)提高2~5倍;XRD和FTIR谱图分别从晶相结构和官能团证明了Fe_3O_4/GO-IIP的成功合成。对制备材料进行磁分离后洗脱再利用,结果表明Fe_3O_4/GO-IIP具有良好的重复利用性。该结果对于含铅废水处理和铅回收具有重要的意义。     

铬蓝黑R负载活性炭对Cr（Ⅲ）和Pb（Ⅱ）的吸附性能

研究了新型吸附材料铬蓝黑R（钙试剂）负载改性的活性炭对样品中Cr（Ⅲ）和Pb（Ⅱ）的固相萃取（SPE）并用电感耦合等离子体-原子发射光谱法（ICP-AES）进行检测.优化了pH值、吸附剂用量、流速等条件以达到定量吸附（≥95％）,同时研究了洗脱剂的最佳洗脱条件以及共存离子干扰等问题.本法测定Cr（Ⅲ）和Pb（Ⅱ）的检出限分别为0.91ng·mL-1和0.65ng·mL-1,将其应用于土壤沉积物、猪肝、黄河水中的Cr（Ⅲ）和Pb（Ⅱ）含量的测定,加标回收率在98％-101％之间;用于测定标准物质中Cr（Ⅲ）和Pb（Ⅱ）的含量,结果与标准物参照值一致.     

电场作用下S修饰C24N24从CO2/N2混合气体中选择性吸附

在燃烧后气体中选择性捕获CO2,对减缓因CO2浓度过高引发的环境问题具有十分重要的意义。本文采用第一性原理计算的方法,研究了外加电场作用下S修饰C24N24富勒烯对CO2的选择性吸附性能。首先研究了S@C24N24的结构和性质,发现其具有良好的稳定性。其次,研究了无电场时S修饰C24N24富勒烯对CO2的吸附行为,发现其吸附为弱的物理吸附。另外,进一步研究了外加电场作用下S@C24N24对CO2的吸附行为。结果表明,结合距离（CO2与S）和CO2的键角（O=C=O）随电场的增大而减小;当电场增加到0.018 au时,物理吸附转变为化学吸附。关闭电场时,化学吸附又转化为物理吸附。此外,即使在相同的电场条件下,S修饰C24N24富勒烯对N2的吸附也为弱的物理吸附。这表明,通过控制外加电场的开/关,S@C24N24可以从CO2/N2混合气体中选择性捕获/释放CO2,可作为选择性捕获CO2的优良候选材料。     

Pb(Ⅱ)印迹磁性复合吸附剂在水溶液中吸附行为的FAAS法分析

以壳聚糖为单体,磁性纳米Fe₃O₄为载体,环氧氯丙烷为交联剂,利用本体聚合法制备的Pb(Ⅱ)印迹磁性复合吸附剂,可实现从水溶液中快速吸附分离Pb(Ⅱ)。印迹和非印迹吸附剂采用FTIR表征, FAAS法分析吸附过程中pH、吸附时间、初始浓度和温度等影响。结果发现,随着溶液pH值的增加, Pb(Ⅱ)-MICA对Pb(Ⅱ)的吸附容量在溶液pH 5~6时达到最大,当吸附时间为120 min, 最大吸附容量为32.48 mg·g-1。吸附剂对Pb(Ⅱ)的Pb2+/Cu2+, Pb2+/Cd2+, Pb2+/Ni2+, Pb2+/Zn2+的相对选择性系数分别是MNICA的28.11, 91.14, 76.54, 33.06倍, 显示出对Pb2+具有良好的吸附选择性。Langmuir等温吸附模型与平衡吸附数据吻合(r2=1,饱和吸附容量为33.87 mg·g-1)。动力学和热力学研究结果表明,吸附过程属于Langmuir型单层吸附,受化学作用控制,是自发、放热、焓驱动的过程。     

