碳羟基磷灰石除废水中铬(Ⅵ)吸附动力学和热力学研究

利用废弃蛋壳合成碳羟基磷灰石(CHAP)对含铬(Ⅵ)离子废水进行吸附实验研究,考查了溶液的pH值、吸附时间和温度对吸附平衡的影响,并探讨了吸附动力学和热力学行为.结果表明:常温下,吸附时间为30min、pH=3.0、5g/L CHAP对50mg/L的铬(Ⅵ)离子的吸附率达到98.3%以上,CHAP对铬(Ⅵ)离子的吸附机理符合Langmuir和Freundlich方程;准二级动力学模型比准一级动力学模型能更好地描述CHAP对含铬(Ⅵ)离子吸附动力学行为;不同温度下的吸附热力学的吉布斯自由能以及熵变和焓变显示该吸附过程为自发吸热反应.     

凹凸棒黏土负载纳米TiO_2-Fe_3O_4吸附剂的制备及Cr(Ⅵ)的脱除

采用溶胶-凝胶法、一锅反应法制备了负载纳米TiO_2和Fe_3O_4的凹凸棒黏土(TiO_2-Fe_3O_4-ATP)吸附剂,并进行了模拟废水中Cr(Ⅵ)的吸附及脱附性能的研究。通过扫描电子显微镜(SEM)、X射线衍射(XRD)、傅里叶变换红外光谱(FT-IR)和EDS等分析方法对ATP负载纳米TiO_2-Fe_3O_4前后结构进行了表征,考察了物料配比及吸附时间、pH值、温度、投加量和初始质量浓度对Cr(Ⅵ)吸附率的影响。结果表明,吸附剂在Ti元素含量与负载总量的摩尔比为3∶4时吸附效果最佳。当吸附剂质量为0. 6 g,Cr(Ⅵ)离子初始质量浓度小于0. 8 mg/L时,pH=6,温度20℃,吸附剂对Cr(Ⅵ)的吸附率为79. 8%。TiO_2-Fe_3O_4-ATP吸附剂对Cr(Ⅵ)离子吸附满足Freundlich模型。在20～40℃条件下,吸附过程ΔG 0、ΔS=-43. 55 J/(mol·K)、ΔH=-14. 36 k J/mol,表明该吸附是个自发、熵减、放热的过程。吸附过程符合准二级动力学模型,吸附速率控制步骤以表面化学反应为主。TiO_2-Fe_3O_4-ATP吸附剂在循环使用4次后,吸附率仍能达到65%以上。     

氨基功能化纳米Fe3O4磁性高分子吸附剂对废水中Cr(Ⅵ)的吸附研究

采用分散聚合法通过共聚、开环反应,对纳米Fe3O4进行表面功能化修饰,得到富含NH2官能团的纳米磁性高分子复合材料.通过透射电镜(TEM)、振动样品磁强计(VSM)、热重差热分析(TGA)、X射线衍射(XRD)、红外光谱(IR)等对其进行表征,着重研究了其作为吸附剂对Cr(Ⅵ)的吸附性能.结果表明:该吸附剂对Cr(Ⅵ)的吸附能在10 min内达到平衡;废水溶液pH值能显著影响吸附剂对Cr(Ⅵ)的吸附效果,pH为2.5时效果最佳.废水中Cr(VI)的初始浓度、吸附时间、温度等因素对吸附效果均有不同程度的影响.结合相应pH值下Cr(Ⅵ)的形态分布,探讨了这种新型材料对Cr(Ⅵ)的吸附机理.结果表明:其吸附机理及吸附容量与废水中Cr(Ⅵ)的离子形式有关;吸附过程以离子交换与静电引力为主.等温吸附数据符合Langmuir模型,T=308 K pH=2.5,V=40 mL时,吸附剂的饱和吸附容量qm=25.58 mg/g.吸附为吸热过程,焓变△H=8.64 kJ/mol.     

聚苯胺@碳纳米纤维复合材料对放射性核素铀的高效去除

本文通过原位聚合方法成功制备了聚苯胺改性的碳纳米纤维(PANI@CNF)复合材料,并用于水溶液中放射性核素铀(U(VI))的高效去除.扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线衍射(XRD)、傅里叶红外光谱(FTIR)和X射线光电子能谱(XPS)等表征证明所制备的材料具有丰富的官能团和优良的物理化学性质.批实验方法系统研究了周围环境(pH、背景电解液、反应时间和温度)的变化对U(Ⅵ)去除结果的影响.结果表明,pH对于U(Ⅵ)去除影响很大,而离子强度没有影响,表明二者之间的作用机理为内层表面络合.吸附能够在30 min内快速达到平衡,且符合拟二级动力学模型.吸附等温线符合Langmuir等温线,表明U(Ⅵ)的去除是单分子层均匀吸附过程.在pH=5.0和T=298 K时, PANI@CNF对U(Ⅵ)的最大吸附量高达319.4 mg/g,远远高于单纯的CNF(133.9 mg/g). U(Ⅵ)主要与材料表面的含氮和含氧官能团形成了稳定的内层络合物,从而达到高效去除的目的.以上分析表明, PANI@CNF具有快速反应动力学和高效吸附能力,可以作为放射性核素高效去除的潜在储备材料,为我国核废料治理工作提供理论依据.     

NiFe_2O_4/NiO纳米复合材料的制备及电催化水氧化性能

以镍铁水滑石为单一前驱体,通过高温焙烧制备了NiFe_2O_4/NiO纳米复合材料,对该纳米复合材料在碱性介质中电催化水的氧化性能进行了研究.结果表明,相比于化学共沉淀法制备的单独NiFe_2O_4、NiO及其物理混合物NiFe_2O_4+NiO,NiFe_2O_4/NiO纳米复合材料具有更高的电催化水氧化活性和更好的循环稳定性.电流密度为10 m A/cm2时过电位仅为364 m V.     

