驻点壁面催化速率常数确定的研究

以平衡流动作为热环境估算的依据，提出了用数值求解非平衡NavierStokes方程和实验测量热流值确定模型表面材料催化速率常数的方法。用5组分17个化学反应DunnKang空气化学模型和轴对称热化学非平衡NavierStokes方程，对激波管中球头和平头圆柱模型绕流流场进行了数值模拟，给出了驻点热流随催化速率常数变化的分布，并根据激波管实验测量的热流值确定了表面材料Pt、SiO2、Ni和某种飞船材料的催化速率常数，建立了数值分析高焓流动边界层催化特性的软件。

二茂铁衍生物电催化氧化NADH及催化速率常数的测定

用微盘电极研究了二茂铁衍生物的电化学行为及电催化氧化二氢烟酰胺腺嘌吟二核苷酸（ＮＡＤＨ）。用微电极测定了二茂铁衍生物（磺酸基二茂铁，乙酰基二茂铁，羧酸基二茂铁，α－羟乙基二茂铁，α，α＇－二经乙基二茂铁）的扩散系数（分别为３．４×１０￣（－６），６．９×１０￣（－６），１．７×１０￣（－６）．６．２×１０￣（－７），１．５×１０￣（－６）ｃｍ￣２／ｓ）及乙酞基二茂铁电催化氧化ＮＡＤＨ的催化速率常数（４．６８×１０￣３（ｍｏｌ／Ｌ）￣（－１））。探讨了温度、ｐＨ及β－环糊精的络合效应对催化反应的影响。

织物负载TiO_2光催化剂的制备及活性红MS光催化动力学

实验采用溶胶-凝胶法制备纳米TiO2溶胶,棉织物经过浸渍TiO2溶胶—烘干—焙烘法处理,在织物表面低温制备TiO2薄膜。采用X射线衍射仪(XRD)、扫描电子显微镜(SEM)等方法对样品结构和形貌进行分析和表征。在紫外灯照射下,以活性红MS为降解物,研究了制备条件包括TiO2浓度、TiO2溶胶pH值、焙烘温度和焙烘时间对薄膜光催化性能的影响。结果表明在低温下制备的TiO2主要是锐钛矿型,并且薄膜的光催化活性与处理工艺有关。在TiO2浓度为0.423mol/L、TiO2溶胶pH值为1.67、焙烘温度为80℃、焙烘时间为2min的条件下,活性红MS的光催化降解速率常数最大,拟合紫外光下光催化薄膜降解活性红MS为一级反应。

聚苯胺修饰金电极传感器的制备及在废水4-硝基苯酚检测中的应用

4-硝基苯酚(4-NP)为典型具有“三致”效应的环境优先控制污染物。建立废水中4-NP快速、灵敏的检测方法,对提高监测时效具有重要意义。在酸性水溶液中,以过二硫酸铵作引发剂,采用化学氧化法制备聚苯胺(PANI),对4-NP表现出良好的电催化性能。用扫描电镜对电极的表面形貌进行了表征,4-NP在该电极表面的反应为受扩散控制的两电子转移过程,修饰电极的有效面积是裸电极的1.72倍。采用计时电流法、计时电量法分别计算了催化速率常数k_(cat)=1.50×10^(4)L/(mol·s)和4-NP的扩散系数D=5.12×10^(-4)cm^(2)/s。最优条件下,在7.50×10^(-7)~2.31×10^(-3)mol/L浓度范围内,△I与4-NP浓度的对数(lgc)呈良好的线性关系,检出限为0.4μmol/L(S/N=3)。该电化学传感器重复性好、稳定性高、有一定的抗干扰性。对实际水样中4-NP的含量进行了测定,其加标回收率在89.08%~102.30%的范围之间。

二(2-苯并咪唑亚甲基)胺合锰(Ⅱ)配合物水解切割DNA

本文合成并表征了二(2鄄苯并咪唑亚甲基)胺合锰髤配合物。我们利用凝胶电泳实验研究,发现该配合物在近生理条件下,能有效地切割双链pBR322DNA。通过采用在反应体系中加入自由基清除剂,无氧操作实验,脱水丙二醛产物分析,以及T4DNA连接酶连接实验等方法,确认该切割反应是通过水解途径进行的。进一步地,我们对切割反应进行了较详细的动力学研究,求出其催化速率常数Kcat为0.72±0.02h-1(pH=8,37℃)。

