对甲烷氧化偶联W－Mn／SiO＿2催化剂Na＿2WO＿4的流失及其影响的考察

用ＸＲＤ、ＦＴ－ＩＲ、ＥＳＲ、Ｈ２－ＴＰＲ和ＴＰＯ等方法，对Ｎａ２ＷＯ４－Ｍｎ２Ｏ３／ＳｉＯ２催化剂和其经水煮处理的一系列样品进行了表征．实验发现该催化剂中的结晶态Ｎａ２ＷＯ４易于流失，单层分布的Ｎａ２ＷＯ４在苛刻的处理条件下也有可能流失．依此，探讨了上述流失现象与Ｎａ２ＷＯ４－Ｍｎ２Ｏ３／ＳｉＯ２催化剂的催化活性及该催化剂在长时间反应中发生的ＳｉＯ２相变之间的关系，证明了结晶态Ｎａ２ＷＯ４的流失对该催化剂甲烷氧化偶联反应的催化活性只有轻微的影响，单层分布Ｎａ２ＷＯ４的流失可造成催化剂中Ｍｎ从Ｍｎ３＋转变为Ｍｎ２＋，并使催化剂的催化活性明显降低．但在水煮条件下，无论是结晶态的还是单层分布，Ｎａ２ＷＯ４的流失都没有对ＳｉＯ２的α－方石英结构产生影响     

水蒸汽对负载型催化剂丙烷脱氢性能的影响：Ⅰ.反应性能的研究

研究了ＭｇＡｌ２Ｏ４，ＺｎＡｌ２Ｏ４负载的Ｐｔ－Ｓｎ催化剂在氮气及水蒸汽中的丙烷脱氢性能。考察了还原温度，反应温度，催化剂载量对Ｐｔ－ＳＳｎ／ＭｇＡｌ２Ｏ４催化剂丙烷脱氢性能的影响。     

La0.8Sr0.2MnO3/YSZ电极氧电化学还原反应动力学

用线性极化、循环伏安、电位阶跃等方法详细研究了Ｌａ０．８Ｓｒ０．２ＭｎＯ３／ＹＳＺ高温电极上进行的氧化学还原反应。实验结果表明，该反应存在两条路径：低温下氧还原反应主要发生在气相－ＬＳＭ电极－ＹＳＺ电解质接触的三相界面（ＴＰＢ），速度控制步骤为氧原子在ＬＳＭ表面的浓差扩散，高温下由于氧空位在ＬＳＭ表面的形成，氧还原反应区扩展至ＬＳＭ电极表面，速度控制步骤为氧的电荷转移反应，实验同时发现：氧空位的形     

合成气制低碳烯烃K－Fe－MnO／MgO催化剂的研究Ⅰ．MnO助剂的作用

采用ＣＯ加氢反应、ＣＯ－ＴＰＤ、ＣＯ／Ｈ＿２－ＴＰＳＲ及Ｃ＿２Ｈ＿４／Ｈ＿２－ＴＰＳＲ等手段，研究合成气制低碳烯烃反应Ｋ－Ｆｅ－ＭｎＯ／ＭｇＯ催化剂中ＭｎＯ的助剂作用。结果表明ＭｎＯ能大幅度提高低碳烯烃的选择性，尤其是乙烯的选择性；ＭｎＯ能抑制催化剂表面的乙烯加氢，因而有利于提高低碳烯烃的选择性及烯／烷的比值。     

Ti／SnO2＋Sb2O3／PbO2阳极的性能研究

以ＳＥＭ、ＥＤＳ和ＸＲＤ研究Ｔｉ／ＳｎＯ２＋Ｓｂ２Ｏ３／ＰｂＯ２阳极，测定该阳极在１ｍｏｌ／ＬＨ２ＳＯ４中的使用寿命及其电化学参数ａ，ｂ，ｉ０并用双位垒模型讨论了其动力学参数。结果表明该电极具有优良的电化学性能和较长的使用寿命。     

