Strong Morphological Effect of Mn3O4 Nanocrystallites on the Catalytic Activity of Mn3O4 and Au/Mn3O4 in Benzene Combustion

Gold nanoparticles (3–4 nm) were deposited on Mn₃O₄ nanocrystallites with three distinct morphologies (cubic, hexagonal, and octahedral). The resulting structures were characterized, and their activities for benzene combustion were evaluated. The dominant exposed facets for the three kinds of Mn₃O₄ polyhedrons show the activity order: (103)≈(200)>(101). A similar activity order was derived for the interfaces between the Au and the Mn₃O₄ facet: Au/(200)≈Au/(103)>Au/(101). The metal–support interactions between the Au nanoclusters and specific facets of the Mn₃O₄ polyhedrons lead to a unique interfacial synergism in which the electronic modification of the Au nanoparticles and the morphology of the Mn₃O₄ substrate have a joint effect that is responsible for a significant enhancement in the catalytic activity of the Au/Mn₃O₄ system.     

2-巯基苯并噻唑对铜缓蚀行为的表面增强红外光谱研究

2-巯基苯并噻唑(MBT)是Cu的高效缓蚀剂,但是缓蚀机理存在较大争议.本文通过电化学极化曲线从宏观角度对缓蚀效率进行评估,并利用原位衰减全反射-表面增强红外光谱技术结合理论计算研究了电位控制下的微观吸附构型.结果表明:在较高电位(大于0 V,相对饱和甘汞电极(SCE))下,MBT和金属Cu之间发生电子转移,MBT以硫醇式的环外S和N与金属Cu(I)离子配位在表面形成聚合物膜;在较低电位(小于0 V,vs SCE)下,MBT通过环外S原子以硫醇离子形式在金属Cu表面直立吸附.表面膜阻止了腐蚀介质的侵蚀,起到了较好的缓蚀效果.     

固态研磨-燃烧法制CuO-ZnO-ZrO2/HZSM-5二甲醚合成催化剂

以柠檬酸为燃烧剂,采用固态研磨-燃烧法和机械混合法制备了CuO-ZnO-ZrO2/HZSM-5CO2加氢一步合成二甲醚双功能催化剂.采用固定床反应器,在反应温度270℃、压力为3.0 MPa、空速4 200 h-1条件下,考察了催化剂对CO2加氢一步合成二甲醚的反应性能,并采用XRD、BET、H2-TPR、NH3-TPD及XPS对催化剂的结构进行了表征.评价结果表明:随柠檬酸量的增加,二甲醚选择性和收率呈峰形变化趋势;当柠檬酸的量等于化学计量比的100%时,制备的催化剂具有较好的催化性能:CO2单程转化率为24.8%、二甲醚(DME)的选择性和收率分别为35.3%和8.7%.表征结果表明:柠檬酸的量影响催化剂的比表面积、还原性能以及CuO和ZnO的晶粒尺寸等,进而影响催化剂反应性能.     

Trapped modes along a periodic array of freely floating obstacles

We consider the coupled problem describing the motion of a linear array of three‐dimensional obstacles floating freely in a homogeneous fluid layer of finite depth. The interaction of time‐harmonic waves with the floating objects is analyzed under the usual assumptions of linear water‐wave theory. Quasi‐periodic boundary conditions and a simplified reduction scheme turn the system into a linear spectral problem for a self‐adjoint operator in Hilbert space. Based upon the operator formulation, we derive a sufficient condition for the nonemptiness of its discrete spectrum. Various examples of obstacles that generate trapped modes are given. Copyright © 2014 John Wiley & Sons, Ltd.     

Double‐injection capillary electrophoresis for the identification of analytes

This paper presents a new approach for identifying analytes by CE. The compound to be identified is analyzed together with the corresponding reference standard during a double injection capillary electrophoretic run. The inter‐plug distance is regulated by applying an electrical field over the capillary for a predetermined time period (t_PE). The migration time of an analyte being exposed to the partial electrophoresis was calculated from the partial migration time (t_mig(p)) as described in this paper. The identification is based on the closeness of agreement between the calculated migration time (t_mig(c)) and observed migration time (t_mig) of the reference standard. The validity of the derived equations was checked by analyzing several substances such as caffeine, melamine, acetyl salicylic acid, paracetamol, ibuprofen, metoprolol, naproxen, somatropin, several insulin analogs, as well as different pharmaceutical and natural products. The migration time ratios for the identified solutes varied between 0.996 and 1.006 (i.e., 1.001 ± 0.005), indicating good agreement between the observed and calculated migration times.     