干废弃啤酒酵母菌对铅离子的吸附及FTIR分析

以啤酒厂废弃啤酒酵母菌为原料,利用原子吸收光谱(AAS)、扫描电子显微镜/X射线能谱仪(SEM/EDS)、傅里叶红外光谱(FTIR)等手段,研究其对Pb2+的生物吸附规律,并对吸附机理进行了探讨。结果发现实验条件下,啤酒酵母菌对Pb2+的吸附是一个快速过程,实验进行30 min时酵母菌的吸附量为47.6 mg·g-1,吸附效率已达到91.6％,90 min时基本达到吸附平衡,此时酵母菌实验吸附量为48.8 mg·g-1,吸附效率接近94.0％以上。SEM分析发现吸附Pb2+后部分酵母菌出现细胞壁破裂和脱离现象,且认为胞内的溶出物质为酵母菌对Pb2+后期吸附有一定贡献。EDS分析进一步证明Pb2+被吸附到酵母菌细胞上。FTIR分析发现,不同pH和吸附时间红外光谱图均有所差异,特别是羟基、羧基及酰胺的氨基等基团变化显著,认为细胞上的多糖、蛋白质酰胺更多地参与了对Pb2+的化学吸附过程。利用啤酒厂废弃啤酒酵母菌菌体为原料处理工业污水中的Pb2+是一种价格低廉,吸附效果理想的有效途径。     

XAFS研究不同pH下土壤对Pb的吸附

利用X射线吸收精细结构光谱(XAFS)研究了不同初始pH条件下土壤吸附Pb(Ⅱ)的微观结构及吸附机理。表明土壤对Pb(Ⅱ)的吸附以形成Pb4(OH)44+的内圈吸附作用为主,其次为外圈吸附。同时,在吸附Pb(Ⅱ)过程中,Pb(Ⅱ)通过置换作用取代土壤中碳酸钙Ca(Ⅱ)的位置,形成含Pb碳酸钙(PbCaCO3)沉淀。土壤对Pb的吸附随初始pH(6.0~8.5)的增大,第一配位层(Pb—O)半径减小(0.172 7~0.166 6nm),内圈吸附比重加大,表明土壤对Pb(Ⅱ)的吸附机制受初始pH的影响。     

油菜秸秆对水溶液中Pb(Ⅱ)吸附条件优化与机理的研究

探究油菜秸秆髓芯、外壳、籽荚对水溶液中Pb(Ⅱ)的吸附能力及其吸附机理。以水溶液中Pb(Ⅱ)最大去除率为评价指标,采用响应面法Box-Behnken Design实验来分析溶液pH、Pb(Ⅱ)初始浓度、粒径大小、油菜秸秆各部位投加量和时间因素对油菜秸秆吸附Pb(Ⅱ)的影响程度并建立多元回归模型,优化出最佳吸附条件参数组合;应用吸附动力学、等温吸附线模型来拟合油菜秸秆各部位对Pb(Ⅱ)吸附过程,评价其吸附行为;用红外光谱对吸附水溶液中Pb(Ⅱ)前后的油菜秸秆髓芯、外壳、籽荚进行表征,探讨其基团变化情况。结果表明： 水溶液pH与油菜秸秆髓芯、外壳、籽荚的投加量两个因素是影响油菜秸秆对水溶液中Pb(Ⅱ)去除的关键因素。模型回归决定系数分别是R2_髓芯=0.9664,R2_外壳=0.970 1,R2_籽荚=0.964 9,方程拟合较好,模型可用。油菜秸秆髓芯、外壳、籽荚对Pb(Ⅱ)的吸附行为符合二阶动力学方程与Langmuir等温线模型,对水溶液中Pb(Ⅱ)最大吸附量分别为135.14,78.74和90.09 mg·g-1。通过比较油菜秸秆髓芯、外壳、籽荚吸附水溶液中Pb(Ⅱ)前后红外光谱图发现,油菜秸秆各部位基团(羟基、羧基、酰胺等基团)发生了峰波数位移、强度降低的变化,提示这些基团在吸附水溶液Pb(Ⅱ)过程中发挥重要作用。     