无载体离子有机共沉淀分离-石墨炉原子吸收光谱法测定海水中铜铅铬镍

以吡咯烷二硫代氨基甲酸铵(APDC)氧化物作为共沉淀剂,建立了无载体离子有机共沉淀分离、石墨炉原子吸收光谱法测定海水中铜、铅、铬、镍的方法。考察了海水样品pH、共沉淀剂APDC和氧化剂H_2O_2的用量、陈化时间等因素对共沉淀分离效果的影响,优化了实验条件。结果证明,在p H4~5的海水样品中,加入4 m L 30 g/L APDC,1 m L H_2O_2,静置60 min,待测元素能与海水基体很好的分离。铜和铬含量在0~20μg/L范围内呈良好的线性关系,线性相关系数R0.999;镍含量在0~30μg/L,铅含量在0~40μg/L范围内呈良好的线性关系,线性相关系数R0.998;检出限分别为0.31,0.30,0.20,0.25μg/L,方法精密度好,加标回收率为88.8%~101.4%。方法可用于海水样品中铅、铜、镍、铬的常规检测。     

聚苯胺/凹凸棒石黏土纳米纤维复合材料对溶液中痕量Cr(Ⅵ)的吸附性能

采用原位聚合法合成了盐酸掺杂聚苯胺/凹凸棒石黏土(PANI/ATP)纳米纤维复合材料.研究了它对含痕量Cr(Ⅵ)废水的吸附,考察了物料配比、投料质量、吸附时间、吸附温度和pH值对其吸附性能的影响.结果表明,复合材料中的物料配比为m(An):m(ATP)=2:1,用暈为0.4 g,50 min时对Cr(Ⅵ)的吸附量达到99.8%,符合Langmuir等温吸附方程.该复合材料充分发挥了有机和无机吸附材料的协同作用,具有成本低、再生性能良好的特点.     

钼酸根阴离子印迹陶瓷膜的制备与吸附性能

以三氧化二铝陶瓷膜为载体,以钼酸根阴离子为模板离子,1-乙烯基咪唑为功能单体,1,6-二溴己烷为交联剂,采用表面印迹和接枝聚合方法制备了能选择性吸附Mo(Ⅵ)的新型印迹陶瓷膜(IIP-PVI/CM).采用红外光谱、X射线光电子能谱、热重分析及扫描电子显微镜等方法对陶瓷膜进行结构表征.研究了pH值对吸附性能的影响,当pH值范围为2~4时,IIP-PVI/CM具有良好吸附能力;动力学和热力学结果表明,IIP-PVI/CM对Mo(Ⅵ)的吸附符合准二级动力学模型和Langmuir吸附模型;当pH=4.0和温度为30℃时,IIP-PVI/CM对Mo(Ⅵ)具有良好选择性,Mo(Ⅵ)对W(Ⅵ)的选择性系数高达7.48;动态吸附结果表明,IIP-PVI/CM对W(Ⅵ)和Mo(Ⅵ)的吸附饱和时间分别为24和47 min,饱和吸附量分别为0.163和0.672 mmol/100 g,动态吸附时IIP-PVI/CM亦具有良好选择性;经9次吸附与解吸后,IIP-PVI/CM对Mo(Ⅵ)吸附容量仍可达到初始值的92%,再生和循环使用性能良好.     

浊点萃取-石英双缝管捕集火焰原子吸收光谱法分析铬价态

在不同pH值的缓冲溶液中,亚硝基苯胲铵盐(铜铁试剂)可与Cr(Ⅵ)及Cr(Ⅲ)络合生成中性疏水络合物,以Triton X-114为萃取剂,浊点萃取分离富集Cr(Ⅵ)及总铬,石英双缝管原子捕集-火焰原子吸收光谱法(STAT-FAAS)测定铬价态.实验对浊点萃取时溶液的pH值、铜铁试剂和Triton X-114的用量、离心分离时间、平衡温度和时间等影响因素进行了研究.结果表明,分别在pH=3.0和6.0的溶液中,40 ℃恒温加热15 min后,离心5 min,Triton X-114浊点萃取Cr(Ⅵ)及总铬的富集倍数达到50倍(100 mL起初样品溶液/2 mL最终测定液).和普通火焰原子吸收光谱法(FAAS)相比,利用石英双缝管原子捕集技术,STAT-FAAS法测定铬的灵敏度提高了近5倍.本方法测定Cr(Ⅵ)及总铬的线性范围分别为0.005～0.5 mg/L和0.01～1.2 mg/L;检出限分别为0.66 μg/L和0.81μg/L.     

聚苯胺/凹凸棒石纳米纤维复合材料对溶液中痕量Cr(VI)的吸附性能

采用原位聚合法合成了盐酸掺杂聚苯胺/凹凸棒石黏土(PANI/ATP)纳米纤维复合材料。 研究了它对含痕量Cr(Ⅵ)废水的吸附,考察了物料配比、投料质量、吸附时间、吸附温度和pH值对其吸附性能的影响。 结果表明,复合材料中的物料配比为m(An)∶m(ATP)=2∶1,用量为0.4 g,50 min时对Cr(Ⅵ)的吸附量达到99.8%,符合Langmuir等温吸附方程。 该复合材料充分发挥了有机和无机吸附材料的协同作用,具有成本低、再生性能良好的特点。     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.