用封闭循环反应器对碳与二氧化碳气化反应中碱金属催化作用的研究

用封闭循环式反应器考察了在K_2CO_3存在下用二氧化碳气化碳的反应,并在反应进行过程中测定了吸附于焦表面的氧量,并对焦表面吸附氧量与K_2CO_3添加量和气化反应速率的关系以及反应温度和压力对焦表面吸附氧量的影响进行了研究。结果表明,反应过程中的焦表面吸附氧量与K_2CO_3添加量成正比,气化速率随反应时间的变化与焦表面吸附氧量随时间的变化具有很好的对应关系。根据实验结果,认为在反应过程中CO_2首先在催化金属形成的活性中心被解离吸附,形成表面氧化物,气化反应速率由该表面氧化物的数量决定,并认为碳与CO_2的反应是以包括有非催化反应的表面金属氧化物的氧化还原机理进行。     

阶跃过渡应答技术研究Mo-V/Al_2O_3催化剂上乙烷氧化脱氢制乙烯反应的暂态动力学 Ⅱ.乙烷氧化脱氢反应的机理和动力学参数的求取

通过一系列应答实验,证实了氧在MoO_3-V_2O_3催化剂上的吸附和吸附态氧转变为晶格氧的过程是慢过程,是乙烷氧化脱氢反应的速度控制步骤;乙烯的深度氧化是乙烯与催化剂表面上吸附态氧作用的结果,而不是与催化剂上晶格氧作用的结果。结合第Ⅰ部分的实验结果,提出了乙烷氧化脱氢制乙烯反应的机理,并用Treanor法和DPP法求取了各基元步骤的速率常数、活化能和指前因子等动力学参数。用计算所得的结果进行拟合,其结果与实验曲线吻合。     

复合稀土铝阳极氧化膜的耐蚀性研究

用金属氧化物前驱体法,在前处理阶段添加稀土再进行阳极氧化,获得了Nd和Ce改性的铝阳极氧化膜.稀土含量在靠近氧化膜/基体界面处达到0.9%左右,由内向外逐渐降低,氧化膜外表面处的含量约为0.5%.稀土前处理后制备得到的阳极氧化膜耐蚀性能比普通硫酸阳极氧化膜有明显提高,其中Ce改性的氧化膜作用尤为明显;经过NaCl溶液浸泡15 d以后,经稀土改性的阳极氧化膜仍然保持良好的耐腐蚀性.稀土引入后,阳极氧化膜的孔径变小,膜更加致密,显微硬度提高.XPS测试表明氧化膜中的稀土Ce以CeO2和Ce2O3形式存在,而Nd以Nd2O3形式存在.阻抗测试表明氧化膜阻挡层的阻抗值增大,说明稀土除了改变氧化膜生长机制外,也可能通过掺杂作用改变氧化膜结构.     

阶跃过渡应答技术研究Mo-V/Al2O3催化剂上乙烷氧化脱氧制乙烯反应的暂态动力学Ⅱ.乙烷氧化脱氢反应的机理和动力学参数的求取

通过一系列应答实验，证实了氧在ＭｏＯ３－Ｖ２Ｏ５／Ａｌ２Ｏ３催化剂上的吸附和吸附态氧转变为晶格氧的过程是慢过程，是乙烷氧化脱氢反应的速度控制步骤；乙烯的深度氧化是乙烯与催化剂表面上吸附态氧作用的结果，而不是与催化剂上晶格氧作用的结果。结合第Ⅰ部分的实验结果，提出了乙烷氧化脱氢制乙烯反应的机理，并用Ｔｒｅａｎｏｒ法和ＤＦＰ法求取了各基元步骤的速率常数、活化能和指前因子等动力学参数。用计算所得的结果进     

银电极电解氢氧化钠水溶液的阳极反应

本文通过计算和实验证实了用银电极电解氢氧化钠水溶液时，在阳极上首先发生的反应是银的氧化而不是析出氧。从而使本属可溶性阳极的银电极成为不可溶性阳极──银－氧化银电极。     

