Characterization of light and heavy hydrated magnesium carbonates using thermal analysis

Upon heating, hydrated magnesium carbonates (HMCs) undergo a continuous sequence of decomposition reactions. This study aims to investigate the thermal decomposition of various commercially produced HMCs classified as light and heavy, highlight their differences, and provide an insight into their compositions in accordance with the results obtained from thermal analysis and microstructure studies. An understanding of the chemical compositions and microstructures, and a better knowledge of the reactions that take place during the decomposition of HMCs were achieved through the use of SEM, XRD, and TG/differential thermal analysis (DTA). The quantification of their CO 2 contents was provided by TG and dissolving the samples in HCl acid. Results show that variations exist within the microstructure and decomposition patterns of the two groups of HMCs, which do not exactly fit into the fixed stoichiometry of the known HMCs in the MgO-CO2-H2O system. The occurrence of an exothermic DTA peak was only observed for the heavy HMCs, which was attributed to their high CO2 contents and the relatively delayed decomposition pattern. © 2013 Akadémiai Kiadó, Budapest, Hungary.

Characterisation of different commercial reactive magnesia

Reactive magnesia (MgO) has emerged as an essential component in a new family of cements with significantly superior technical and environmental performance over Portland cement. The physical characteristics of different reactive magnesia, which are likely to affect their engineering performance, vary considerably depending on their origin and manufacturing processes. To appropriately utilise such a material, it is essential to develop a better understanding of the characteristics of different magnesia from various sources. In this study, the detailed characterisation of 14 commercial magnesia in terms of reactivity, textural properties, X-ray diffraction pattern, pH value and hydration behaviour and morphology is presented and correlation between them is developed. Relationships were developed between the reactivity, specific surface area, agglomeration ratio and hydration rate based on the experimental observations. As a result, the reactive magnesia used in this study were grouped into three categories and their characteristics and anticipated performances in different applications were discussed.

Properties and microstructure of GGBS-magnesia pastes

Reactive magnesia (MgO) was used as an alkali activator for ground granulated blast-furnace slag (GGBS) and its activating efficiency was investigated compared with hydrated lime. GGBS-MgO and GGBS-hydrated lime paste samples with different compositions and different water to solid ratios were prepared and cured for different periods. A range of tests was conducted to investigate the properties and microstructure of the pastes, including compressive strength, X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, energy dispersive X-ray and thermogravimetric analysis. The results showed that the reactive MgO acts as an effective alkali activator of GGBS, achieving higher 28-day compressive strength than that of the corresponding GGBS-hydrated lime system. The extensive microstructural investigation indicated that the main hydration product of reactive MgO-activated GGBS and hydrated lime-activated GGBS systems was hydrated calcium silicate, but there was much more hydrotalcite present in the former, which contributed to its superior 28-day compressive strength.

Band-gap bowing and p-type doping of (Zn, Mg, Be)O wide-gap semiconductor alloys: a first-principles study

Using a first-principles band-structure method and a special quasirandom structure (SQS) approach, we systematically calculate the band gap bowing parameters and p-type doping properties of (Zn, Mg, Be)O related random ternary and quaternary alloys. We show that the bowing parameters for ZnBeO and MgBeO alloys are large and dependent on composition. This is due to the size difference and chemical mismatch between Be and Zn(Mg) atoms. We also demonstrate that adding a small amount of Be into MgO reduces the band gap indicating that the bowing parameter is larger than the band-gap difference. We select an ideal N atom with lower p atomic energy level as dopant to perform p-type doping of ZnBeO and ZnMgBeO alloys. For N doped in ZnBeO alloy, we show that the acceptor transition energies become shallower as the number of the nearest neighbor Be atoms increases. This is thought to be because of the reduction of p-d repulsion. The N-O acceptor transition energies are deep in the ZnMgBeO quaternary alloy lattice-matched to GaN substrate due to the lower valence band maximum. These decrease slightly as there are more nearest neighbor Mg atoms surrounding the N dopant. The important natural valence band alignment between ZnO, MgO, BeO, ZnBeO, and ZnMgBeO quaternary alloy is also investigated.

