选择性有机可焊保护剂在印制电路板铜金表面选择性沉积机理

通过紫外分析有机可焊保护剂(OSP)膜厚、SEM形貌观察和EDS元素分析等方法研究了不同OSP工艺流程对印制电路板铜金选择性沉积的过程和机理。结果表明:取代苯并咪唑衍生物和1价铜化合物的OSP配合反应需要一定的活化能;2价铜离子、3价铁离子以及苯并咪唑小分子均可以降低该反应的活化能,具有正向催化作用,而锌离子不具备催化OSP反应的能力;利用铁离子的催化特性和不参与成膜的特点可以使OSP在铜、金之间形成选择性,利用苯并咪唑小分子不与金原子络合的特点也可以使OSP在铜、金之间形成选择性;配套预浸前处理的含锌离子OSP体系的选择性显著优于含铁离子OSP体系的选择性;OSP成膜反应不会改变铜表面和金表面的微观形貌。     

高分子负载铁催化剂的制备及其甲苯选择性氯化反应性能

通过金属铁离子与高分子载体进行螯合反应,制备高分子负载铁催化剂,用原子吸收光谱法测定催化剂中Fe3+含量,并利用傅里叶变换红外光谱仪、扫描电子显微镜、热重分析对制备的催化剂分子结构、微球形貌和热稳定性进行表征,并研究有机硫助催化剂的添加对高分子负载铁催化剂催化甲苯选择性氯化性能的影响。结果表明,铁离子与乙酰丙酮基的两个氧原子形成了六元螯合环的强相互作用,使Cl2分子更易极化,提高了催化反应速率;有机硫助催化剂不仅改变Cl—Cl键的强度,而且增大了亲电试剂的空间位阻,从而显著提高对位选择性和稳定性。1%(占甲苯的质量分数)高分子负载铁催化剂/0.05%(占甲苯的质量分数)有机硫助催化剂催化甲苯选择性氯化反应表现出最佳的催化性能,氯化反应2 h,甲苯转化率超过90%,对氯甲苯选择性55.74%,多氯甲苯质量分数低于1%。催化剂可重复使用。     

α,β-不饱和羰基化合物中共轭碳碳双键的有机小分子选择性催化还原

α,β-不饱和羰基化合物的选择性还原具有很重要的应用意义,同时具有很大挑战性,利用有机小分子催化剂、以二氢吡啶酯为氢源可以高化学选择性、高对映选择性地催化还原α,β-不饱和羰基化合物的共轭双键。综述了有机小分子催化剂在α,β-不饱和醛、酮、酯以及串联反应中共轭碳碳双键选择性催化还原的研究进展,总结了每一催化体系的优缺点。     

二氧化硫水溶液在修饰硫化镉粉末上的光催化反应

本文从应用意图出发,采用CdS、混Pt/CdS和镀Pt/CdS三种光催化剂,研究(1)反应温度,(2)催化剂表面含Pt量,(3)修饰方法和催化剂表面结构形貌对光催化SO_2水溶液生成H_2SO_4同时放H_2反应的活性和选择性的影响。结果表明:(1)本反应有明显温度效应,利用太阳能中约占50％的红外段辐射来提高反应温度到70℃可使活性增至7倍,但选择性下降,(2)估算了反应活化能为21kJ·mol~(-1),(3)得出60℃为反应较佳温度,(4)表面含Pt量在5％左右活性最高,(5)混Pt/CdS体系形成高分散、细颗粒分布,其催化活性比镀Pt/CdS体系为高。根据实验结果对反应机理进行了一些讨论。     

2,2,6,6-四甲基哌啶-1-氧自由基在醇氧化研究中的应用

2,2,6,6-四甲基哌啶-1-氧自由基（TEMPO）作为有机小分子,形成的催化醇氧化反应体系相对传统醇氧化具有高效性、高选择性、反应条件温和等优点,可以解决传统醇氧化工艺中反应条件苛刻、成本高以及产生大量污染物的问题,是目前最具前景的醇氧化技术之一。本文综述了近年来关于TEMPO体系在催化醇氧化方面的相关研究进展,重点介绍了均相环境下过渡金属（铜、铁、钌等）参与和无过渡金属参与的TEMPO催化醇氧化,以及多相环境下的固载型TEMPO催化醇氧化,并根据催化反应效率、氧化成本、实际应用性等因素比较总结了均相催化和非均相催化两种类型催化氧化体系的优缺点。指出离子液体与TEMPO的耦合体系、廉价过渡金属掺杂的TEMPO体系和高稳定性碳基材料负载型TEMPO体系是该类型催化剂优化调控的目标与方向。     

乙炔选择性加氢反应催化机理的分子模拟研究

以Pd-Ag合金为活性组分、Al₂O₃为载体的催化剂作为研究对象,运用量子力学理论和Monte Carlo方法对乙炔选择性加氢反应的催化机理进行探索性研究,得到Pd-Ag的分散状况与催化剂活性和选择性之间的关系。结果表明,助催化剂Ag的增加,使乙烯在催化剂表面的脱附能力增强,降低乙烯形成乙烷的可能性,从而增强乙炔加氢的选择性;计算得到在催化剂表面H2解离过程、乙炔以及乙烯加氢反应过程的活化能;乙炔选择性加氢最佳条件为：温度（70～80） ℃,氢气分压（0.03~0.04） MPa     

