酸处理活性炭催化水合肼还原硝基苯(英文)

以水合肼为还原剂,采用硝酸、盐酸、硫酸及氮气或氢气氛处理的活性炭为催化剂,考察了其催化硝基苯还原反应性能.结果表明,经化学处理后,活性炭表面形成了各种含氧官能团,它们可引发水合肼分解,并影响硝基苯的吸附.活性炭表面形成的含氧官能团越多,其催化硝基苯还原速率越快.其中经盐酸处理的活性炭表面形成的含氧官能团最多,因而表现出最高的硝基苯还原活性.     

硝基苯在铜电极上的电还原特性研究

应用循环伏安法和线性扫描伏安法研究水溶液中硝基苯在铜电极上的电还原特性及其电还原为苯胺的中间步骤和反应机理.结果表明:铜电极上硝基苯的还原电位在-0.58V和-1.32V左右(vs.SCE),溶液的酸性和碱性均有益于该还原反应的发生;还原过程伴有反应物吸附现象,当硝基苯浓度较大时,还原过程受传质过程控制;随着厌氧程度的提高,还原速率加快.     

碳材料催化硝基苯还原反应

本文对碳材料(主要是碳纳米管)催化硝基苯的还原反应进行了系统研究.通过热重分析、程序升温脱附、透射电子显微镜、物理吸附以及拉曼光谱等表征,发现碳材料表面的含氧官能团在反应中起着重要的作用,而比表面、孔结构、形貌、结构缺陷以及可能存在的铁杂质对反应没有显著影响.羰基的作用非常重要,但是羧基和酸酐对反应不利.除此之外,材料的π电子体系也很关键,因为它可以传递电子,并且利于硝基苯的吸附.硝基苯还原按照直接路径进行,反应过程中生成的中间体亚硝基苯可以迅速转化为苯胺.     

硝基苯的电还原特性研究

采用准稳态极化、循环伏安、线性扫描和恒电位阶跃等测试方法,对Ｈ２ＳＯ４溶液中硝基苯的电还原特性进行研究,评价了硝基苯在Ｃｕ、Ｃｕ－Ｈｇ和Ｃｕ－Ｎｉ电极的电还原反应活性,研究了硝基苯电还原为ＰＡＰ的中间步骤,并对反应机理进行了探讨。结果表明,硝基苯在酸性介质中的电还原反应存在中间步骤,并伴有反应物吸附现象,硝基苯电还原反应受硝基苯及其还原产物在溶液中的液相传质步骤控制．     

暂态电化学表面增强拉曼光谱研究对硝基苯硫酚分子的电化学还原过程

对硝基苯硫酚是表面增强拉曼光谱研究中最常用的探针分子之一,对硝基苯硫酚在电极表面电化学还原反应的研究有助于对芳香族硝基化合物还原机理的认识. 本文应用暂态电化学-表面增强拉曼光谱技术,研究了对硝基苯硫酚在循环伏安和计时电流法过程中的表面增强拉曼光谱. 结果表明,实验实现了完全与电化学检测时间分辨率同步的表面增强拉曼光谱检测,以最快5毫秒的时间分辨率研究了对硝基苯硫酚分子在金电极表面的还原过程. 结果分析推测其此反应过程极快,在5毫秒的时间分辨率下仍难以捕获其中间物种. 本研究为人们更深层次研究和认识硝基苯类化合物电化学还原过程提供了参考和方向.     