催化消除NO_x复合氧化物催化剂的研究

氮的氧化物(NOx)是大气中的一种重要的污染物，是酸雨的主要来源，目前氮氧化物的无毒处理已经是国际环保研究中最关键的课题之一。本论文选择了两种复合氧化物：一种是钙钛石结构的含Cu的层状复合氧化物；另一种是以水滑石为前体经焙烧后得的复合氧化物为催化剂对它们的物化性质和对催化消除NOx的活性进行了系统的研究，得到了一些有意义的结果。第一部分：钙钛石型结构的含Cu层状复合氧化物钙钛石复合氧化物由于具有独特的物理化学性质，长期以来一直受到固态物理、固体化学和催化领域的科技工作者的重视。尤其近年来对它们在催化消除NOx反应中的活性的研究引起了催化工作者的极大兴趣，这是由于，一方面，钙钛石类复合氧化物对处理NOx的反应活性比较高，有希望取代贵金属催化剂；另一方面，探讨复合氧化物的固态物理、化学性质与处理NOx反应催化性能的关系，有利于揭示处理NOx反应的催化作用本质，为寻找高效实用的催化剂提供理论依据。本论文系统研究了三个系列含Cu钙钛石型复合氧化物的固态物理化学性质和对NO-CO反应的催化性能，并讨论了二者的关系。主要的工作和结论如下：1) 以La_2CuO_4为模型化合物研究了制备方法对它的性质的影响：用四种制备方法：柠檬酸络合爆炸法，聚乙二醇凝胶法，聚丙烯酰胺凝胶法，DTPA络合法合成了La_2CuO_4。比较了四种方法的特点，和制备方法对La_2Cu0_4的结构的影响，并对所得La_2CuO_4在NO-CO反应中的催化活性的影响进行了研究。结果发现聚乙二醇凝胶法和DTPA络合法有利于形成好的晶形，而聚乙二醇凝胶法和聚丙烯酰胺凝胶法对NO-CO反应有较好的活性，这是由于由不同制备方法得到的样品中的缺陷的种类和含量不I司所致。2) La_(1-x)Ba_xCuO_(3-λ)系列中Ba含量对它的性质的影响：用柠檬酸络合法合成了LaBa_2Cu_3O_(7-λ)，LaBaCu_2O_(5-λ)，La_2BaCu_3O_(7-λ) La_4BaCu_5O_(13-λ)及YBa_2Cu_3O_(7-λ)五种钙钛石结构的复合氧化物。XRD分析表明此系列样品均为层状ABO_3结构（分别为二，三，五层）。用XPS和O_2-TPD对样品中的氧种进行了研究，结果显示样品中存在着两种活性氧种：α氧种和β氧种。在O_2-TPD中低温脱附的是α氧种，它可归属于化学吸附氧与样品中的氧空位的浓度有关。β氧种的脱附温度较高，它归属于晶格氧。利用H_2-TPR和化学分析的手段对样品中的金属离子和活性氧的稳定性进行了表征。结果显示大量的氧空位和Cu~(3+)存在于样品中，并且它们的浓度受Ba离子浓度的影响。此系列样品对CO还原NO的活性研究表明：它们的活性远远高于结构类似的Ln_2CuO_4和Ln_2NiO_4等复合氧化物，在低于300 ℃时N0转化率已接近100％．分析结果表明Cu~(3+)和氧空位对活性起很重要的作用。Ba离子的作用是：一方面使含Cu的ABO_3结构稳定；另一方面使样品更容易吸附NO。3) La_4BaCu_5O_(13-λ)中Mn或C0逐步取代Cu对样品性质的影响合成了两系列分别由Mn或Co逐步取代Cu的样品，XRD分析表明它们仍旧是钙钛石结构。通过XPS，O_2-TPD和化学分析方法对样品中的活性氧种进行了表征，结果表明，当Mn逐步取代Cu离子时，晶格氧增加，而吸附氧开始变化较小，当Mn含量大于Cu含量时，吸附氧迅速减少。在Co取代样品的O_(1s)的XPS谱中，氧种变化较Mn取代的小，这表明Co离子对样品中的氧空位含量的影响较Mn离子的小。氧化还原性能的研究表明当Cu离子被Mn或Co离子部分取代后，Cu离子变得更容易被还原，这表明Cu-M(Mn或CO)之间发生了协同作用，使Cu离子更活泼。当Mn或Co部分取代Cu离子之后，样品对CO还原NO反应的催化活性明显提高，当取代含量达到一定程度时（即X ≥ 3），催化活性迅速降低，这表明Cu离子在反应中起着很重要的作用，经过分析我们认为反应机理如下：Cu~(3+)-O~=-Cu~(3+) + CO → Cu~(2+)-□-Cu~(2+)+CO_2 Cu~(2+)-□-Cu~(2+) → Cu~(3+)-□-Cu~(2+) Cu~(3+)-□-Cu~(2+) + NO~-Cu~(3+)-NO-Cu~(2+) 2Cu~(3+)-NO-Cu~(2+) → 2Cu~(3+)-O~=-Cu~(3+) + N_2 式中□是氧空位，Cu~(3+)-□ 是F心。掺杂部分Mn或Co后，催化活性的提高可以归属于Cu-M之间发生的协同作用使Cu离子更活泼，表征结果表明Cu-Co之间的协同作用较Cu-Mn之间的弱（这可能是由于Co，Cu之间化学性质相似），但掺杂Co的样品的活性较掺杂Mn的要高，同时我们在反应中发现，Co含量较高的样品中反应产物中N_2O比掺杂Mn的样品高出许多，因此我们认为Co离子对反应中反应中间产物N_2O的生成比Mn离子要活性。