柴油车氧化催化技术研究进展

 柴油车氧化催化剂(DOC)主要作用在于氧化尾气中的CO、碳氢化合物(HC)和NOx;此外,氧化过程产生一定的热量,有助于下游组分的起燃。本文综述了近年来柴油车氧化催化技术的研究进展。柴油车氧化催化器由壳体、减振层、载体及催化剂四部分构成,其中催化剂是整个催化器的核心部分,决定着DOC的主要性能指标。DOC常用的活性组分有铂、铑和钯等贵金属,助剂为铈、镧等稀土元素和铜、铁、铬、锰等过渡金属,以及碱金属和碱土金属氧化物。本文论述了柴油车氧化催化技术反应过程原理,包括CO氧化、HC氧化和NO_x氧化反应机理;对柴油车氧化催化剂的失活机制包括热失活和化学失活及再生机制进行了综述;最后对柴油车氧化催化技术的发展进行了展望。     

Research advances in the catalysts for the selective oxidation of ethane to aldehydes

Selective oxidation of ethane to aldehydes is one of the most difficult processes in the catalysis researches of low alkanes. The development of selective oxidation of ethane to aldehydes (formaldehyde, acetaldehyde and acrolein) is discussed. The latest progress of the catalysts, including bulk or supported metal oxide catalysts, highly dispersed and isolated active sites catalysts, and the photo-catalytic ethaneoxidation catalysts, partial oxidation of ethane in the gas phase, and the proposed reaction pathways from ethane to aldehydes are involved.     

透镜状砂岩体油藏成藏运移机理

油藏开发与成藏运移都具有借助流体传递能量建立动态平衡的特征,二者具有动态相似性.作者运用油藏开发中的毛管压力曲线对透镜状砂岩体油藏成藏运移的机理给予了合理解释,并分别对透镜状砂岩体油藏烃源岩的幕式排烃机理和砂岩体阶段式充注机理进行了系统阐述.透镜状砂岩体油藏成藏运移过程中幕式排烃和阶段式充注是相对独立的两个过程,只有当二者协调一致时,才能完成透镜状砂岩体油藏成藏过程.     

铈部分取代镧的La—Mn系钙钛矿型催化剂性能研究

采用共沉淀法制得了Ｃｅ＾４＋部分取代Ｌａ＾３＋的Ｌａ１０ｘＣｅｘＭｎＯ３钙钛矿型催化剂，结果表明，随Ｃｅ＋＋取代量ｘ的增加，Ｌａ１－ｘＣｅｘＭｎＯ３催化剂越易还原，其还原活化能逐渐降低，对ＣＯ、ＣＨ４氧化反应其活性有一最佳值，对ＣＯ反应ｘ为０．４；对ＣＨ４反应ｘ为０．２，这是由于随ｘ的增大，催化剂晶格缺陷增多，晶格氧的化学势增大而造成的。     

均苯三甲酸合成条件的研究

以均三甲苯为原料制取均苯三甲酸，其产率偏低一直是困扰合成者的问题．作者分别从温度、酸碱性、溶剂和催化剂等影响因素出发，对实验条件进行了较全面的探索，得到了有规律性的结论，寻找到了提高产率的较好途径，并对这些影响因素进行了深入讨论．     

Equilibrating metal-oxide cluster ensembles for oxidation reactions using oxygen in water.

Although many enzymes can readily and selectively use oxygen in water-the most familiar and attractive of all oxidants and solvents, respectively-the design of synthetic catalysts for selective water-based oxidation processes utilizing molecular oxygen remains a daunting task. Particularly problematic is the fact that oxidation of substrates by O2 involves radical chemistry, which is intrinsically non-selective and difficult to control. In addition, metallo-organic catalysts are inherently susceptible to degradation by oxygen-based radicals, while their transition-metal-ion active sites often react with water to give insoluble, and thus inactive, oxides or hydroxides. Furthermore, pH control is often required to avoid acid or base degradation of organic substrates or products. Unlike metallo-organic catalysts, polyoxometalate anions are oxidatively stable and are reversible oxidants for use with O2 (refs 8,9,10). Here we show how thermodynamically controlled self-assembly of an equilibrated ensemble of polyoxometalates, with the heteropolytungstate anion [AIVVW11O40]6- as its main component, imparts both stability in water and internal pH-management. Designed to operate at near-neutral pH, this system facilitates a two-step O2-based process for the selective delignification of wood (lignocellulose) fibres. By directly monitoring the central Al atom, we show that equilibration reactions typical of polyoxometalate anions keep the pH of the system near 7 during both process steps.     