氮掺杂碳包覆纳米钴颗粒用于硝基芳烃室温选择性加氢（英文）

通过硝基芳烃选择性加氢能高效地制备芳香胺和环胺,其中芳香胺作为重要的化工中间体应用于多个领域(精细化工、商业产品和聚合物).在加氢反应过程中,硝基的还原伴随着生成一些副产物(如亚硝基和偶氮化合物).同时对于含还原性基团的取代硝基苯,硝基的选择还原也面临着很大的挑战.金属钴是常用的硝基加氢催化剂活性成分,但是由于对反应底物的过度吸附,导致其选择性不高.早期研究发现,氮掺杂碳催化剂能有效吸附硝基基团,从而在硝基苯加氢中表现出一定活性,但对分子氢的活化不足.因此,氮掺杂碳作为吸附材料与钴构建复合催化剂,能够发挥吸附和活化氢的协同作用,从而高效催化硝基苯加氢.基于此,本课题组发展了一种制备方法,可将钴颗粒尺寸限制在10 nm左右,且包覆在氮掺杂碳中,并应用于对硝基苯酚的室温选择性加氢反应中,发现相较于碳负载钴和氮掺杂碳催化剂,所制催化剂在室温下表现出了很好的活性和选择性.在此基础上,本文采用元素分析、X射线光电子能谱(XPS)和拉曼光谱(Raman)等手段对催化剂形貌和结构进行了研究.表征结果表明,保持钴前驱体的量不变,随着氮化碳加入量的增加,催化剂中氮掺杂浓度提高;当氮化碳/钴1时,氮掺杂浓度不变.红外结果表明,与普通碳载体相比,氮掺杂碳对硝基苯有很强的吸附作用,而氮掺杂碳包覆的钴催化剂也表现出同样的结果.通过调节氮的掺杂浓度,一方面可以修饰碳载体的电子结构,增加表面缺陷的浓度,提高与反应底物的相互作用;另一方面可以促进电子由钴颗粒转移至与之相连的氮原子上,因此进一步促进钴颗粒对分子氢的活化作用.该复合结构的催化剂实现了底物吸附和氢活化的协同作用,氮掺杂碳将反应底物吸附在表面,钴颗粒活化氢,随后解离的氢原子与表面吸附物反应,从而实现硝基苯的高效加氢.其中Co@NC-1催化活性最高,并在循环套用10次后,仍维持较高的催化活性,同时对含其它取代基的硝基苯均表现很高的活性和选择性.     

胺化木质素对水中硝基苯吸附性能的研究

含硝基苯的工业废水对环境造成了严重的污染.本文用环氧氯丙烷、乙二胺对碱木质素进行改性制备胺化木质素,详细研究了溶液pH、接触时间、温度、浓度等因素对胺化木质素吸附水溶液中硝基苯性能的影响.结果表明:溶液pH对吸附有较大的影响,吸附的最佳pH为8,胺化木质素对硝基苯吸附3h后达到平衡,与准一级吸附动力学模型有较好的拟合;...     

离子注入钯的钛电极上硝基苯的电化学还原

在室温下将１×１０￣（１７）～５×１０￣（１７）Ｐｄ￣＋·ｃｍ￣（－２）离子注入到钛基体中．通过ＡＥＳ测量了注入电极表面的组成和各元素的浓度－深度分布．用循环伏安法研究硝基苯在碱性溶液中,Ｐｄ／Ｔｉ电极上的电化学过程,结果表明,注钯的钛电极对硝基苯的电化学还原显示高的催化活性．用现场ＥＳＲ与电化学方法联用检测到硝基苯的单电子还原产物硝基苯阴离子自由基,用现场ＵＶ光谱法也检测到硝基苯的电还原产物苯胺．根据实验结果讨论了硝基苯电化学还原的机理．     

镍负载量对邻氯硝基苯加氢制邻氯苯胺Ni/TiO2催化剂性能的影响

 用等体积浸渍法制备了一系列不同镍负载量的负载型Ni/TiO2催化剂,并将其应用于邻氯硝基苯加氢制邻氯苯胺的反应. 采用N2吸附、 X射线衍射、程序升温还原、透射电镜、 H2化学吸附及间歇加压釜式反应器活性评价等方法,考察了镍负载量对Ni/TiO2催化剂的物化性质及邻氯硝基苯加氢反应性能的影响. 结果表明,随着镍负载量的增加, Ni/TiO2催化剂上邻氯硝基苯的转化率逐渐提高; 当镍负载量超过30%时,催化剂的活性和选择性不再明显变化. 当催化剂中镍负载量高于20%时,在温度343 K、 氢压1.0 MPa和催化剂/邻氯硝基苯质量比1/10的条件下反应210 min后,邻氯硝基苯的转化率和邻氯苯胺的选择性均高于99%, 催化剂具有良好的应用前景. 分析表明,影响Ni/TiO2催化剂性能的主要因素为催化剂表面镍晶粒的活性表面积以及载体TiO2与金属镍之间的强相互作用.     