第二部分以水滑石化合物为前体的复合氧化物水滑石类化合物属于一种阴离子粘土，由带正电荷的金属氧化物／氢氧化物和层间阴离子及水分子组成。以水滑石为母体经焙烧制得的氧化物催化剂用于氧化反应的实例尚不多，且大多用于液相催化反应。最近有文献报道含Co，Cu，Ni水滑石经焙烧后对N_2O分解有很好的活性，但还没有关于此类化合物应用于NO还原和分解的文献报道。我们首次将以水滑石为母体经焙烧制得的尖晶石催化剂用于催化消除NO_x的反应中，考察和表征了变更过渡金属离子时Co-M-Al系列和Mg-M-Al系列催化剂在CO还原NO，NO吸附和NO分解反应中的活性。1) 以Mg-M-Al水滑石为前体的催化剂用共沉淀法合成了一系列Mg-M-Al水滑石（M = Cr，Fe，Mn，Co，Ni，Cu；Mg/M/A1 = 3/1/1）。XRD表征表明所有化合物均为典型的水滑石化合物。通过TG-DTA考察了焙烧对样品的结构和组成的影响。450 ℃焙烧后所有样品的XRD图中仅能发现MgO相，表明过渡金属氧化物均匀地分散在MgO-Al_2O_3中，换句话说，所得样品焙烧后是过渡金属氧化物负载在MgO-Al_2O_3载体上。H_2-TPR研究进一步证实过渡金属氧化物在载体上得到了稳定。此系列样品对C0还原N0反应活性的测定表明Mg-Al-Cu样品表现出远远高于其它样品的活性，而Mg-Al和Mg-Ni-Al在550 ℃以下对反应几乎没有活性，其它样品表现出一定的活性。2) 以Co-M-Al水滑石为前体的催化剂体系经共沉淀法合成了Co-M-Al水滑石（M = 过渡金属），经焙烧后发现样品中有尖晶石相出现。比表面研究表明，在500-700 ℃之间比表面变化较小大约在80m~2/g左右，在更高温度焙烧后比表面迅速下降。此系列样品对NO的吸附性能研究表明Co-Al，C0-Ni-Al，Co-Cr-Al，Co-Fe-Al表现出较高的吸附性能，尤其是Co-Ni-Al在100 ℃对NO表现出100％的吸附；其它样品对NO的吸附较低。用过渡金属离子中d轨道电子在吸附前后的晶体场稳定化能的变化可以很好地解释此系列样品对NO的吸附性能。对NO分解的活性测定表明Co-Ni-A1，Co-Cr-A1和Co-Al表现出了较好的活性，其中Co-Ni-Al的活性最高。其它样品在600 ℃以下几乎没有活性。分析结果表明样品对NO分解有活性的催化剂必须具备两个条件：1：对NO有较好的吸附性能；2: NO分解后产生的氧可以容易的脱附。除Co-Al外，所有样品对CO还原NO表现出很高的活性：在150 ℃即有较高的NO转化率，在180 ℃NO转化率即可达到100％。催化剂的氧化还原性能在反应中起着很重要的作用，H_2-TPR研究发现掺杂其它过渡金属后Co离子的还原温度明显降低，表明Co离子得到了活化。3) 以Co-Cu-Al水滑石为前体的样品用共沉淀法合成了一系列Co/Cu/Al含量不同的水滑石化合物，包括Co/Cu/Al分别为7/1/1，3/1/1及1/1/1和仅含Co或Cu的Co/Al = 3/1，Cu/Al = 3/1等一系列样品。XRD结果表明除Cu-Al外其它样品经焙烧后均出现了尖晶石相。Cu-Al样品经焙烧后出现了CuO相表明样品为CuO负载于Al_2O_3上。NO和CO的TPD研究表明三组份样品对NO和CO的吸附明显高于二组份样品，而且含CO量高的样品对NO和CO的吸附能力更好，表明Co起较强的作用。在三组份样品的NO-TPD脱出物中发现有N_2O和N_2，表明NO在样品表面的吸附为活化吸附。对CO还原NO反应活性的研究表明，三组份样品的活性远远高于二组份样品，且含Co量高的样品活性较高，表明在此系列样品中Co离子起决定性作用，而Cu离子起助催化作用。通过对反应中各组份含量的变化分析，我们认为反应机理如下：CO + O-Cat → CO_2 + □-Cat NO + □-Cat → NO-Cat 2(NO-Cat) → N_2O + O-Cat + □-Cat N_2O + □-Cat → N_2O-Cat N_2_O-Cat → N_2 + O-Cat 2(N_2O-Cat) → N_2 + 2(O-Cat) O-Cat是样品中的晶格氧，在Co-Al中加入其它过渡金属离子使样品中的晶格氧得到活化，因此，催化活性得到提高。用以水滑石为前体，共沉淀法和固相反应法等三种制备方法合成了一系列Co-Cu-Al催化剂，发现以水滑石为前体的样品不论是对NO，CO的吸附性能还是对NO-CO反应的催化活性都远远高于其它方法制备的样品，这可能是由于水滑石可以起到一个模版作用，使Cu, Co离子分散的更均匀，以及使催化剂表面的含氧基团丰富。