Carbon-heteroatom bond formation catalysed by organometallic complexes

At one time the synthetic chemist's last resort, reactions catalysed by transition metals are now the preferred method for synthesizing many types of organic molecule. A recent success in this type of catalysis is the discovery of reactions that form bonds between carbon and heteroatoms (such as nitrogen, oxygen, sulphur, silicon and boron) via complexes of transition metals with amides, alkoxides, thiolates, silyl groups or boryl groups. The development of these catalytic processes has been supported by the discovery of new elementary reactions that occur at metal-heteroatom bonds and by the identification of factors that control these reactions. Together, these findings have led to new synthetic processes that are in daily use and have formed a foundation for the development of processes that are likely to be central to synthetic chemistry in the future.     

Crystal structure of a membrane-bound metalloenzyme that catalyses the biological oxidation of methane

Particulate methane monooxygenase (pMMO) is an integral membrane metalloenzyme that catalyses the conversion of methane to methanol. Knowledge of how pMMO performs this extremely challenging chemistry may have an impact on the use of methane as an alternative energy source by facilitating the development of new synthetic catalysts. We have determined the structure of pMMO from the methanotroph Methylococcus capsulatus (Bath) to a resolution of 2.8 A. The enzyme is a trimer with an alpha3beta3gamma3 polypeptide arrangement. Two metal centres, modelled as mononuclear copper and dinuclear copper, are located in soluble regions of each pmoB subunit, which resembles cytochrome c oxidase subunit II. A third metal centre, occupied by zinc in the crystal, is located within the membrane. The structure provides new insight into the molecular details of biological methane oxidation.     

氮化合物对饱和烃氧化性能的影响

采用液相氧化法和循环动态吸氧法研究了喹啉及吲哚对饱和烃氧化性能的影响。循环动态吸氧实验结果表明 ,低氮浓度的氮化合物能促进饱和烃的氧化 ,高氮浓度的氮化合物能提高饱和烃氧化的诱导期。但在诱导期的前后阶段内 ,氮化合物对饱和烃氧化的影响程度不一致。液相氧化实验结果表明 ,催化剂的形态也是影响饱和烃氧化的重要因素 ,吲哚与金属铜具有协同促进饱和烃氧化的作用 ,而吲哚与环烷酸铜则有很好的抑制饱和烃氧化的效果。当有硫化合物共存且硫氮原子比不同时 ,喹啉和甲基苄基硫醚分别是影响饱和烃氧化最显著的因素。所以氮化合物对饱和烃氧化的作用受氮化合物浓度、氧化反应时间、催化剂的形态及硫、氮之间的相互作用等复杂因素的影响     

水处理高级氧化技术研究进展

随着水污染问题的日益严重,可以产生大量自由基的高级氧化技术(AOPs)得到了越来越多人们的关注。对Fenton氧化法、臭氧氧化法、湿式氧化法、光催化氧化法、超临界水氧化法、超声波氧化法及过硫酸盐氧化法在废水领域的研究现状与发展进行了详细介绍。如何产生更多的羟基自由基(·OH)是AOPs应着手解决的首要问题。研究成本低廉、氧化效率良好的氧化剂和催化性能优异、稳定的催化剂以及高级氧化联合技术的开发是未来AOPs的主要发展趋势。     