空气中氟代硝基苯类的采集与检测

利用硅胶管采样管富集空气和废气中的氟代硝基苯类化合物,用甲醇解析,结合气相色谱-电子捕获检测器进行分析检测.对采集流速、采集时间、吸附样品总量和硅胶管储放时间等条件进行优化,结果表明:当采集流速低于1.0 L·min-1,采样时间在20～40 min时,硅胶管对总量小于10μg的氟代硝基苯类化合物具有较好的吸附效率.采用超声解析硅胶管,氟代硝基苯类化合物解析率为90%～110%,所得方法的相对标准偏差为0.4%～4.1%,可满足实际分析的需要.     

Copper Corrosion: Comparison between Naturally Aged Papers and Artificially Aged Model Papers

Summary: Copper corrosion on paper works of art is commonly explained by copper ion-catalysed cellulose oxidation, usually reflected by discoloration of pigment and surrounding paper as well as by loss of mechanical strength. In this study, model paper and historic paper samples, both containing copper pigments, were compared using fluorescence labelling of carbonyl groups and subsequent GPC analysis. The historic paper samples did not show any typical sign of copper pigment induced discoloration, but high brittleness. In artificially copper-corroded paper samples the distribution of carbonyl groups in combination with the molecular weight distribution of cellulose clearly indicated the occurrence of oxidative processes. In contrast, only insignificant oxidative damage was detected in the case of the paper fragments from an original work of art, a codex from the 15^th century. Here, mostly degradation by hydrolytic action was revealed. There was no introduction of carbonyl groups into the bulk section of the molecular weight distribution, and the gain in new carbonyl groups corresponded to the number of reducing end groups newly generated by hydrolysis.     

Evaluation of the effect of cleaning on the morphological properties of ancient paper surface

In the conservation field, the original morphology and texture of the paper surface represent an important aspect to be preserved as historical evidence of the papermaking process. The aim of this preliminary research is to evaluate the effects of aqueous (cellulose ethers, rigid gels of Agar and Gellan gum) and not aqueous cleaning treatments (a typical dry cleaning treatment with wishab sponge) on the original surface morphology of late nineteenth century paper. Nineteenth century newspaper paper was chosen because it is strongly affected by cellulose oxidation and depolimerization due to the rough materials (wood pulp) and the papermaking process used at the time and to the environmental conditions (light, humidity, temperature) to which such paper has been subjected. A preliminary characterization of the paper with Herzberg and Phloroglucinol reactives and Fourier Transform infrared Spectroscopy analysis was performed to understand the paper composition and the type of inorganic fillers used. The paper surface microtopography was then measured by contact profilometry to analyze the effects of the cleaning treatments on paper surface roughness. The effects of the cleaning action was qualitatively evaluated by means of stereo microscopy and scanning electron microscopy. Preliminary results suggest that the treatments which are most respectful of the original surface micromorphology of the paper are those based on the use of rigid gels (Agar and Gellan gum), because they determine the smallest variation in the roughness of surface paper, unlike the application of cellulose ethers by brush. This finding was confirmed by statistical analysis of the roughness results by means of ANOVA and Tukey HSD post hoc test.     