Ce-基催化剂上CH_4低温催化燃烧的研究

Ce-基催化剂在汽车尾气净化，工业废气处理，烃类重整，烃类选择加氢等方面均有广泛的应用。近几十年来关于如何制备高活性、高稳定性的非贵金属复合氧化物催化剂一直是催化研究的重要课题之一。Ce-基催化剂主要都是通过其它金属氧化物M掺杂到CeO_2中形成Ce_(1-x)M_xO（M为掺杂物）固溶体。本文选用CeO_2作为主要研究对象，用柠檬酸法有目的的引入化学特性、离子半径不同的另一组分，用x值表示各元素间的化学计量比，优化催化剂的组成、结构，来调节所合成固溶体氧化物的物理化学性质。分别以碱土金属Ca、稀土金属La以及过渡金属Ni和Mn为掺杂物制备出含其它不同离子的Ce-基催化剂；将具有较高活性的Ni_(0.7)Ce_(0.3)O负载在ZrO_2上，以CH_4燃烧为模型反应，考察催化剂活性和氧化还原性的关系。1．Ce-Ca-La-O体系单独Ca或La分别加入到CeO_2中后催化剂的活性比单独的CeO_2的活性要高出很多，完全转化温度要下降近100℃，而且它们的H_2-TPR实验也证实了其氧化还原能力有很大的提高。将Ca和La同时引入到CeO_2的复合氧化物Ce-La-Ca-O材料，其活性比无La的Ce-Ca-O的活性没有明显的提高，而且反而要比Ce-La-O的活性低，且其HZ一TPR实验也显示出和复合氧化物Ce-Ca-O的轮廓一样。2．Ce-Ni-Mn-O体系对NiO、MnO_x、CeO_2三种金属氧化物，在优化两种金属氧化物最佳配比（组成）后，在复合氧化物中掺杂第三种金属氧化物以考察第三种金属对其甲烷燃烧活性的影响。（l）CeO_2-MnO_x体系中，在Ce_(0.8)Mn_(0.2)O掺杂NiO后，发现当Ni的摩尔量为-10％时，活性提高幅度的很大，完全燃烧的温度下降了近50℃，可在550℃将CH_4完全氧化到CO_2。（2）CeO_2-NiO体系中，Ce_(0.3)Ni_(0.7)O可在530℃将CH_4完全氧化到CO_2。向其中掺杂Mn后，复合氧化物的活性反而下降，要在550oC才能将CH4完全氧化到C02。这可能是阴离子缺陷减少所致。（3）NIO一Mnox体系中，Nio，IMn090掺杂Ce后，催化活性有大幅度提高，特别是Nio．ICeyMno90（0．3三y生0．8）中催化剂的活性更高，可在530oC体系中，其中y＝0．5时更突出。3．Ni-Ce-O／ZrOZ体系（1）Ni1-x一Cex一O体系中，独立的CeOZ相促进了NIO的还原和表面积增加。（2）少量的CeOZ的掺杂明显改善了NIO对cH4完全氧化反应的活性。继续增加Ce的量催化活性弱有增加，然后下降。在Ce的掺杂量为30％时，即Nio7Ceo3O，催化活性最佳，此时甲烷完全转化的温度为530oC。（3）催化剂Ni07Ceo3O具有很好的稳定性，900oC下焙烧，还能在540oC将CH4完全氧化到COZ。（4）催化剂Pd／Ni07Ceo30的催化活性与Pd／A12O3的活性相当。（5）催化剂Ni07Ce03O负载在不同的载体上，发现ZrOZ作载体效果最佳，其次为5102，这可能是ZrOZ、5102对NIO、CeOZ相对惰性有关；而MgO、A1203虽表面积较大，但作为载体效果却不好，可能其易与NIO、CeOZ发生反应有关。（6）Nio7Ceo3O负载在ZrOZ上，提高了表面积同时促进了Nio7Ceo3O还原性，以负载量为50％时活性最好。结构分析发现有两个新相生成，Ni4Zro和CeZO3。（7）通过对比发现Nio7Ceo3O（50％）／ZrOZ体系高活性除了ZrOZ作为载体提高表面积外，Zr02和Ce在这里还起到助催化剂的作用。4．还探讨了Pr掺杂到CeO2，以及YSZ作为载体负载过渡金属氧化物在甲烷催化燃烧反应种的作用。

