紫外吸收光谱法研究ZnO/碳纳米管复合材料催化降解偶氮染料

以Zn(NO₃)₂和酸化多壁碳纳米管为原料采用水热法合成了ZnO/碳纳米管复合材料,产物经X射线粉末衍射(XRD)和透射电子显微镜(TEM)表征,表明六方晶相的ZnO颗粒大小约为28 nm。紫外吸收光谱研究表明, 该复合材料在太阳光照下具有较高的光催化降解偶氮染料的活性。探究了光照时间﹑催化剂用量﹑染料浓度以及不同的染料结构等因素对催化效率的影响,结果表明随光照时间的延长,偶氮染料位于400 nm的特征峰强度逐渐减弱,且偶氮染料的降解呈准一级的反应。该复合材料对三种染料：酸性橙﹑酸性大红﹑酸性嫩黄的溶液都具有较好的降解能力,反应速率分别为0.09,0.28,0.22 mg· L-1·min-1,此光催化降解速率的差异是由于偶氮染料分子中有机官能团的不同所造成。当选用最优条件时,该复合材料可以迅速降解染料,且经过五次循环后,其催化效率仍高于50％。     

南极海洋芳香烃低温降解微生物的拉曼光谱分析

激光镊子拉曼光谱技术可以实现在自然状态下对单个细胞或细胞器较长时间的观察研究.应用激光镊子拉曼光谱技术实时观察南极微生物低温降解芳香烃过程中单个南极细菌的细胞生长和胞内生物大分子的动态变化过程,收集、分析其拉曼光谱,结果发现:单细胞的拉曼光谱反映了其细胞内部的生命物质组成,南极动球菌 NJ41 和希瓦氏菌 NJ49 生...     

红外光谱分析醋酸酯淀粉包膜尿素膜降解特征

采用傅里叶变换红外吸收光谱(FTIR)方法分析醋酸酯淀粉包膜尿素及与生化抑制剂结合的四种肥料在棕壤中膜降解特征,为包膜尿素肥料的应用提供科学依据。分析表明,膜化学成分,分子结构和膜组成没有因加入不同的抑制剂而改变。膜特征峰主要是H-O,—OH,CO2,C=O,—CH2,—CH3,C—O,C—O—H,C—O—C的不对称、对称伸缩振动吸收。在棕壤中,最高峰吸收强度总趋势0>15>30>60>90>120>150>310d,前15d降解相对缓慢。150d大部分膜物质已降解。经过310d,膜主要官能团或分子结构发生了实质性改变,不同抑制剂对膜降解速度没有显著影响。红外吸收光谱完全可以测定与描述醋酸酯淀粉膜降解特征,并可揭示膜降解速度差异。     

GC/MS和GC/FTIR分析细菌降解呋喃丹的产物

采用液体萃取法在不同的降解时期提取了细菌CDS-1(Sphingomonas sp.)降解呋喃丹的产物,经气谱-质谱联用(GC/MS)分析,分离鉴定出呋喃丹的首步代谢产物呋喃酚.通过化合物质谱行为分析,基本确定了分子量为182的未知化合物为2-羟基-3-叔丁醇基-苯酚,并且确定其为呋喃酚的下一步代谢产物.经气-质联用与气谱-傅里叶红外光谱联用(GC/FTIR)分析,确定细菌在降解呋喃丹后期产生的具有刺激性气味的物质的主要成分为藏茴香酮.     

优化条件下过氧化氢降解壳聚糖的光谱学研究

在最佳反应条件下制备过氧化氢对壳聚糖的降解产物,通过测定原料及降解产物(Mw=1 500～166.53 kDa)的氮、碳含量,分析它们的红外光谱、核磁共振碳谱、X射线衍射谱及圆二色谱,考察各产物是否保持其天然结构。结果表明：各降解产物与原料的碳含量,氮含量及脱乙酰度的最大相对偏差分别为2.4%,2.3%与6.9%,且后两者随着反应时间的延长而减小;各降解样品的红外光谱及核磁共振碳谱与原料壳聚糖的相似,说明降解过程几乎不改变原料的化学结构;经相同方法处理过的原料及降解产物在2θ=10.4°和19.8°处均存在X射线衍射峰,在210 nm处均存在一个负的圆二吸收峰,表明产物的固态结构与其在溶液中的构象均没有发生变化。说明在优化的降解条件下过氧化氢氧化降解没有改变壳聚糖的天然结构。     