La0.8Sr0.2MnO3／YSZ高温电极交流阻抗研究

用交流阻抗方法研究了Ｌａ０．８Ｓｒ０．２ＭｎＯ３电极上进行的氧化电化学还原反应。实验表明反应速度控制步骤随反应温度，氧分压及过电位发生显著变化，近平衡下反应的ｒｄｓ为氧的解离吸附过程。强阳极极化下，电解质表面产生大量电子空穴；强阴极极化下，ＬＳＭ电极表面形成大量氧空位，二者的结果均使界面电导增加，电化学反应区扩展。     

Pt—SPE电极中MnO2粒子的电催化行为及反应溶剂对肉桂醇电解氧化的影响

讨论了ＭｎＯ２在Ｐｔ／ＳＰＥ电极中的电催化行为，指出与电化学反应相比，化学反应是慢步骤。因此提高后续化学反应的速度对提高反应的电流效率至关重要。并讨论了溶剂对肉桂醇电解氧化的影响，指出在水中溶解度大的溶剂有利于肉桂醇的氧化，当以ＴＨＦ作为溶剂进行电解时，电极电位低，生成肉桂醛的电流效率较高。     

苯酚在热氧化法制备的SnO2/Ti电极上的电氧化研究

以热氧化法制备的ＳｎＯ２／Ｔｉ电极作为阳极用于含苯酚酸性溶液的恒电流电解,测定了苯酚浓度、溶液中化学需氧量（ＣＯＤ）以及瞬时电流效率等随电解时间的变化。结果表明,用ＳｎＯ２／Ｔｉ电极代替铂作为阳极可使相同氧化电量下的ＣＯＤ明显下降,而平均电流效率提高了３倍,讨论了两种电极上苯酚氧化的反应机理。     

Pt－SPE电极中MnO_2粒子的电催化行为及反应溶剂对肉桂醇电解氧化的影响

讨论了ＭｎＯ２在Ｐｔ／ＳＰＥ电极中的电催化行为，指出与电化学反应相比，化学反应是慢步骤。因此提高后续化学反应的速度对提高反应的电流效率至关重要。并讨论了溶剂对肉桂醇电解氧化的影响，指出在水中溶解度大的溶剂有利于肉桂醇的氧化，当以ＴＨＦ作为溶剂进行电解时，电极电位低，生成肉桂醛的电流效率较高。     

Na-W-Mn/SiO2催化剂活化甲烷的研究Ⅱ.活性氧物种

制备了不同Ｎａ、Ｗ、Ｍｎ组分的Ｎａ－Ｗ－Ｍｎ／ＳｉＯ２催化剂,并进行了Ｏ２程序升温脱附（Ｏ２－ＴＰＤ）和不同温度下Ｎａ－Ｗ－Ｍｎ／ＳｉＯ２催化剂的ＣＨ４脉冲反应（ＣＨ４－ＰＲ）。研究结果表明,Ｎａ－Ｗ－Ｍｎ／ＳｉＯ２催化剂活化甲烷的活笥氧物种是Ｗ和Ｍｎ提供的、高温下易于流动的表面晶格氧（Ｏ＾２－）。Ｎａ和Ｏ＾２－的活泼性具有重要的促进作用,它可以极化Ｗ、Ｍn的金属一氧键,促进Ｏ＾２－的流动性。Ｎａ     

在线超声Mn~(3+)非均相氧化甲苯制备苯甲醛

在一定的硫酸浓度条件下,以高锰酸钾和硫酸锰为原料,采用均相液相氧化法获得了稳定性良好的Mn3+溶液。并以此溶液为氧化剂,在超声波作用下,选择性氧化甲苯制取苯甲醛。探讨了相关因素对Mn3+溶液的稳定性和苯甲醛收率的影响。实验结果表明,在硫酸浓度为4.0 mol/L,高锰酸钾和硫酸锰物质的量比为1∶12时,可制得浓度较高、稳定性良好的Mn3+溶液;同时在反应温度60℃,硫酸浓度7.0 mol/L,甲苯与Mn3+物质的量比4∶1时,施加59 kHz和175 W的超声波,可促进甲苯的选择性氧化,获得较高收率的苯甲醛。     