The READY program: Building a global potential energy surface and reactive dynamic simulations for the hydrogen combustion

READY (REActive DYnamics) is a program for studying reactive dynamic systems using a global potential energy surface (PES) built from previously existing PESs corresponding to each of the most important elementary reactions present in the system. We present an application to the combustion dynamics of a mixture of hydrogen and oxygen using accurate PESs for all the systems involving up to four oxygen and hydrogen atoms. Results at the temperature of 4000 K and pressure of 2 atm are presented and compared with model based on rate constants. Drawbacks and advantages of this approach are discussed and future directions of research are pointed out. © 2014 Wiley Periodicals, Inc.     

大同烟煤增压富氧燃烧过程中硫、氯和氟的析出特性

利用高压热重结合傅里叶红外研究了大同烟煤在增压富氧燃烧过程中硫、氯和氟的释放行为,主要考察压力对其析出特性的影响。实验结果表明,压力的改变对煤中硫、氯和氟的迁移转化均有显著影响。随着压力的升高,黄铁矿硫向COS等中间产物的转化率逐渐增加,导致SO2的收率逐步上升,但在3 MPa时,燃煤SO2收率却有所降低。此外,压力升高后反应气氛中CO分压的增加促进了COS的生成,导致其收率逐渐上升。因为煤中有机氯析出和转化与挥发分的释放密切相关,所以高压下挥发分释放量的增加使得煤中有更多的有机氯析出并转化为HCl,而且压力升高后,挥发分燃烧速率和温度的升高促进了无机氟化物分解,HF生成量相应增加。此外,高压下水解反应的强化也提高了HF的收率。     

增压O_2/CO_2气氛下煤燃烧特性实验研究

增压O2/CO2燃烧是一种可高效分离回收CO2的新兴燃烧技术,其燃烧机理与常压空气、常压O2/CO2燃烧存在较大差异。在加压热重分析仪上研究了增压条件下总压、氧浓度、气氛及粒径等反应参数对美国烟煤和淮北无烟煤燃烧特性的影响,确定了煤的着火温度,并对其进行燃烧动力学分析。结果表明,增压O2/CO2气氛下,随着压力或氧浓度的增加,DTG曲线向低温区移动,煤样整体燃烧速率加快。压力提升、氧浓度增加及煤粉细化均可改善O2/CO2气氛下煤样的着火特性。常压O2/CO2气氛下煤粉燃烧基本属于一级反应;增压O2/CO2气氛下,低温区属于0.5级反应,而高温区属于1.5级反应。     

Molecular Dynamics in 1- and 2-D Confinement as Studied for the Case of Poly(Cis-1,4-Isoprene)

Broadband Dielectric Spectroscopy (BDS) is used to probe the molecular dynamics of Type A polymer, poly(cis-1,4-isoprene), when confined in the 1-dimensional (1D) exploring space of thin layers and the 2-dimensional (2D) constraining geometry of unidirectional anodic aluminum oxide (AAO) nanopores. For both cases, it was observed that the structural relaxation remains bulk-like in its mean relaxation rate, although the distribution of its relaxation times is broadened in 2D confinement. Furthermore, the fluctuation of the end-to-end vector is interrupted, with the 1D case being relatively less pronounced. By this clear-cut comparison, it is demonstrated that the effects of confinement on molecular dynamics depend, inter alia, on the dimensionality of the restricting space.     

Topologically protected interface mode in plasmonic waveguide arrays

Recent realization of nontrivial topological phases in photonic systems has provided unprecedented opportunities in steering light flow in novel manners. Based on the Su–Schriffer–Heeger (SSH) model, a topologically protected optical mode was successfully demonstrated in a plasmonic waveguide array with a kinked interface that exhibits a robust nonspreading feature. However, under the same excitation conditions, another antikinked structure seemingly cannot support such a topological interface mode, which appears to be inconsistent with the SSH model. Theoretical calculations are carried out based on the coupled‐mode theory, in which the mode properties, excitation conditions, and the robustness are studied in detail. It is revealed that under the exact eigenstate excitations, both kinked and antikinked structures do support such robust topological interface modes; however, for a realistic single‐waveguide input only the kinked structure does so. It is concluded that the symmetry of interface eigenmodes plays a crucial role, and the odd eigenmode in a kinked structure offers the capacity to excite the nonspreading interface mode in the realistic excitation of a one‐waveguide input. Our finding deepens the understanding of mode excitation and propagation in coupled waveguide systems, and could open a new avenue in optical simulations and photonic designs.