Electrochemistry of ABTS at Glassy Carbon Electrodes

The electrochemical and the mass transport behavior of ABTS2-/ABTS＇- （2,2＇-azinobis（3- ethylbenzothiazoline-6-sulfonate）） redox couple at glassy carbon electrode （GCE） in phos- phate buffer solution （PBS, pH=4.4） is studied in detail by cyclic voltammetry combined with rotating disk electrode system. From the i-E curves recorded at different electrode rotating rate, rate constant, and transfer coefficient for ABTS 2-←→ABTS^-＋e reaction at GCE electrode and the diffusion coefficient of ABTS2- in PBS are estimated to be 4.6× 10^-3 cm/s, 0.28, and 4.4× 10^-6 cm^2/s, respectively. The transfer coefficient with a value of ca. 0.28 differs largely from the value of 0.5 that is always assumed in the literature. The origins for the difference of the rate constant determined and the challenges for estimating the stan- dard rate constant are discussed. The performance for such ABTS2- mediated bio-cathode toward oxygen reduction reaction is discussed according to the over-potential drop as well as current output limit associated with the charge transfer kinetics of ABTS2- ←→ABTS-＋e redox reaction and/or the mass transport effect.

Kinetics of esterification of methanol and acetic acid with mineral homogeneous acid catalyst

In this work, esterification of acetic acid and methanol to synthesize methyl acetate in a batch stirred reactor is studied in the temperature range of 305.15–333.15 K. Sulfuric acid is used as the homogeneous catalyst with concentrations ranging from 0.0633 mol·L-1to 0.3268 mol·L-1. The feed molar ratio of acetic acid to methanol is varied from 1:1 to 1:4. The influences of temperature, catalyst concentration and reactant concentration on the reaction rate are investigated. A second order kinetic rate equation is used to correlate the experimental data. The forward and backward reaction rate constants and activation energies are determined from the Arrhenius plot.The developed kinetic model is compared with the models in literature. The developed kinetic equation is useful for the simulation of reactive distillation column for the synthesis of methyl acetate.

Effect of catalytic activities of mixed nano ferrites of zinc and copper on decomposition kinetics of lanthanum oxalate hydrate

Nanostructured zinc-copper mixed ferrite was synthesized using sol-gel method. Different compositions of ferrite, Zn_((1-x))Cu_xFe_2O_4(x=0.0, 0.25, 0.50, 0.75), characterized by XRD, reveal single phase inverse spinel in all the samples. With increasing copper content, the crystallite size increases. The surface morphology of all the samples, studied by SEM, shows porous structure of particles. The prepared samples were also analyzed by FT-IR and TEM. Catalytic activity of the samples was studied on lanthanum oxalate decomposition by thermogravimety.The rate constant k has the highest value with x=0.75 and 5%(mole fraction) of the catalyst and is attributed to high copper content, the mixed sites Cu^(2+)-Fe^+ and/or Cu^+-Fe^(2+) ion pairs besides the one component sites Cu^(2+)-Cu^+, Fe^(3+)-Fe^(2+), as a result of mutual charge interaction. In other words, the increasing activity of mixed oxides is attributed to increase in the content of active sites via creation of new ion pairs. With increasing Zn content, particle size increases. Variation of catalytic activity of ferrite powders is due to the changes of the valence state of catalytically active components of the ferrites, which oxidizes the carbon monoxide released from lanthanum oxalate.

Kinetics and Selectivity in Thermal Hydrocracking and Catalytic Hydrocracking of Asphaltenes

A pentane-insoluble mixture of asphaltenes was processed by thermal hydrocracking and catalytic hydrocracking over Ni-Mo/γ-Al2O3 catalyst in a microbatch reactor at 430 ℃.The experimental data of asphaltene conversion adequately fit second-order kinetics to give the apparent rate constants of 2.435×10-2 and 9.360×10-2 (wt frac)-1 min-1 for the two processes,respectively.A three-lump kinetic model is proposed to evaluate the rate constants for parallel reactions of asphaltenes producing liquid oil (k1) and gas+coke (k3),and consecutive reaction producing gas+coke (k2) from this liquid oil.The evaluated constants for asphaltenes hydrocracking,in the presence and absence of the catalyst,respectively,show that k1 is 2.430×10-2 and 9.355×10-2 (wt frac)-1 min-1,k2 is 2.426×10-2 and 6.347×10-3 min-1,and k3 is 5.416×10-5 and 4.803×10-5 (wt frac)-1 min-1.As compared with the thermal hydrocracking of asphaltenes,the catalytic hydrocracking of asphaltenes promotes liquid production and inhibits coke formation effectively.