掺杂ZnS半导体纳米微晶材料的研究进展

对以ＺｎＳ：Ｍｎ＾２＋为代表的掺杂半导体纳米微晶材料的制备与应用进行了综述并对其发展进行了展望。     

Ab initio prediction of MnOH2/MnOH2 electron transfer reactivity at electron correlation level

An ab initio calculation of electron transfer reactivity of Mn²⁺OH₂/Mn³⁺OH₂ redox system, in gas and in solution, has been made in this paper. The detailed geometry optimization and the scanning of the potential energy surfaces have been carried out at UMP2 (full)/6-311+G^* level. The relevant energy quantities (such as the activation energy and the binding energy) are calculated at different levels of theory (HF, MP2, MP3, MP4 and QCISD and corresponding spin-projection PUHF, PMP2 and PMP3) with the same basis set (6-311+G^*). Both all-electrons and valence electrons have been correlated in energy calculations. The electronic transmission coefficient is calculated using the ab initio potential energy surface slopes and the coupling matrix element determined from the two-state model and the Slater-type d-electron wave functions. The pair distribution function is obtained using both a classical sphere approximation scheme and a novel scheme. The relevant kinetic parameters are obtained at different ab initio levels in terms of the new model. The contact-distance dependence of these parameters and the applicability of the presented models are also discussed.     

LaMgAl11O19∶R(R＝Tb,Mn)的真空紫外光谱特性

采用高温固相反应法合成了LaMgAl11O19∶R (R=Mn, Tb)荧光体, 测量了荧光体的真空紫外激发光谱和相应的发射光谱, 观察到基质吸收带位于170 nm附近, Mn2+离子的吸收位于170～510 nm范围, Tb3+ 离子的4f-5d吸收位于170～250 nm范围. 在147 nm激发下, 它们发射绿光. 真空紫外光谱特性的研究表明, 基质与激活离子之间存在较好的能量传递.     

Effects of Mn2+ on the chrome‐free colored Ti/Zr‐based conversion coating on 6063 aluminum alloy

The conversion coating with golden color and improved corrosion resistance had been prepared by adding Mn²⁺ in the Ti/Zr conversion coating solution. Comparing with that of conversion coating without Mn²⁺, the optimal treatment time of this conversion coating was much shorter and the corrosion resistance was obviously improved. The effect of Mn²⁺ on the formation of golden Ti/Zr conversion coating was thoroughly investigated by means of energy dispersive X‐ray spectroscopy, SEM, XPS, and Raman and electrochemical workstation. The results showed that the conversion coating had a double‐layer structure: the outer layer consisted of the metal‐organic complex and the inner layer was mainly made up of Na₃AlF₆. Mn²⁺ was oxidized into MnOOH in solution and precipitated on the substrate surface which provided the nucleus to Na₃AlF₆ crystal and accelerated Na₃AlF₆ crystal formation and also made the microstructure of conversion coating change to the cubic. The mechanism of the formation of the conversion coating can be deemed as nucleation, growth of Na₃AlF₆ crystal, and formation of metal‐organic complex. Copyright © 2015 John Wiley & Sons, Ltd.     

锌,锰对K—Fe／ZSM—48CO加氢催化反应性能的影响

锌、锰对ＫＦｅ／ＺＳＭ４８ＣＯ加氢催化反应性能的影响范彬彬马静红樊卫斌李瑞丰曹景慧（太原工业大学精细化工研究所，太原０３００２４）关键词ＣＯ加氢，ＺＳＭ４８，助剂效应ＫＦｅ／ＺＳＭ４８在一氧化碳加氢合成低碳烯烃的反应中表现出良好的性能。沸石载体不仅...     