超疏水滤纸的制备与应用

对SiO2纳米粒子进行硅烷化改性,再将其修饰到滤纸上,制备出静态水接触角＞150°的超疏水滤纸,对制备条件进行了优化。 用热重分析及扫描电子显微镜对超疏水滤纸表征后发现,二氧化硅纳米粒子在滤纸纤维表面形成一层包裹层,即纳米级粗糙结构,这种结构对滤纸的疏水性具有关键作用。 对滤纸的油水分离性能进行了研究,发现其对非均相体系和高粘度油水混合物具有很好的分离效果。     

Characterization of paper finishes by use of infrared spectroscopy in combination with canonical variate analysis

The finishing process used by the paper industry involves subjecting the paper surface to the action of chemicals and physical treatments in a series of operations intended to provide an end-product suitable for its intended use. In this work, we studied various paper finishes by using infrared spectra processed with appropriate chemometric techniques. To this end, we used a wide range of paper samples supplied in various finishes (coated, offset and cast-coated) by several paper manufacturers. Fourier transform middle-infrared (FTIR) spectra for the paper samples were recorded by using an ATR module, and reflectance near-infrared (NIR) spectra with the aid of a fibre-optic probe. Both techniques are fast and require no sample pretreatment.The primary aim of this work was to develop a new methodology affording the accurate classification and identification of paper finishes in samples other than those used to construct the calibration model. To this end, we used the discriminant chemometric techniques principal component analysis (PCA) and canonical variate analysis (CVA), application of which was followed by that of the k-nearest neighbour algorithm to the samples in the prediction set. This procedure was also used to classify the coated samples into three subgroups. Both FTIR and NIR spectroscopy allowed most of the samples in the prediction sets to be accurately classified and identified.     

Improvement in Tensile Strength and Water Repellency of Paper after Treatment with Methyltrimethoxysilane Oligomer Using Titanium Butoxide as a Catalyst

The improvement in the tensile strength and water repellency of paper after treatment with a 2-propanol solution of a methyltrimethoxysilane (MTMS) oligomer was studied using filter paper. Titanium butoxide introduced in the solution as a catalyst effectively reacted with the MTMS oligomer, and a Si–O–Ti bond was generated inside the paper. The tensile strength of the paper was remarkably improved by this treatment of impregnation and polymerization of the MTMS oligomer. It was speculated that the reaction proceeded by consuming water that existed among the cellulose fibers by hydrogen bonding, because there was little difference in the tensile strength between the paper treated in air and the paper treated in a dry box. The methoxy groups in the MTMS oligomer demonstrated their good ability of making a three-dimensional network, and at the same time, the methyl groups in the oligomer showed their excellent water repellency. As a result, the treated paper had a good tensile strength even under wet conditions.     

Chemical reactive filter paper prepared by radiation-induced graft polymerization—I

Chelating filter papers with chemically bonded amidoxime groups were synthesized by radiation-induced grafting of acrylonitrile onto filter paper (W3) followed by chemical treatment with hydroxylamine. The effect of grafting conditions such as absorbed dose, dose rate, monomer concentration and filter paper thickness on the grafting yield was studied. It was found that the degree of grafting increases with increasing absorbed dose and dose rate, and then tends to level off at high doses. The order of the dependence of the initial grafting rate on the dose is found to be of 0.33. An increasing monomer concentration was accompanied by a significant increase in grafting. At high monomer concentration the initial rate of grafting is fast followed by a slow rate. The rate of grafting is controlled by the filter paper thickness and the diffusion of monomer into the interior of the filter paper. Mechanical properties of the prepared filter paper were improved over the ungrafted paper. The amidoxime filter papers were examined for adsorption of uranium concentration ranging between 10–100 ppm.     