大连化物所发现“冷冻”铜催化剂可实现选择性加氢产物的调控

正近日,中国科学院大连化学物理研究所在多步催化加氢反应的选择性控制研究方面取得新进展。该团队发现了一种可替代贵金属的铜基加氢催化剂,在加氢反应中表现出与传统铜催化剂完全不同的催化性能。与同族的金和银等贵金属相比,非贵金属铜在催化反应中更易失去外围电子,在氧化或加氢等催化反应中常表现出铜零价和一价共存的化     

限制邻二甲苯催化氧化制苯酐达到高选择性的因素

藉Ｖ２Ｏ５／ＴｉＯ２催化剂,在工业条件下邻二甲苯选择性氧化所得苯酐的选择性不超过７５－８０％,非选择性氧化的机理很少引起兴趣。本文对反应和催化的基本特点评述。注意到在催化剂表面不是高氧化状时,低转化率下形成聚合物状副产物,这导致碳的氧化物生成;但在高转化率下,有可能吸附中间产物,与还原钒基点进行副反应,或者说暴露出钛离子,结果只可能导致氧化碳的生成。     

二氧化铈载金催化剂催化CO氧化的研究进展

将金纳米颗粒负载在二氧化铈上,形成负载型催化剂,能应用于多种反应体系,表现出良好的催化活性,有着广阔的发展前景。综述了二氧化铈载金催化剂在一氧化碳催化氧化中的应用研究进展,介绍了二氧化铈载金催化剂中金的结构、价态和纳米尺寸,载体二氧化铈的形貌、结构、尺寸和氧空位以及金和载体二氧化铈两者之间的相互作用对一氧化碳催化氧化性能的影响。     

负载型纳米金催化剂在乙炔选择性加氢反应中的研究进展

介绍了乙炔选择性加氢制乙烯催化剂的研究和开发进展。针对负载型纳米金催化剂的发展趋势及其对乙炔加氢反应产物中乙烯的独特选择性,重点对比单金属纳米金催化剂及合金型催化剂的催化性能差异,发现合金型纳米金催化剂具有较高的乙炔转化率和稳定性。影响催化性能的主要因素有纳米粒子的大小及活性组分之间的相互协同作用。分析积炭的形成以及导致催化剂失活的原理。展望低温条件下具有高转化率与高稳定性的合金型纳米金催化剂的应用前景。     

Selective Separation of Cu,Zn, and As from Solution by Flotation Techniques

Abstract

The selective precipitation and flotation of copper, zinc, and arsenic ions from dilute aqueous solutions were investigated. Phase separation was accomplished effectively by the dissolved-air technique for the production of fine gas bubbles, and a short-chain xanthate was applied as the collector for copper ions, dialkyldithiocarbamate for zinc, and ferric sulfate for the pentavalent arsenic. The procedures followed were ion flotation for copper and zinc, and adsorbing colloid flotation for arsenic (without a surfactant).     

Silica-Supported Gold Catalyst Modified by Doping with Titania for Cyclohexane Oxidation

Amorphous silica was modified by doping with titania through a surface sol–gel process and applied as the support for depositing gold. These doped silica-supported gold catalysts were tested in the selective cyclohexane oxidation to cyclohexanone and cyclohexanol using oxygen. Under the oxidation conditions of 150 °C, 1.5 MPa and 3 h, a selectivity of 91.7% for cyclohexanone and cyclohexanol could be reached over the gold catalyst, affording a cyclohexane conversion of 8.4% and a turnover frequency up to 40,133 per hour. Moreover, the catalytic activity and selectivity could be well retained in 4 recycling oxidation reactions, showing a high stability of the gold catalyst supported on titania-doped silica.     

Fabrication of palladium coated nanoporous gold film electrode via underpotential deposition and spontaneous metal replacement: A low palladium loading electrode with electrocatalytic activity

An electrochemical approach to nanoporous film-based gold catalyst design using the underpotential deposition and redox replacement technique is presented. The procedure consisted of the underpotential deposition (UPD) of copper on the gold nanoporous film, with subsequent replacement of the copper by palladium at open circuit in a palladium containing solution. The resulting electrode was studied using cyclic voltammetry and scanning electron microscopy. The electrocatalytic activity of as-prepared palladium nanoporous gold film electrodes toward the oxygen reduction reaction is presented.     

An Artificial Supramolecular Nanozyme Based on β-Cyclodextrin-Modified Gold Nanoparticles

An artificial nanozyme model was developed by the supramolecular complexation of a β-cyclodextrin-modified gold nanoparticle and metal catalytic centers. The cyclodextrin-based monolayer was first constructed on the surface of gold nanoparticle by using the thiol modified cyclodextrin, subsequently the cyclodextrin-modified gold nanoparticle was utilized as a backbone to install metal catalytic centers by supramolecular assembly of the copper complex of triethylnetetramine-adamantane and β-cyclodextrin receptors immobilized on the surface of gold nanospheres via hydrophobic interaction. The catalytic behaviors of β-cyclodextrin-modified gold nanoparticles with adjacent multi-metal catalytic centers were investigated as an esterase mimic. Strong hydrolase activities for catalyzing the cleavage of an active ester 4,4′-dinitrodiphenyl carbonate (DNDPC) were observed. A detailed kinetic study on nanozyme-catalyzed hydrolysis of ester DNDPC has been described.     