氧化反应对胜利褐煤水蒸气气化反应的促进作用Ⅱ.作用机理研究

在φ80×3 000 mm耐高温不锈钢管反应器中,进行了N2/N2+O2/N2+H2O/N2+O2+H2O气氛下800和900℃的胜利褐煤气化实验,采用红外光谱、X射线光电子能谱、拉曼光谱和烟气在线分析等研究了添加氧气前后半焦的物理结构、官能团及煤气组成的变化,旨在探讨氧化反应促进水蒸气气化反应的作用机理。结果表明,氧化反应对水蒸气气化反应的促进作用可用半焦的微观结构变化和水蒸气气化解离吸附机理解释。氧化反应的开孔和扩孔作用使碳颗粒微孔数量、比表面积、孔容、吸附量明显增加,更多的碳表面活性位暴露出来,也促进了半焦中甲基、亚甲基、C=O键、C-O键的断裂和高活性的羧基COO-和大量氢自由基的生成,这些都有利于水蒸气气化反应的进行,尤其在高温和水蒸气含量较高时。同时,氧气的加入改变了反应气氛中CO2、CO、H2相对含量和水蒸气分子/活性炭原子内能,也有利于水蒸气气化反应的进行,这与水蒸气气化解离吸附机理相吻合。     

H~2S对硫酸溶液中铁腐蚀作用的CNDO/2研究

动电位扫描得出工业纯铁在含H~2S的H~2SO~4溶液中腐蚀的电化学行为。应用CNDO/2法确定了阴、阳极电位下H~2S,HS^-在金属Fe晶面上的稳定吸附取向与最佳吸附间距,通过对吸附物总能量、结合能、净电荷分布的计算,得出H~2S体系阴、阳极反应被加速的微观机制。阳极电位下,大量HS^-为S原子的平行吸附方式,HS^-负电荷大部分向Fe转移,促进铁的溶解。阴极电位下,少量H~2S则为H原子的平行吸附方式,Fe表面负电荷向H~2S分子中与Fe作用的H转移,促进析氢。在CNDO/2法计算的基础上,圆满地解释了实验结果。     

金属离子在液相氧化中的催化作用VII.第四周期过渡金属氧化物在异丙苯液相氧化中的催化作用

在液相中研究了第四周期过渡金属氧化物在异丙苯氧化中的多相催化作用。和均相催化氧化所得结果相对照,证明金属离子的催化氧化活性和选择性由元素的原子序数所决定,和其存在的状态无关。所得动力学参数值说明,反应系按络合—链锁反应机理进行,氧化物催化剂通过吸附分子氧(配位)主要起引发作用。     

Au2n-(n＝1, 2)催化CO氧化反应机理的理论研究

采用密度泛函理论B3LYP方法研究了金团簇阴离子 和 催化CO氧化反应的详细机理. 计算结果表明, O2分子比CO分子更容易吸附到金团簇上. 第二分子CO能有效降低较强O—O键断裂所需能量. CO氧化反应过程需要两个CO分子协同进行. 和 催化CO氧化反应均通过碳酸根中间体进行, 活化能分别为0.607 和0.658 eV. 和 都能在常温下有效催化CO氧化反应. 这些结果与以前的实验和理论研究一致.     

银表面甲醇氧化反应机理的ab initio计算研究 1: 银表面静态吸附物种的几何构型和吸附性质

本文用原子簇模型(CM)的从头计算方法, 计算了银表面甲醇氧化反应中的静态吸附物种的优化几何构型及吸附性质。计算表明在清洁银表面甲醇、甲醛只存在物理吸附; 当表面存在吸附氧原子时, 甲醇可在银表面形成两种分子态吸附;甲醛与表面羟基OH(a)或氢原子H(a)共存时在银表面能够形成化学吸附, 且CH2O(a)极易与O(a)反应生成深度氧化中间体η^2-甲二氧基; 中间产物甲氧基在无氧的银表面能够形成稳定吸附, 在富氧银表面极易进一步氧化脱氢生成产物甲醛。通过计算与实验结果的对照, 我们对反应机理作了初步讨论。     