氧化物气敏半导体与H_2O(g)、O_2(g)及还原性气体相互作用的研究

本文采用自行设计的均速增加加热电压改变元件温度的方法以及动、静态气敏特性测试方法并借助其它测试手段（X光衍射、BET、扫描电流）系统地研究了表面电导控制型SnO_2系元件和体电导控制型γ-Fe_2O_3元件在变温过程中与H_2O(g)、O_2(g)和还原性气体相互作用的规律。实验结果表明：添加剂Al_2O_3、MgO、Pd、Pt和Sb_2O_3均对元件的体电阴均有调制作用。Al_2O_3是以微粒状存在于元件内，它为元件提供了活化中心，提高了元件的灵敏度。而γ-Fe_2O_3具有超微细结构。SnO_2系元件和γ-FeO_3元件取样电压(V_L)与温度（T）的变化关系在空气和惰性气氛中均是非线性的。材料组份不同的元件，其V_L～T变化规律不同。各元件在空气和惰性气氛中的变化，除阻值不同外，其V_L～T变化规律基本相同。综合考虑添加剂(Al_2O_3、MgO)和气氛（空气、惰性气氛、纯氧气）的影响，SnO_2系元件的V_L～T变化规律不仅是由于氧在元件表面上的吸附及吸附状态的不同所引起，很大程度上取决于元件材料的组成和温度对材料内载流子浓度和逐移率的影响。基于对SnO_2系元件的V_L～T变化规律的分析，γ-Fe_2O_3元件V_L随温度的变化也是由于环境中的氧和材料内载流子迁移率随温度的变化所致。SnO_2系元件和γ-Fe_2O_3元件在不同温度所测的V_L～T变化关系表明：SnO_2元件在低温(<72%RH)条件下，具有与干燥空气中相同的V_L～T变化关系；在高温度(>72%RH)的空气中，H_2O(g)的存在对元件低温区(<100 ℃) (200 ℃-400 ℃)的V_L值均有影响，在低温区的V_L值较干燥空气中的V_L值高；中温区的V_L值较干燥空气中的V_L值低。把在约98%RH的空气和氩气中的V_L～T变化曲线比较表明：中温区的实验现象是由于空气中H_2O(g)与O_2(g)共存所致。γ-Fe_2O_3元件在不同温气气氛中的V_L～T变化规律相同，且在元件工作温度（129 ℃～320 ℃）范围内V_L值相同，但均较干燥空气中该条件下的V_L值高。在实验中亦观察到SnO_2元件在温度低于72%RH中长期放置亦可观察到与实验中温度>72%RH条件下相同的V_L～T变化。SnO_2元件在空气和惰性气氛中对还原性气体均有气敏性。而且在惰性气氛中对微量还原性气体（H_2）的灵敏度比在空气中的灵敏度高。掺贵金属Pd或Pt的SnO_2元件在惰性气氛中，当H_2浓度高于8000ppm时，元件电导突变式增加。我们认为SnO_2系元件在空气中检测还原性气体的工作机理是表面化学反应过程；在惰性气氛中其工作机理是表面解离吸附过程。γ-Fe_2O_3元件在空气中对C_4H_(10)具有较高的选择性。但在惰性气氛中对还原性气体不具有气敏性。我们认为环境中氧是体电导控制型气敏元件气敏性不可缺少的中间媒介。其检测机理是微观可逆氧化-还原过程。