从糖精废水中提取金属铜及废水综合利用

利用废铁卷与含铜酸性废水作用制备金属铜和聚合硫酸铁,并用聚合硫酸铁作絮凝剂处理酯化废水. 实验结果表明,1 t含铜酸性废水可制得8.5 kg铜粉及230 kg Fe3+浓度为158~160 g/L的聚合硫酸铁,处理后酸性废水中的硫酸含量降低了83.5%, Cu2+含量降低了85.0%. 在优化条件下,沉降30 min,酯化废水的COD及色度去除率分别达到了86.8%和88.5%.     

Catalytic growth of ZnO nanostructures by r.f. magnetron sputtering

The catalytic effect of gold seed particles deposited on a substrate prior to zinc oxide (ZnO) thin film growth by magnetron sputtering was investigated. For this purpose, selected ultra thin gold layers, with thicknesses close to the percolation threshold, are deposited by thermal evaporation in ultra high vacuum (UHV) conditions and subsequently annealed to form gold nanodroplets. The ZnO structures are subsequently deposited by r.f. magnetron sputtering in a UHV chamber, and possible morphological differences between the ZnO grown on top of the substrate and on the gold are investigated. The results indicate a moderate catalytic effect for a deposited gold underlayer of 4 nm, quite close to the gold thin film percolation thickness.     

Treatment of wastewater containing copper,zinc, nickel and cobalt using Duolite ES‐467

Duolite ES‐467 was used to treat wastewater containing heavy metal ions. Sorption experiments were carried out at varying pH values, agitation speeds, reaction times, and metal ion and sorbent concentrations. Each of the parameters affects the sorption behaviour of individual metal ions. Copper sorption was greater compared with other metal ions such as zinc, nickel and cobalt. The presence of other metal ions affects copper sorption. Equilibrium isotherm curves were developed. These were used to predict that the metal ion concentration would be reduced from 100 to less than 1 mg dm^?3. Fixed bed tests were conducted to investigate the efficiency of Duolite ES‐467 for the selective removal of copper ions from multi‐metal solutions. Breakthrough curves were obtained using Duolite ES‐467 for solutions containing copper, nickel and copper, zinc, nickel and cobalt. Elution studies were also carried out using sulfuric acid. © 2002 Society of Chemical Industry     

Ballistic Modification of Composite Modified Double-Base Propellants containing ammonium perchlorate

The effect of certain lead and copper salts of organic acids and metallic oxides was studied on the burning rates and heat of explosion of CMDB propellants containing AP. Among lead and copper salts, basic lead salicylate gave increased burning rates, whereas lead methylene disalicylate and basic copper salicylate did not produce catalytic effect. In the case of metallic oxides, ferric oxide and cobalt oxide gave better catalytic activity than copper and chromium oxides. On crosslinking of nitrocellulose with an isocyanate, catalytic activity of ballistic modifiers was reduced. Burning rates obtained in a rocket motor (2-kg propellant) were higher by about 15%-20% than by strand burner (Crawford Bomb) method.     

Vapour phase oxidation of toluene in V/Al2O3–TiO2 catalytic reactors

The catalytic membrane reactor and the inert packed bed membrane reactor were studied in the vapour phase selective oxidation of toluene. Different feeding policies for the membrane were explored and their influence on the selectivity to the desired products (benzaldehyde and benzoic acid) was investigated. The active phase was prepared by depositing vanadium on a Al₂O₃–TiO₂ support prepared through the sol–gel technique. Higher selectivity to benzaldehyde was obtained using the catalytic membrane reactor. Differences were seen in the catalytic membrane reactor performance only when the active phase was heavily charged along the membrane cross-section.     

多金属复杂硫化铜矿中有价金属的分离研究现状与进展

综述了复杂铜铅硫化矿中铜锌及铅等有价金属的分离回收技术。通过阐述最近的几种处理复杂硫化铜矿的方法,分析和比较了各处理方法的特点,展望了研究趋势。指出:氧化焙烧预处理-浸出法和硫酸化焙烧-水浸法尽管工艺流程短且简单,但焙烧过程产生的SO₂气体对环境污染严重;硫化焙烧-酸浸法能有效降低SO₂气体的排放量,但其焙烧条件苛刻,难以实现工业化;高价铁盐浸出法存在高价铁盐损耗大、再生难的问题;使用氯盐体系直接浸出时还存在Cl^-对设备腐蚀严重等问题;而氧压浸出和微生物浸出虽然也存在一些不足,但在处理复杂硫化铜矿过程中无有害废气产生,环境友好并且硫以单质硫的形式回收,能有效解决硫酸储存难问题,相信其在今后处理复杂多金属硫化矿中具有广阔的发展前景。