高分子类卟啉金属配合物催化活化分子氧研究

综述了近年来高分子类卟啉金属配合物催化活化分子氧的研究,如平面型聚金属卟啉络合物,高分子担载２,２’－联吡啶金属络全物、高分子担载邻菲罗啉金属络合物、高分子担载希夫碱金属络合物及高分子担载单杂环金属络合物等在催化分子氧氧化烷基苯、环己烯、长链烯烃反应中的应用。     

含铌硅磷铝双功能分子筛催化剂的合成及结构表征

合成了铁磷铝(FeAPO-5)、铁硅磷铝(FeSAPO-5)和铌铁硅磷铝(NbFeSAPO-5)分子筛催化剂,并采用XRD、红外光谱和固体魔角旋转核磁共振等方法对合成的催化剂进行了结构表征。结果表明:合成的分子筛具有AlPO4-5的骨架结构,并且铁、硅和铌金属杂原子进入了分子筛骨架。以丙酮醛和甲醇作为合成丙酮酸甲酯的原料,考察了NbFeSAPO-5分子筛催化剂的催化氧化及催化酯化性能,结果表明铁元素进入分子筛骨架使催化剂具有良好的催化氧化性能,而硅和铌的引入提高了分子筛的酸性和催化酯化性能,使NbFeSAPO-5分子筛催化剂成为同时具有催化氧化和催化酯化性能的双功能催化剂。     

在自制钒催化剂上SO_2氧化反应动力学模型的识别——(一)机理模型方程的推导

SO_2在钒催化剂上的氧化反应机理,至今仍未有定论。为了应用,各作者提出适应不同钒催化剂的动力学模型。数年来,我们用云南硅藻土作载体研制钒催化剂,为对其催化反应特征有所了解,采用Yang—Hougen方法,推导出四个机理模型的13个反应动力学方程,作为与实验数据拟合的竞争模型,以建立所研制的钒催化剂的动力学方程,供工艺条件选择和反应器设计参考,本文仅报道模型方程的推导,后文再报道识别结果,以求系统。     

Tunable gold catalysts for selective hydrocarbon oxidation under mild conditions

Oxidation is an important method for the synthesis of chemical intermediates in the manufacture of high-tonnage commodities, high-value fine chemicals, agrochemicals and pharmaceuticals: but oxidations are often inefficient. The introduction of catalytic systems using oxygen from air is preferred for 'green' processing. Gold catalysis is now showing potential in selective redox processes, particularly for alcohol oxidation and the direct synthesis of hydrogen peroxide. However, a major challenge that persists is the synthesis of an epoxide by the direct electrophilic addition of oxygen to an alkene. Although ethene is epoxidized efficiently using molecular oxygen with silver catalysts in a large-scale industrial process, this is unique because higher alkenes can only be effectively epoxidized using hydrogen peroxide, hydroperoxides or stoichiometric oxygen donors. Here we show that nanocrystalline gold catalysts can provide tunable active catalysts for the oxidation of alkenes using air, with exceptionally high selectivity to partial oxidation products ( approximately 98%) and significant conversions. Our finding significantly extends the discovery by Haruta that nanocrystalline gold can epoxidize alkenes when hydrogen is used to activate the molecular oxygen; in our case, no sacrificial reductant is needed. We anticipate that our finding will initiate attempts to understand more fully the mechanism of oxygen activation at gold surfaces, which might lead to commercial exploitation of the high redox activity of gold nanocrystals.     

分子水氧化催化剂及其光电催化分解水研究进展

 总结了近年来基于不同第一过渡系列金属的分子水氧化催化剂，包括贵金属分子水氧化催化剂和非金属分子水氧化催化剂；以及常用的氧化物半导体电极材料，例如α-Fe₂O₃、WO₃和BiVO₄等。概述了目前分子水氧化催化剂在电极表面的负载方式，包括物理吸附方式、共价键结合方式、分子催化剂修饰吸附基团方式、静电作用和π-π堆积作用等。提出构建高效稳定的光致水分解分子器件需要解决的问题，从而实现利用太阳能大规模裂解水制备清洁能源的设想。     