纳米二氧化钛介孔微球光催化降解水中BPA的机理

描述了两种不同三维二氧化钛介孔球对水悬浮液中BPA的光降解效果,结果发现紫外线照射下两种三维二氧化钛介孔球的光催化效果要优于P25型二氧化钛,且微球孔隙越小,对BPA的降解效果越好;运用HPLC-MS以及HPLC-MS-MS联用技术对降解中间产物进行定性分析,并且对BPA光催化降解机理进行分析。发现在光催化降解过程中形成5种主要的中间产物并对它们的演变过程进行了讨论。根据分析测定得到的降解中间产物,提出了一个关于两种二氧化钛介孔球光催化剂对BPA降解的详细路径。     

灭多威的超声降解研究

研究了灭多威模拟废水在超声作用下的降解反应动力学、降解产物、降解途径、以及影响降解速率的因素等问题.结果表明,灭多威经超声作用35min,可被完全转换为无机物,其降解过程为假一级反应;浓度增加时,降解减慢;Fe     

超声波条件下降解染料废水的工艺条件研究

采用Fenton试剂对模拟染料废水的降解效果进行研究。结果表明,H2O2投加量、Fe2+投加量、pH值条件、超声处理时间的改变对染料废水的处理效果影响很大。对酸性染料:当pH为4.5,30%H2O2投加的体积分数为30mL/L,Fe2+投加的质量浓度为400mg/L,反应时间为40min时为降解反应的最佳操作条件。对碱性染料,正交试验表明当pH为4、30%H2O2投加的体积分数16mL/L、Fe2+投加的质量浓度为300mg/L、反应时间为60min时为降解反应的最佳操作条件,其降解率达98.46%,COD的去除率达到96.7%。     

光助Fenton氧化反应降解染料亮绿SF

研究了光助Fenton氧化反应降解染料亮绿SF。研究内容包括：亮绿SF的紫外-可见吸收光谱曲线、亮绿SF的浓度-吸光度标准曲线、Fe2+的用量试验、H₂O₂的用量试验、初始pH值对降解效果的影响、不同光源对降解效果的影响、引入阳离子交换树脂作为载体固定Fe2+对降解效果的影响。通过研究获得了降解亮绿SF染料溶液的优化实验条件。研究表明,太阳光照能够有效地促进亮绿SF染料的降解脱色,且大大缩短反应时间;在引入阳离子交换树脂后,可增强Fenton氧化反应的活性,降解效果更好。     

光助Fenton催化氧化反应降解孔雀石绿试验研究

研究了光助Fenton催化氧化反应降解染料孔雀石绿。研究的主要内容包括：孔雀石绿的特征波长及吸光度曲线、孔雀石绿的浓度-吸光度标准曲线、初始pH值对降解效果的影响、Fe2+的优化用量试验、H₂O₂的优化用量试验、不同光源对孔雀石绿降解效果的影响、引入阳离子交换树脂作为载体固定Fe2+对降解脱色的影响。通过研究获得了降解孔雀石绿染料溶液的优化实验条件。研究表明,太阳光照能够有效地促进孔雀石绿染料的降解脱色,且大大缩短反应时间;在引入阳离子交换树脂后,可增强Fenton试剂氧化反应的活性,降解效果更好。     