Graphene nanocomposites of CdS and ZnS in effective water purification

The present work deals with syntheses of CdS/graphene and ZnS/graphene nanocomposites by hydrothermal reaction of graphene oxide and morpholine-4-carbodithioate complex of Cd and Zn, respectively. The corresponding nanocomposites has been investigated separately as photocatalyst in the decomposition of methylene blue in the presence of UV light and also as adsorbents in the removal of Cd(II) and Pb(II) ions in contaminated water. These studies have established that CdS/graphene and ZnS/graphene are effective photocatalyst as well as effective adsorbents in the removal of Cd(II) and Pb(II) ions to an extent of 97 and 99 % by ZnS/graphene and CdS/graphene nanocomposite, respectively, under 1 g L^?1 of adsorption dose and at pH ~7. Further studies also established Langmuir model befitting for the adsorption of Pb(II) and Cd(II) ions on CdS/graphene and ZnS/graphene, respectively. The presence of interfering ions on extent of Cd(II) and Pb(II) removal has also been reported.     

Hg(II) Selective Complexation by Chromoionophoric Calix[4]arene Derivative

The present article describes an exploration regarding Hg(II) selective complexation behavior of 5,11,17,23-tetrakis[(N,N-dimethylamino)methyl]-25,26,27,28-tetrahydroxycalix[4]arene (4). The binding affinity of 4 toward selected transition metal ions such as Cd(II), Co(II), Cu(II), Hg(II), Ni(II), Pb(II) and Zn(II) have been investigated by UV-visible and fluorescence spectroscopies. From the results it has been noticed that 4 confers a pronounced preference for Hg(II) in complexation phenomenon even in the presence of other metal ions. The results of Job's plot analysis reveal 1:1 host-guest complex formation between Hg(II) and 4. The FT-IR spectroscopy also supports the complexation affinity of 4 for Hg(II).     

Influence of Fe(III) on the Fluorescence of Lysozyme: a Facile and Direct Method for Sensitive and Selective Sensing of Fe(III)

Lysozyme is widely used for the synthesis of nanomaterials (e.g., gold nanoparticle) to fluorescently sense metal ions. However, the effect of metal ions on the fluorescence of lysozyme is not studied yet. Herein, we have explored the interactions of lysozyme with different metal ions to develop a direct sensing platform for Fe(III). It has been observed that the fluorescence of lysozyme was slightly decreased in the presence of Cu(II), Hg(II), As(V), Co(II), Cd(II), Cr(II), Fe(II), Mn(II), Pb(II), and Zn(II), while a significant decrease in the lysozyme fluorescence was observed for Fe(III). The effect of thermal stability on the fluorescence quenching was also studied from 25 to 60 °C. In the present study, the lysozyme sensing probe was able to selectively and accurately detect 0.5–50 ppm of Fe(III) with a LOD of 0.1 ppm (1.8 µM) at 25 °C.

     

A Highly Selective Turn-On Fluorescent Chemosensor for Zinc Ion in Aqueous Media

In the paper, a novel rhodamine6G based fluorescent chemosensor bearing 3-carbaldehyde chromone was designed and synthesized. According to the fluorescence behavior toward several metal ions, it showed highly selectivity and sensitivity to Zn(II) over other commonly coexistent metal ions (Cu(II), Cd(II), Hg(II), Mg(II), K(I), Pb(II), Fe(III) and Cr(III)) in aqueous environment (pH?=?7.4). Meanwhile the binding constant between Zn(II) and chemosensor achieved 6.21?×?10¹¹ M^?1 in aqueous media. Moreover, according to the Job plot, 1:1 stoichiometry between Zn(II) and sensor was deduced in aqueous media (pH?=?7.4). The good selectivity and sensitivity in aqueous media effectively enhanced the application value of the fluorescent chemosensor for Zn(II).     