Stability of LaNiO3 gas diffusion oxygen electrodes

In this work LaNiO₃ perovskite-type oxide, prepared by a self-combustion method, was optimized for activity and stability as an anode material for water electrolysis. A full electrochemical study was conducted in order to kinetically characterize electrodes prepared using carbon paper as a base for porous gas-diffusion electrodes in alkaline media, regarding water oxidation and oxygen reduction reactions at room temperature. An electrode stability study was performed by potential cycling and at constant current density, using cyclic voltammetry and electrochemical impedance spectroscopy to check on stability after cycling with complementary scanning electron microscopy/energy dispersive X-ray spectrometry (SEM/EDS) analysis of fresh and degraded electrodes. Comparison was made using nickel foam as a support for LaNiO₃ deposition. Carbon instability in the potential region of interest contrasted with the lower contact resistance between the oxide and support of the Ni foam. Higher metal oxide loadings and dimensional stability were also possible.     

H型电解池中CO2电化学还原的阳极电解液问题

采用自制的H型电解池开展了KHCO₃溶液中电化学还原CO₂制甲酸的研究. 研究发现,在电解池中长时间电解时阴阳两极间的电压（槽电压）会持续升高,导致电解过程不可持续. 经过恒电位电解、恒电流电解、pH测试以及电解前后阳极室KHCO₃浓度分析等实验研究,作者发现,这是由以下过程引起的：阳极上的析氧反应产生的H⁺与电解液中的HCO₃^-反应生成水和CO₂,导致阳极室的HCO₃^-的消耗,之后阳极室的K⁺被迫扩散进入阴极室而导致阳极室电解质浓度下降. 因此,阳极室电解液导电性下降,进而引起阳极电位的升高. 研究发现,阳极电解液具有碱性时,都可能发生此种现象,因此,为了保证电解过程可持续且保持高的能量转换效率,阳极液的电解质不能是任何具有碱性的物质.     

Indirect Electrochemical Oxidation of 4-Amino-dimethyl-aniline Hydrochloride

Introduction4Amino dimethyl anilinehydrochlorideisoneof themaincomponentsofthewastewaterresultedfrom vanillinproduction[1]whichinhibitsthenormalactivity ofthemicroorganismsofmicrobialpopulation,thereby affectingthebiologicaltreatmentprocessofvanillin.Comm…     

Studies on the occurrence of atoms and molecules of aluminum, gallium, indium and their monohalides in an electrothermal carbon furnace

Molecular absorption spectra of monohalides (MX; X = F, Cl and Br) of aluminum, gallium and indium have been observed, where the monohalide species were produced in the electrothermal carbon furnace. In the spectra, some characteristic band structures have been identified for each metal halide. Generally, aluminum halides and/or metal fluorides provided clear and sharp band structures. The spectral bandwidth, background absorptions, and co-existing cations influenced the analytical features of molecular absorption spectrometry utilizing the monohalide bands. The time-dependent signal profiles of atoms and molecules at the stage of atomization in the carbon furnace have been observed for discussing the mechanisms of atomization and molecule formation of the Group III elements. Alkali and alkaline earth ions enhanced the molecular absorptions of monohalides, and transition metal ions reduced the background absorptions due to cutting the oxide. In addition, the application of the molecular absorptions of monohalides to the determination of trace halogens has also been investigated using the electrothermal vaporization technique.     

Metal anodes oxidation rate forecasted by results of electrolysis

This work represented the results from electrolysis tests of low-melting cryolite-alumina melts at temperatures of 790 and 850°C using metal anodes based on Cu-Fe-Ni and Cu-Al. The duration of experiment was at least 72 h. With these results, oxide layer dissolution/erosion rate and anodic material oxidation depth was calculated in arbitrary units (alloy cm/year) with examples of extrapolated (forecasted) experimental data of oxidation depth and oxide layer thickness for a long period. The oxide layer formed on the anode surface by electrolysis of the studied materials was found to decelerate further oxidation all over the period of tests.     