过硫酸盐氧化降解2,4-二硝基甲苯的光谱特征变化解析

随着人类活动不断增加,难降解有机物已成为污染地下水主要物质之一。贫营养、厌氧的地下水环境将加剧难降解有机物的长期风险。2,4-二硝基甲苯(2,4-DNT)作为难降解的硝基苯类物质,对其污染地下水修复治理一直是环境领域的难点和热点问题。目前,零价铁活化过硫酸盐高级氧化技术被用于修复地下水中2,4-DNT,具有较高的效率。为了更好地识别降解过程,一般采用质谱识别氧化降解的中间产物和降解产物以及生成的顺序,但无法有效的识别氧化降解过程中有机物官能团的变化顺序。因此,采用三维荧光技术、傅里叶红外光谱技术以及二维相关分析技术耦合识别过硫酸盐氧化体系中2,4-DNT的光谱变化及官能团转化顺序。结果表明,未出现荧光峰的2,4-DNT降解生成的具有荧光基团的新产物,反应初期荧光产物的生成主要是因苯环上硝基的变化,而苯环未受到破坏。通过对5个区域体积积分可知,随着反应进行苯环破裂,生成不饱和脂肪酸,类富里酸结构的产物不断被降解,而类腐殖质结构的产物后期逐渐被降解,导致区域Ⅱ和区域Ⅳ中积分的荧光强度占比不断增加,后期产物中的2,4-二氨基甲苯(2,4-DAT)含量不断增加,导致体系中的荧光不断增强,其来源于过量的Fe0还原2,4-DNT反应;红外吸收峰主要有3334,2844,2954,2357,2126,1643,1410,1110和700 cm^-1,表明产物中主要官能团有氨基、亚甲基、羧基、酚羟基及烯烃类等,但不同反应阶段的红外吸收峰差异性较小,表明氧化体系中苯环上甲基被氧化为羧基或酚羟基,硝基被还原转化为氨基,苯环破坏生成不饱和脂肪酸和烯烃类结构物质。通过对时间变化过程中水相的FTIR数据进行二维相关分析,发现同步谱图中出现了4个自相关峰,其位置为λ1/λ2=3334/3334,1643/1643,1015/1015和700/700,同时在λ1/λ2=1643/3334,1015/3334,700/3334,1015/1634,700/1634和700/1015处出现6个正相关交叉峰,且峰值均为正值,谱带强度变化方向一致,表明以上4种官能团均随时间变化而生成,转化/降解存在同步性;异步谱出现同步谱中相同位置的5个负相关交叉峰和1个正相关峰。结合同步异步谱交叉相关峰正负关系,可知光谱变化特征次序为:3334>1634>1015>700,故发现随着时间延长,2,4-DNT降解体系中基团出现的先后顺序:氨基>羧基>烯烃类>酚羟基。综上表明降解过程中苯环上的硝基先转化为-NH2,其次苯环上的甲基被氧化为-COOH,酚羟基和烯烃类应该是苯环结构破坏后的碳链转化。相关研究可为过硫酸盐高级氧化降解官能团变化及路径识别提供一定的依据。     

拟除虫菊酯光解产物的红外图谱研究

本文研究了胺菊酯、甲醚菊酯、丙烯菊酯和氯氰菊酯在液相中的光解作用，并用离心薄层层析方法对光解混合物进行了分离。对光解产物的ＦＴＩＲ红外光谱谱图和标样的ＦＴＩＲ红外光谱谱图的研究表明，光解产物的ＦＴＩＲ红外光谱图发生了较大变化，有羟基和环氧化结构产生，即有氧化产物生成；甲醚菊酯和丙烯酯光解产物的元素分析结果与表明产物中氧的含量有明显提高、证实氧参与了拟除虫菊酯的光解过程。     

Study on mechanism of chitosan degradation with hydrodynamic cavitation

Hydrodynamic cavitation is an effective method for chitosan degradation, of which the mechanism directly determines the molecular weight distribution of degradation products. In this study, based on the Monte Carlo simulation and experimental results, the mechanism of chitosan degradation with hydrodynamic cavitation and molecular weight distribution of products were analyzed. The results showed that the algorithm established in the simulation could effectively analyze degradation mechanism and the factors that influenced degradation mechanism and molecular weight distribution of products. The degradation with hydrodynamic cavitation was caused by chemical and mechanical effects, of which the former dominated the degradation process. The outlet and inlet angles and throat length of the cavitator had major and minor influences on the degradation pattern, respectively. The chemical effect led to random cuts resulting in wide distribution of the products, while the mechanical effect led to central cuts resulting in narrow distribution of the products. With more central cuts, the slide-shaped molecular weight distribution curve of degradation products was gradually transferred into a bell-shaped curve. These results provide instructions for researches on the molecular weight distribution of chitosan products degraded with hydrodynamic cavitation.     

GC-MS(n) and LC-MS/MS couplings for the identification of degradation products resulting from the ozonation treatment of Acetochlor

The degradation of the chloracetamide herbicide acetochlor has been studied under simulated ozonation treatment plant conditions. The degradation of acetochlor included the formation of several degradation products that were identified using GC/ion-trap mass spectrometry with EI and CI and HPLC/electrospray-QqTOF mass spectrometry. Thirteen ozonation products of acetochlor have been identified. Ozonation of the deuterated herbicide combined to MS(n) and high-resolution mass measurement allowed effective characterization of the degradation products. At the exception of one of them, the product B (2-chloro-2', ethyl-6', methyl-acetanilide), none of the identified degradation products has been already reported in the literature. Post-ozonation kinetics studies revealed that the concentrations of most degradation products evolved noticeably with time, particularly during the first hours following the ozonation treatment. This raises concerns about the fate of degradation products in the effluents of treatment plants and suggests the need for a better control on these products if their toxicity was demonstrated.     