Adsorption competition study between chromate and phosphate from their solutions by total reflection X ray fluorescence spectrometry

This paper explores the application of Total Reflection X‐Ray Fluorescence (TXRF) spectrometry for chromate (CrO₄^2?) and phosphate (PO₄^3?) determinations in synthetic solutions after their adsorption onto dolomite. The competition between both contaminants is also evaluated. Adsorption processes are considered an inexpensive, non‐contaminating alternative for retaining, on a selected substrate, a variety of pollutants present in different effluents. For a specific adsorbent, an important factor to be taking into account is the competition among different possible species. Variables such as concentration, temperature, ionic strength and pH were evaluated. Dolomite, a natural mineral based on calcium and magnesium carbonates, was employed as adsorbent. TXRF is an efficient, fast trace element analytical technique and requires only minimum specimen preparation, for that reason is suitable for this study. The experiments were carried out in batch systems; pH and ionic strength of the solution were measured and controlled. The results obtained in individual systems (phosphate‐dolomite or chromate‐dolomite) indicate a 70.5% for phosphate and 22.7% for chromate removal. The adjustment of the ionic strength had no influence on the removal of the anions. According to this study, the adsorption of chromate was reduced to 14% when the pH increased; this fact did not affect phosphate removal. The removal of both ions increased at pH under than 6. The presence of both ions at different concentrations did not change the removal value for the phosphate, whereas the removal of chromate was almost null, indicating a strong interference of the phosphate in the removal of chromate.     

Evaluation of cerium doped tin oxide nanoparticles as a sensitive sensor for selective detection and extraction of cobalt

Chemo-sensor technology demands to design a single, preconcentrator based sensing system having higher sensitivity, sufficient selectivity and efficient removal of metal ions with simple operating and recognition methodology. Here we effectively deliberated Ce doped SnO₂ nanoparticles based sensing system which can be exploited for the recognition and extraction of Co(II) ions in a single step by strong interaction between Ce doped SnO₂ nanoparticles and Co(II). The sensing ability of Ce doped SnO₂ nanoparticles were deliberated for a selective removal of cobalt using inductively coupled plasma-optical emission spectrometry. The sensing ability of Ce doped SnO₂ is studied for various metal ions, such as Cd(II), Co(II), Cr(III), Cu(II), Fe(III), Ni(II) and Zn(II) but the designed sensor was most selective toward Co(II) which was 5000 time more sensitive to Co(II) rather than different interfering metal ions. In addition, the desorption study for regeneration of Ce doped SnO₂ nanoparticles was carried out. This novel approach provides a new route for simultaneous detection and removal of Co(II) in a single step and can be a time and cost alternative tool for environmental safety.     

光度法研究聚乙二醇-硫酸铵-邻苯三酚红体系中铋(Ⅲ), 铁(Ⅲ), 铜(Ⅱ), 镍(Ⅱ), 钴(Ⅱ), 铅(Ⅱ)的萃取分离

本文研究了在聚乙二醇(PEG)-硫酸铵[(NH_4)_2SO_4]-邻苯三酚红(PR)体系中Bi(Ⅲ),Fe(Ⅲ),Cu(Ⅱ),Ni(Ⅱ),Co(Ⅱ),Pb(Ⅱ)的萃取行为。实验结果表明,Bi(Ⅲ)在pH3.5～6.5及Fe(Ⅲ)在pH4.0～7.0范围内可以被PEG相几乎完全萃取,而Cu(Ⅱ),Co(Ⅱ)在pH1.0～7.0,Pb(Ⅱ)在pH2.0～7.0,Ni(Ⅱ)在pH1.0～4.5则不被萃取。从而实现了将Bi(Ⅲ)(pH3.5),Fe(Ⅲ)(pH5.0)与Cu(Ⅱ),Co(Ⅱ),Pb(Ⅱ),Ni(Ⅱ)混合离子的定量分离。同时探讨了PEG相的萃取机理。     