Regulating sulfur removal efficiency of fuels by Lewis acidity of ionic liquids

It is urgent to develop a new deep desulfurization process of fuels as the environmental pollution increases seriously. In this work, a series of Lewis acidic ionic liquids （ILs） [C43MPy]Cl/nZnCl2 （n=1, 1.5, 2, 3） were synthesized and used in extraction and catalytic oxidative desulfurization （ECOD） of the fuels. The effects of the Lewis acidity of ILs, the molar ratio of H2O2/sulfur, temperatures, and different substrates including dibenzothiophene （DBT）, benzothiophene （BT） and thiophene （TS）, on sulfur removal were investigated. The results indicated that [C43MPy]Cl/3ZnCl2 presented near 100% DBT removal of model oil under conditions of 323 K, H2O2/DBT molar ratio 6：1. Kinetics for the removal of DBT, BT and TS by the [C43MPy]Cl/3ZnCl2-H2O2 system at 323 K is first-order with the apparent rate constants of 1.1348, 0.2226 and 0.0609 h-1, and the calculated apparent activation energies for DBT, BT and TS were 61.13, 60.66, and 68.14 kJ/mol from 298 to 308 K, re- spectively. After six cycles of the regenerated [C43MPy]Cl/3ZnCl2, the sulfur removal had a slight decrease. [C43MPy]Cl/ 3ZnCl2 showed a good desulfurization performance under optimal conditions.

Koutecky-Levich analysis applied to nanoparticle modified rotating disk electrodes： Electrocatalysis or misinterpretation？

The application of naive Koutecky-Levich analysis to micro- and nano-particle modified rotating disk electrodes of partially covered and non-planar geometry is critically analysed. Assuming strong overlap of the diffusion fields of the particles such that transport to the entire surface is time-independent and one-dimensional, the observed voltammetric response reflects an apparent electrochemical rate o constant koapp, equal to the true rate constant ko describing the redox reaction of interest on the surface of the nanoparticles and the ratio,ψ, of the total electroactive surface area to the geometric area of the rotating disk surface. It is demonstrated that Koutecky-Levich analysis is applicable and yields the expected plots of I-1 versus ω-1 where I is the current and ω is the rotation speed but that the values of the electrochemical rate constants inferred are thereof koapp, not ko. Thus, for ψ 〉 1 apparent electrocatalysis might be naively but wrongly inferred whereas for ψ 〈 1 the deduced electrochemical rate constant will be less than ko. Moreover, the effect of ψ on the observed rotating disk electrode voltammograms is significant, signalling the need for care in the overly simplistic application of Koutecky-Levich analysis to modified rotating electrodes, as is commonly applied for example in the analysis of possible oxygen reduction catalysts.

A comparative study of the electrooxidation of C1 to C3 aliphatic alcohols on Ni modified graphite electrode

Nickel modified graphite electrodes （G/Ni） prepared by galvanostatic deposition were examined for their redox process and electrocatalytic activities towards the oxidation of methanol, ethanol, 1-propanol and 2-propanol in alkaline solutions. The methods of cyclic voltammetry （CV）, ehronoamperometry （CA） and impedance spectroscopy （EIS） were employed. In CV studies, the electrochemical response, peak current varied in the order of MeOH 〉 EtOH 〉 1-PrOH 〉 2-PrOH. Under the CA regime, a higher catalytic rate constant obtained for methanol oxidation was in agreement with CV measurements. Lower charge transfer resistance was obtained for low carbon alcohols oxidation and significantly higher exchange current density was obtained for methanol oxidation.

Portable wastewater treatment system based on synergistic photocatalytic and persulphate degradation under visible light

Highly efficient,low-cost,and portable wastewater treatment and purification solutions are urgently needed for aqueous pollution removal,especially at remote sites.Synergistic photocatalytic (PC) and persulphate (PS) degradation under visible light offers an exceptional alternative for this purpose.In this work,we coupled a TiO^(2-)based PC system with a PS oxidation system into a portable advanced oxidation device for rapid and deep degradation of organic contaminants in wastewater.Using hydrogenation,we fabricated hydrogenated anatase branched-rutile TiO_(2) nanorod (H-AB@RTNR) photocatalysts which enable the PC degradation to occur under visible light and improve the utilization of solar energy.We also discovered that the addition of PS resulted in the synergistic degradation of tenacious and persistent organics,dramatically improving the extent and kinetics of the degradation.A degradation rate of 100%and a reaction rate constant of 0.0221 min^(-1)for degrading 1 L rhodamine B(20 mg L^(-1)) were achieved in 120 min in a specially designed thin-layer cell under visible light irradiation.The superior performance of the synergistic PC and PS degradation system was also demonstrated in the degradation of real industrial wastewater.Both remarkable performances can be attributed to the heterophase junction and oxygen vacancies in the photocatalyst that facilitate the catalytic conversion of PS anions into highly active radicals (·SO_(4)-and·OH).This work suggests that the as-proposed synergistic degradation design is a promising solution for building a portable wastewater treatment system.