Ca10(Si2O7)3Cl2:Eu2+Mn2+单-基质白光荧光粉的发光性质

用高温固相法合成了颜色可调的Ca10(Si2O7)3Cl2:Eu2+Mn2+荧光粉.研究了它的发光性质和Eu2+与Mn2+之间的能量传递.Eu2+离子在Ca10(Si2O7)3Cl2晶体中形成了峰值为426 nm和523 nm的5d→4f跃迁发光,Eu2+中心向Mn2+中心传递能量,敏化Mn2+离子4T1(4G)-6A1(6S)跃迁而产生585 nm的黄光发射.黄绿蓝3个发射带叠加在单一基质中实现了白光发射.3个发射带的激发谱范围位于250-480 nm处,Ca10(Si2O7)3Cl2:Eu2+Mn2+在紫外-近紫外波段(350～410 nm)范围内有很强的激发,是一种适合InGaN管芯激发的单一基质白光LED荧光粉.     

Microcalorimetric Studies on the Product Inhibition of Hydrolysis of L-arginine Catalyzed by Bovine Liver Arginase

A new thermokinetic reduced extent method for the product inhibition of single substrate enzyme-catalyzed reactions is proposed and compared with the traditional initial rate method in this paper. The arginase-catalyzed hydrolysis of L-arginine to L-ornithine and urea was studied at 37°C in 40 mM sodium barbiturate-HCl buffer solution (pH=9.4). Michaelis constant (K _m) for arginine and maximum velocity (V _m) of the reaction were determined by initial method and thermokinetic method. The activation of exogenous manganese to this reaction was also studied. The product inhibition constant (K _P), which cannot be obtained directly from the initial rate method, was determined by thermokinetic without adding L-ornithine to the reaction system. When the concentration of Mn²⁺ in cell is 0.1 mM, the enzyme gets its full activity. Incubation arginase with appropriate concentration of Mn²⁺resulted in increased Vmax and a higher sensitivity of the enzyme to product with no change in the K _m for arginine. We suggest that the exogenous manganese ions in solution have just recovered the activity of arginase, which was lost in dissolving and dilution, but no effect on the mechanism of the reaction. This revised version was published online in August 2006 with corrections to the Cover Date.     

Mn3+/Mn2+氧化还原体系的旋转圆盘电极法性能

氧化还原液流电池的独特性能受到关注[1～4]。本文综合运用循环伏安法,旋转圆盘电极法研究锰离子浓度较高(0 25～0 35mol·L-1、转速范围较宽(400～4200rpm)、同时考虑过电位的条件下Mn(Ⅲ)/Mn(Ⅱ)电对在RDE铂盘电极上的电极过程动力学并确定有关的动力学参数,了解其影响因素,为该电对作为氧化还原液流电池正极活性材料提供动力学依据。1　实验部分铂电极使用前在铬酸洗液中浸10min,水冲洗干净,蒸馏水淋洗,然后在6 3mol·L-1H2SO4中超声清洗10min,再用CHI660电化学工作站(美国CH仪器公司)控制,以0 05V/s的扫速在-1 0～1 2V之间扫…     

ZnS:Mn2+/聚苯乙烯核壳及ZnS:Mn2+中空球的制备和光谱性质

ZnS:Mn2+ polystyrene (PS) core-shell structures and ZnS:Mn2+ hollow spheres were prepared by a sonoehemical deposition approach. Transmission electron micrograph (TEM) studies show that the PS surface is covered by a thin shell consisted of ZnS: Mn2+ nanoparticles with an average size of 9 nm. ZnS: Mn2+ hollow spheres were obtained by heating the core-shell particles in air at 500 ℃ to drive off PS. The photoluminescence spectrum for the emission band of Mn2+ peaked at 540 nm, and a 45 nm blue shift compared to that of corresponding bulk sample, was discussed based on the Mn-O octahedral distortion induced by shell structure.