Biodeterioration of Paper: A SEM Study of Fungal Spoilage Reproduced Under Controlled Conditions

Biodeterioration phenomena represent a complex of physical and chemical alteration processes in various materials, such as those constituting the objects that represent our cultural heritage. The biodegradation of paper is conditioned by several variables such as the materials from which cellulose is obtained, the manufacturing processes employed, the occurrence of other affecting substances such as lignin or metallic compounds, and by the environmental conditions in which papers are conserved. In this study, biodeterioration of paper was artificially induced in order to evaluate the role of a range of chemical and physical variables on damage caused by cellulolytic fungi. A variable pressure SEM instrument was used to characterise paper samples with different fibre origins, and alterations obtained in vitro. Two fungal strains, Aspergillus terreus Thom and Chaetomium globosum Kunze, which are cellulolytic species frequently associated with paper spoilage, were used to produce stains with characteristics close to those observable on art objects made from paper. The stains obtained on the different samples of paper were compared at both low and high magnification, in order to visualize the macro- and microscopic characteristics of paper fibres, inorganic constituents, impurities, and the deteriorating agents related to the spoiled areas. During this survey it was observed that single paper characteristics can strongly influence the intensity and the results of the fungal action. For example, the activity of a fungal strain on paper grades containing fibres of the same origin, but with different sizing, led to the formation of profoundly different stains and alterations. Moreover fungal structures, analysed by low vacuum SEM, in areas on paper corresponding to the stains appeared in different physiological states suggesting an important effect of paper constituents on fungal growth and their sporulating ability.     

Relationship between the decrease of degree of polymerisation of cellulose and the loss of groundwood pulp paper mechanical properties during accelerated ageing

During natural ageing, paper undergoes colour changes and becomes brittle. It is mainly due to the degradation of cellulose, the main component of paper fibres. From the viewpoint of conservation/protection of paper-based information carriers, as well as of the utilisation of secondary fibres, knowledge of the impact of a decrease of the degree of polymerisation (DP) of cellulose on mechanical properties of paper becomes of key importance. In this paper, correlations between the decrease of DP of cellulose and the loss of paper folding endurance (FE) using three model samples (pure cellulose, groundwood pulp paper, and degraded groundwood pulp paper) at accelerated ageing were investigated. The existence of such correlations between DP and FE is supported by experimental results; the correlations are linear for pure cellulose and groundwood pulp paper ageing, while exponential correlation was observed in case of degraded groundwood pulp paper. The results indicate that the rate of paper degradation can be evaluated by means of the rate of glycosidic bonds breaking in cellulosic polymer chains both for cellulose and groundwood pulp paper.     

Development of Paper Actuators Based on Carbon-Nanotube-Composite Paper

We propose a unique soft actuator—a paper actuator—based on carbon-nanotube-composite paper (CNT-composite paper), which is a composite of carbon nanotubes (CNTs) and paper. CNT-composite paper has highly efficient properties because of the contained CNTs, such as high electrical conductivity and semiconducting properties. We are considering using CNT-composite paper for various devices. In this study, we successfully developed a paper actuator. We determined the structure of the paper actuator by referencing that of bucky-gel actuators. The actuator operates using the force generated by the movement of ions. In addition to making the paper actuator, we also attempted to improve its performance, using pressure as an index and an electronic scale to measure the pressure. We investigated the optimal dispersant for use in paper actuators, expecting the residual dispersant on the CNT-composite paper to affect the performance differently depending on the type of dispersant. Referring to research on bucky-gel actuators, we also found that the addition of carbon powder to the electrode layers is effective in improving the pressure for paper actuators. We believe that the paper actuator could be used in various situations due to its ease of processing.     

Monitoring of the surface of paper samples exposed to UV light by ATR-FT-IR spectroscopy and use of multivariate control charts

The effect of exposure of paper samples to UV light was monitored by use of ATR-FT-IR spectroscopy and multivariate statistical tools. Three types of paper were tested: common laser-printer paper, newsprint, and thermal fax paper. The samples were first characterised by ATR-FT-IR spectroscopy to determine natural experimental variability. They were then exposed to UV light for 30 h and the effects of the exposure were monitored by use of the same spectroscopic technique. Finally, multivariate statistical tools were applied to the final dataset, coupled with construction of multivariate control charts, to identify the effects of UV light on the sample surfaces.