Interface energy and its influence on interface fracture between metal and ceramic thin films in nanoscale

A theoretical model about the size-dependent interface energy between two thin films with different materials is developed by considering the chemical bonding contribution based on the thermodynamic expressions and the structure strain contribution based on the mechanical characteristics. The interface energy decreases with reducing thickness of thin films, and is determined by such available thermodynamic and mechanical parameters as the melting entropy, the melting enthalpy, the shear modulus of two materials, etc. The predicted interface energies of some metal/MgO and metal/Al2O3 interfaces based on the model are consistent with the results based on the molecular mechanics calculation. Furthermore, the interface fracture properties of Ag/MgO and Ni/Al2O3 based on the atomistic simulation are further compared with each other. The fracture strength and the toughness of the interface with the smaller structure interface energy are both found to be lower. The intrinsic relations among the interface energy, the interface strength, and the fracture toughness are discussed by introducing the related interface potential and the interface stress. The microscopic interface fracture toughness is found to equal the structure interface energy in nanoscale, and the microscopic fracture strength is proportional to the fracture toughness. (C) 2010 American Institute of Physics. [doi:10.1063/1.3501090]

Nano-size Effect of Interface Energy and Its Effect on Interface Fracture

An analytical model about size-dependent interface energy of metal/ceramic interfaces in nanoscale is developed by introducing both the chemical energy and the structure stain energy contributions. The dependence of interface energy on the interface thickness is determined by the melting enthalpy, the molar volume, and the shear modulus of two materials composing the interfaces, etc. The analytic prediction of the interface energy and the atomic scale simulation of the interface fracture strength are compared with each other for Ag/MgO and Ni/Al2O3 interfaces, the fracture strength of the interface with the lower chemical interface energy is found to be larger. The potential of Ag/MgO interface related to the interface energy is calculated, and the interface stress and the interface fracture strength are estimated further. The effect of the interface energy on the interface strength and the behind mechanism are discussed.

Light alkenes preparation by the gas phase oxidative cracking or catalytic oxidative cracking of high hydrocarbons

The preparation of light alkenes by the gas phase oxidative cracking (GOC) or catalytic oxidative cracking (COC) of model high hydrocarbons ( hexane, cyclohexane, isooctane and decane in the GOC process and hexane in the COC process) was investigated in this paper. The selection for the feed in the GOC process was flexible. Excellent conversion of hydrocarbons ( over 85%) and high yield of light alkenes ( about 50%) were obtained in the GOC of various hydrocarbons including cyclohexane at 750 degreesC. In the GOC process, the utilization ratio of the carbon resources was high; CO dominated the produced COX (the selectivity to CO2 was always below 1%); and the total selectivity to light alkenes and CO was near or over 70%. In the COC of hexane over three typical catalysts (HZSM-5, 10% La2O3/HZSM-5 and 0.25% Li/MgO), the selectivity to COX was hard to decrease and the conversion of hexane and yield of light alkenes could not compete with those in the GOC process. With the addition of H-2 in the feed, the selectivity to COX was reduced below 5% over 0.1% Pt/HZSM-5 or 0.1% Pt/MgAl2O4 catalyst. The latter catalyst was superior to the former catalyst due to its perfect performance at high temperature, and with the latter, excellent selectivity to light alkenes ( 70%) and the conversion of hexane (92%) were achieved at 850 degreesC ( a yield of light alkenes of 64%, correspondingly).