限制性自洽场开壳层CNDO/2方法

本文采用限制性自洽场CNDO/2方案,在IBM-PC/XT微机上实现了RHF的CNDO/2计算程序。计算了若干开壳层的小分子和含过渡金属的配合物, 得到体系总能量、电荷、键序、结合能, 与UHF的CNDO/2方法计算结果完全符合, 并且图象清晰·RHF的CNDO/2的方法的实现为半经验方法计算开壳层体系电子光谱跃迁强度, 磁超精细结构常数以及酉群的组态相互作用提供了一个好的波函数。     

铝原子簇上化学吸附的尺度效应及其理论模型

对铝原子簇Al_n(n=1～10,12,13)已报导过的理论预测几何构型进行合理选择, 用量子化学CNDO/2法研究了单分子一氧化碳在这些簇上取不同吸附位形时的吸附作用。结果表明吸附强度随簇尺度的变化呈“幻数”特性: Al_2、Al_6、Al_(12)簇具有特别高的吸附能, 与实验观测结果相符。采用作者建议的推广电子壳模型可合理解释这一尺度效应。对Al_(12)和Al_(13)簇电子结构的分析进一步支持了壳模型的观点。随着簇的增大, 尺度效应逐步减弱并趋向于体相铝的性质。     

钯纳米线电极的制备及其应用于乙醇的电化学氧化研究

纳米线作为纳米科学领域中的重要一员,因其优异的光学、电学及磁学等特性引起了凝聚态物理学界、化学界以及材料科学界科学家们的极大关注,并己成为当今纳米科技研究的热点领域[1].纳米线的制备方法有多种,本文提及的模板法制备纳米线结构技术是20世纪90年代初发展起来的一种既经济又简便实用的新工艺[2].     

A combined experimental and theoretical study on the effect of doping and interface formation on Ppv-ether copolymer

We present a detailed optoelectronic and vibrational study devoted to the transformation from neutral to doped PPV-ether copolymer in both powder and thin film states. The full geometries were optimized with the density functional theory (DFT) for neutral and doped states, where a comparative geometric study was established. The lowest singlet excited-state geometries have been investigated by using the configuration interaction single (CIS/3-21G(d)) method. The absorption spectra are then calculated respectively on the basis of the ground- and excited-state geometries. Our calculation results are in close agreement with those available from experiments. The charge distribution and excitation energies of singly charged PPV-ether are calculated, where two subgap absorption features are found to dominate the optical spectrum correlated with the polaron picture. These theoretical results are compared to experimental optical data illustrated by iodine-doped PPV-ether. Next, we have performed a simulation to model the conformations and the electronic structure modifications of interface formation of PPV-ether copolymer thin film with calcium (Ca), magnesium (Mg), and aluminum (Al) metal as a cathode and indium tin oxide (ITO) as anode in polymer LEDs. By providing the optical parameter obtained and the chemical reaction at the interface, we present the energetic diagram near the interface and the energy position of the lowest occupied molecular orbital with respect to the electrode Fermi level.     

Solid-state water electrolysis with an alkaline membrane

We report high-performance, durable alkaline membrane water electrolysis in a solid-state cell. An anion exchange membrane (AEM) and catalyst layer ionomer for hydroxide ion conduction were used without the addition of liquid electrolyte. At 50 °C, an AEM electrolysis cell using iridium oxide as the anode catalyst and Pt black as the cathode catalyst exhibited a current density of 399 mA/cm(2) at 1.80 V. We found that the durability of the AEM-based electrolysis cell could be improved by incorporating a highly durable ionomer in the catalyst layer and optimizing the water feed configuration. We demonstrated an AEM-based electrolysis cell with a lifetime of >535 h. These first-time results of water electrolysis in a solid-state membrane cell are promising for low-cost, scalable hydrogen production.