Streptomyces sp.HJC-D1溶藻过程产物光谱学特征及机理

运用傅里叶红外光谱、三维荧光光谱、透射电镜等技术,研究了溶藻菌株Streptomyces sp.HJC-D1抑制铜绿微囊藻过程中溶解性有机物(DOM)的组成与特性,初步揭示了微生物溶藻机理。结果表明,溶藻菌株发酵液添加量5%(φ)时铜绿微囊藻去除率可达72.6%±5.5%;溶藻产物DOM以类腐殖酸物质为主,平均分子量在1 000Da左右;溶藻过程藻细胞结构遭到明显破坏,推测可能的微生物溶藻机理为:溶藻菌破坏铜绿微囊藻细胞壁,导致藻细胞失活、死亡。     

Sonolysis of chlorobenzene in aqueous solution: organic intermediates

The ultrasonic degradation of 1.72 mM chlorobenzene was investigated. The sonolysis of chlorobenzene followed first-order kinetics. The influence of the pH of the aqueous solution and the effect of the saturating gás, air or argon, was measured. No pH effect was noticed, and saturation with the monoatomic argon accelerated the degradation. Furthermore, the addition of the radical scavenger benzoate demonstrated that no significant degradation took place in the bulk solution. For air-saturated solutions, the following organic degradation products were identified: methane, acetylene, butenyne, butadiyne, benzene, chlorophenols, phenylacetylene and other chlorinated and non-chlorinated monocyclic and dicyclic hydrocarbons. For argon-saturated solutions, the same products were found, except for the chlorophenols. The presence of the chlorophenols in the case of air-saturation only demonstrated the interaction between the radicals formed and oxygen, and no direct degradation by OH. radicals. The kinetics of several organic degradation products and chloride were determined for the sonolysis of air- and argon-saturated solutions.     

Thermooxidative degradation of compositions based on an epoxy oligomer

The work is devoted to studying the nonisothermal thermooxidative degradation of the composition of an epoxy oligomer cured with 4,4-diaminodiphenyl sulfone in a stoichiometric ratio of 30 wt % hardener per 70 wt % oligomer. The relationship between the structure of the composition and the kinetic parameters of the thermooxidation is established. The network structure was varied by changing the temperature and curing time. Specific features of the mechanism and kinetics of the nonisothermal degradation epoxyamine polymer are determined using the thermoanalytical method, namely, differential scanning calorimetry, and analysis of the oxidation products. The composition of the products, the values of the activation energy and preexponential factor for the reactions occurring in the nonisothermal mode at different rates of heating of samples with different structures of the network, showed that their mechanism is controlled by a time-temperature superposition. The rate of heating of the sample determines the participation of bonds of internodal links and network nodes at different stages of the overall process. An increase in the density of the network leads to a decrease in the rate of the thermooxidative degradation of internodal chains and an increase in the rate of decay of network nodes.     

对痕量羊角材料降解产物的表面增强拉曼光谱研究

将一定浓度的硝酸银与柠檬酸三钠混合后,利用微波加热法制备纳米银溶胶,该方法加热速度快、温度分布均匀、反应条件易控制。采用准弹性激光散射技术检测其粒度大小及分布状态的信息,测得其平均粒度为(53.27±2.65)nm,粒度大小集中分布在56 nm左右。然后以之作为表面增强拉曼光谱(SERS)的活性基底,研究测定羊角痕量降解产物的SERS光谱。结果发现,羊角降解产物的表面增强拉曼效应显著,尤其在659,830,850,929,999,1 028,1 280,1 439,1 599 cm-1等多处出现了明显的拉曼振动峰,这些谱峰反映了羊角降解产物的生化成分信息。并且通过对所获得的羊角降解产物SERS信号进行的谱峰归属分析表明,羊角降解产物主要为氨基酸与多肽类物质。运用表面增强拉曼光谱检测角材料的降解产物,获得较高的灵敏度,可测定浓度低至ppm水平的痕量降解产物,本研究表明,SERS可能为羊角等角材料降解产物的检测提供一种快速、直观、准确的新方法。