分子水氧化催化剂及其光电催化分解水研究进展

 总结了近年来基于不同第一过渡系列金属的分子水氧化催化剂，包括贵金属分子水氧化催化剂和非金属分子水氧化催化剂；以及常用的氧化物半导体电极材料，例如α-Fe₂O₃、WO₃和BiVO₄等。概述了目前分子水氧化催化剂在电极表面的负载方式，包括物理吸附方式、共价键结合方式、分子催化剂修饰吸附基团方式、静电作用和π-π堆积作用等。提出构建高效稳定的光致水分解分子器件需要解决的问题，从而实现利用太阳能大规模裂解水制备清洁能源的设想。     

溶胶-凝胶法制备CuMn2O4催化剂及性能研究

采用溶胶-凝胶技术,在不同络合剂体系中制备CuMn2O4催化剂,用XRD、BET法、TPR、二甲苯完全氧化等手段研究了催化剂的晶相、还原性能及催化活性.结果表明加入络合剂对提高催化剂比表面积,降低晶粒尺寸至纳米量级有明显作用,对二甲苯的催化氧化表现出优良的反应活性.     

高分子无机锡配合物催化环己酮Baeyer—Villiger氧化性能研究

将聚酰胺一胺树状分子的一到三代通过固相合成担载于纤维素上,分别用2,4-二羟基苯甲醛和邻羟基苯甲醛对其外围的氨基进行了修饰,再与SnCl2·2H2O反应形成两类树状大分子金属锡配合物．用ICP、IR和XPS对此类配合物的结构进行了表征．将此类配合物用于30％双氧水氧化环己酮的Baeyer-Villiger（B-V）反应的非均相催化剂,研究表明,在此类配合物作用下,环己酮高选择性地转化为ε-己内酯．比较不同配体修饰的催化剂作用下的氧化反应情况,发现配体对金属的担载量和催化活性均有不同程度的影响．此类催化剂以天然高分子纤维素为载体,具有原料来源丰富、制备方法简单、催化反应时间短、可重复利用等特点．     

Platinum-supported mesoporous carbon (Pt/CMK-3) as anodic catalyst for direct methanol fuel cell applications: The effect of preparation and deposition methods

Platinum-supported ordered mesoporous carbon catalysts were prepared employing colloidal platinum reduced by four different reducing agents, viz., paraformaldehyde, sodium borohydride, ethylene glycol and hydrogen, and deposited over ordered mesoporous carbon (CMK-3) synthesized by silica hard template (SBA-15). The resulting platinum nanoparticles supported mesoporous carbon, designated as Pt/CMK-3, catalysts were tested for the electocatalytic oxidation of methanol. The effect of the various reduction methods on the influence of particle size vis- a-vis on the electrocatalytic effect is investigated. All the catalysts were systematically characterized by XRD, BET and TEM. The results of the synthetic methods, characterization techniques and the electrocatalytic performance indicate that the Pt/CMK-3 catalysts are superior to that prepared with activated carbon (Pt/AC) as well as with that of the commercial platinumsupported carbon catalyst (Pt/E-TEK). In particular, the catalyst, Pt/CMK-3, prepared using paraformaldehyde reduced platinum showed much higher activity and long-term stability as compared to the other reducing methods.     

含过渡金属分子筛催化环己醇与空气氧化制备环己酮

分别采用离子交换法、水热合成法和干胶转化晶化法,将非贵过渡金属引入到分子筛中合成出含过渡金属的分子筛催化剂,并将其应用于以空气为氧化剂、多相催化环己醇合成环己酮的反应中,探索高效、环保、廉价的绿色催化氧化反应体系.研究结果表明,采用水热合成法制备的含钴分子筛(CoAlPO-5)在催化空气氧化环己醇制备环己酮的反应中表现出优异的催化活性,通过考察反应温度、空气流速、反应时间、催化剂用量等探索了最佳催化反应条件是:反应温度为100℃、空气流速为40mL/min、反应时间为8h、催化剂用量为100mg时,环己醇转化率可达到38.2%,环己酮选择性达到95.8%.