NOx storage-reduction over Pt/Mg-Al-O catalysts with different Mg/Al atomic ratios

A series of Pt/Mg-Al-O catalysts with different Mg/Al atomic ratios were prepared. The NOx storage capacities of these catalysts were measured by isothermal storage at 350 degreesC. It was found that the NOx storage capacity increased with increasing Mg/Al atomic ratios. The catalytic behaviors of Pt/Mg-Al-O and Pt/MgO were studied with storage-reduction cycles at 400 degreesC. Under oxidizing conditions, NOx concentration in the outlet gas gradually increased with time, which indicated the catalysts could store NOx effectively. After a switch from oxidizing conditions to reducing conditions, NOx desorption peak emerged immediately due to the incomplete reduction of stored NOx, which lowered the total NOx conversion. With increasing Mg/Al atomic ratio in the catalysts, NOx conversion increases. Pt/MgO has the highest NOx conversion because of its best activity in the reduction of NOx by C3H6. It seems that with an increasing amount of MgO in the catalysts, the self-poisoning of Pt-sites by adsorbed species during the reaction of NOx with C3H6 may be inhibited effectively.

Effect of support on chromium based catalysts for the oxidative dehydrogenation of C2H6 with CO2 to C2H4

The oxidative dehydrogenation of ethane (ODE) with CO2 to C2H4 has been studied over a series of Cr-based catalysts using SiO2, Al2O3, (MCM-41 zeolite) MCM-41, MgO and Silicate-2 (Si-2) as the supports. TPR, NH3-TPD, and EPR characterizations of catalysts were carried out to investigate the reduction property of Cr species on different supports, the acidities of catalysts and Cr species of 6Cr/SiO2 catalysts, respectively.

菱镁矿粉尘污染土壤机理及其植物修复

综述了菱镁矿粉尘对土壤的污染和植物的毒害作用机理,分析了镁粉尘污染土壤的改良途径,探讨了植物修复的可行性和关键技术。菱镁矿在开采、生产加工过程中产生的大量粉尘,主要成分为MgCO3和MgO,镁粉尘对土壤的污染和植物的毒害作用主要是通过碱化、板结土壤,以及使土壤中的水溶性钙、镁离子比例失调而造成的。虽然菱镁矿粉尘污染土壤的植物修复研究鲜见报道,但通过植物吸收、植物代谢和植物积累等作用去除土壤中的过量镁具有较强的可行性。

Carbon deposition behavior over copper salts of molybdovanadophosphoric acid catalyst supported by magnesia

MgO supported copper salt of molybdovanadophosphoric acid H4PMo11VO40 catalysts were prepared in alcohol by impregnation and the carbon deposition over these catalysts during the n-hexanol oxidation reaction was studied. The coke predominantly deposited on the catalyst surface in the form of CH., and it was not found that it caused the deactivation of the catalyst. The XRD, IR, XPS characterizations reveal that the Keggin structure of the CPMV was unaffected by carbon deposition. Moreover, it was shown that the supported CPMVs over the MgO surface can be beneficial to eliminate the coke. The temperature programmed oxidation (TPO) study showed that coke was formed over the catalyst on two different sites: (1) deposited on the CPMVs which can be burn off at a low temperature; (2) deposited on the MgO which could only be removed at higher temperature. The coke content reached constant with the reaction time increasing.

Structural characterization and property of in-situ synthesized AZ91-Mg2Si composite

A new-type Mg2Si composite was prepared with Mg-9Al-1Zn (AZ91) alloy and vermiculite as raw materials by melt infiltration method. The results show that the microstructure of composite consists of a large amount Of Mg2Si precipitates and a little amount of MgO embedded in alpha-Mg matrix. The Vickers hardness of the composite is obviously higher than that of matrix of AZ91 alloy. Moreover, the composite exhibits excellent compressive property. The ultimate compressive strength of the material is 290 MPa, the yield strength is 175 MPa, and the elongation is about 5%, which are higher than those of AZ91 alloy.