Bifunctional Calix[4]arene Sensor for Pb(II) and Cr2O7 2− Ions

A readily available chromionophore 5,11,17,23-tetra-tert-butyl-25,27-bis(hydrazidecarbonylmethoxy)-26,28-dihydroxycalix[4]arene (HCC4) was employed as a chromogenic sensing probe selective for Pb(II) and Cr₂O₇ ^2? ions among a series of various ions such as Li(I), Na(I), K(I), Rb(I), Ba(II), Sr(II), Al(III), Cd(II), Co(II), Cu(II), Hg(II), Ni(II), Pb(II) and Zn(II) as well as Cr₂O₇ ^2?, CH₃CO₂ ^?, Br^?, Cl^?, F^?, I^?, ClO₄ ^? and NO₃ ^? that have been examined by UV-visible and fluorescence spectroscopic techniques. The HCC4 in DCM-MeCN system forms 2:1 (ligand-metal) complex with Pb(II). It also shows 2:1 stoichiometry with Cr₂O₇ ^2?. The complexation phenomenon has been confirmed by FTIR spectroscopy that favors the selective nature of HCC4 with Pb(II) and Cr₂O₇ ^2?. Thermal gravimetric analysis (TGA) also supports its utility in drastic conditions.     

Ultrasound-assisted adsorption of copper(II) ions on hazelnut shell activated carbon

The present study was aimed to removal of Cu(II) ions from aqueous solution by ultrasound-assisted adsorption onto the granular activated carbon obtained from hazelnut shells. The attention was focused on modeling the equilibrium and kinetics of Cu(II) adsorption onto the granular activated carbon. The granular activated carbon was prepared from ground dried hazelnut shells by simultaneous carbonization and activation by water steam at 950 °C for 2 h. Adsorption isotherm data were better fitted by the Langmuir model than the Freundlich model in both the absence and the presence of ultrasound. The maximum adsorption capacity of the adsorbent for Cu(II), calculated from the Langmuir isotherms, in the presence of ultrasound (3.77 mmol/g) is greater than that in the absence of ultrasound (3.14 mmol/g). The adsorption process in the absence and the presence of ultrasound obeyed to the pseudo second-order kinetics. The removal of Cu(II) ions was higher in the presence of ultrasound than in its absence, but ultrasound reduced the rate constant. The intraparticular diffusion model indicated that adsorption of Cu(II) ions on the granular activated carbon was diffusion controlled as well as that ultrasound promoted intraparticular diffusion.     

Poly (3,4-ethylenedioxythiophene): polystyrene sulfonate (PEDOT:PSS) Zr(IV) phosphate composite cation exchanger : sol-gel synthesis and physicochemical characterization

An organic-inorganic composite cation exchanger poly (3,4-ethylenedioxythiophene): polystyrene sulfonate (PEDOT:PSS) Zr(IV) phosphate was prepared by the sol-gel method for removal of cadmium, a toxic heavy metal pollutant causing adverse effects on human health. The synthesized material was characterized by various techniques such as thermo gravimetric analysis/differential thermal analysis/differential thermo gravimetry (TGA/DTA/DTG), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray powder diffraction (XRD), and Fourier transform infrared spectroscopy (FT-IR). Organic polymer PEDOT:PSS binds with the inorganic counterpart and prevents the leaching of the inorganic parts, hence PEDOT:PSS Zr(IV) phosphate composite cation exchanger has improved ion exchange capacity than inorganic ion exchanger. The composite cation exchanger was found selective towards Cd(II) ions. The nature and composition of contacting solvents influence the selectivity of composite cation exchanger. The composite cation exchanger may be used for the removal of cadmium a toxic heavy metal ion.