纳米Pt/Graphene复合电极的制备及对甲醇电催化性能的影响

采用一步还原法制备直接甲醇燃料电池纳米Pt/graphene (Pt/G)阳极. XRD和SEM表征表明Pt纳米均匀分散于石墨烯表面.循环伏安和计时电流的电化学测定结果表明:复合纳米Pt/G的催化活性和稳定性优于纯铂;采用计时电量法测定298 K时甲醇在硫酸溶液中扩散系数为1.37×10-9 cm2·s-1,以及在不同阶跃电位下甲醇催化氧化反应速率常数k_f.      

FeVO4-H2O2体系中酸性品红的降解性能研究

为提高印染废水的高效、快速降解,进行了FeVO₄催化降解酸性品红水溶液的研究,考察了双氧水的初始浓度、催化剂用量和反应温度对脱色率和反应速率常数的影响。结果表明:在使用FeVO₄作为非均相Fenton催化剂时,酸性品红的氧化降解反应可以使用假一级反应动力学模型进行描述。FeVO₄投加量的增加和温度的增大都可以显著提高酸性品红降解反应速率常数。在H₂O₂浓度为13.6 mmol·L^-1,FeVO₄投加量为1.0 g·L^-1,温度25 ℃条件下,60 min时FeVO₄对酸性品红水溶液的降解率达到94.5%。同时,根据不同温度下的反应速率常数,并结合Arrhenius方程计算出酸性品红降解过程的假一级反应的活化能Ea为60.24 kJ·mol^–1。为利用多相类Fenton催化剂方法处理含酸性品红的印染废水提供理论依据。     

加压下热钾碱溶液吸收二氧化碳的研究

加压下采用纯二氧化碳气体在压力釜中测定了含碳酸钾26.5(重)%的热碱溶液吸收二氧化碳的速率。实验结果表明,80℃下,压力大于2kg/cm~2(表压),吸收速率系数随压力提高而下降,此时,热碱吸收二氧化碳不符合假一级反应模型。测得的吸收速率以近似解整理,结果是满意的。获得的表观反应速度常数k_(OH)与温度T和溶液的转化度f_C的关联式为lnk_(OH)=23.49-(7396/RT) 3.924×f_C 而液相HCO_3~-(或CO_3~(2-))扩散系数与CO_2扩散系数的相对因子D_C与温度、转化度及CO_2分压差△P的关联式为D_C=exp((2499/T)-8.339 2.039×f_C)×((1 0.2△P)/(1 0.2△P_o))     

高锰酸钾氧化嗅味物质β-环柠檬醛的动力学

采用水处理常用氧化剂高锰酸钾对铜绿微囊藻产生的主要致嗅物质β-环柠檬醛(β-cyclocitral)进行氧化去除和动力学分析,并研究高锰酸钾对铜绿微囊藻细胞的破坏和β-环柠檬醛释出及其降解情况.研究结果表明:高锰酸钾与β-环柠檬醛反应符合准二级动力学模型,在溶液pH=7和温度15℃时其速率常数为107.2 mol-1·L·s-1;溶液pH对反应影响不大;当pH=2～9时,动力学表观速率常数kobs为(0.078±0.016)min-;高锰酸钾的加入造成藻细胞的破裂程度达到90%,使主要存在于胞内的β-环柠檬醛释出并降解;高锰酸钾能将铜绿微囊藻细胞内的β-胡萝卜素氧化成β-环柠檬醛,导致总β-环柠檬醛浓度在氧化过程中先升高后降低.     

DMF对FOX-7热分解的影响

FOX-7作为一种新型高能钝感炸药被广泛研究,其结晶、重结晶等过程均在DMF中进行。为研究FOX-7在DMF中的热安全性,首先使用差示扫描量热-热重(DSC-TG)同步热分析仪研究FOX-7的热分解过程,分别测得升温速率为5℃/min,10℃/min,15℃/min,20℃/min的DSC和热重-微商热重法(TG-DTG)曲线;并得出其分解过程包括一个吸热转晶峰(116℃左右)和两个分解放热峰(226℃和294℃左右)。然后,使用自行设计的临界爆炸温度测试装置,通过小容量法测定FOX-7、DMF以及FOX-7溶液的临界爆炸温度。结果表明,在试验条件下,FOX-7溶液的临界爆炸温度低于纯FOX-7的临界爆炸温度,说明DMF溶液促进了FOX-7的热分解反应。当FOX-7溶液质量分数为5%时,临界爆炸温度最高,热安全性最好。     

对硝基乙苯电还原特性的研究

采用循环伏安法、计时电量法等电化学测试手段,研究了对硝基乙苯的电还原行为,研究表明乙基使峰电位负移,电极过程受扩散控制。测得扩散系数为0.71×10-4cm2/s、反应电子数5.5。恒电位电解电流效率为58%,产品收率43%。     

冰镍的电化学行为 第一部分:硫酸盐体系中硫化镍阳极电化学溶解动力学

本文采用旋转圆盘电极并结合线性扫描、恒电位单阶跃、恒电流电解、循环伏安等电化学测试方法综合考察了Ni_3S_2在硫酸盐溶液中的阳极电化学溶解动力学规律,查明了其活性溶解反应的控制步骤;并利用Au-Hg齐环电极检测到中间硫氧离子的还原电流,提出了Ni_3S_2阳极分段溶解逐步氧化的反应机理。求取了反应速度常数、固相扩散系数、反应活化能等动力学参数。本文是冰镍电化学行为研究工作之一。     

偕胺肟基纤维对Ni2+的吸附动力学

以偕胺肟基纤维(AOCF)为吸附材料,对不同初始浓度的Ni2+溶液进行吸附规律研究.结果显示,室温下AOCF对Ni2+的吸附符合Freundlich等温吸附经验式.由不同初始浓度下吸附时间与溶液浓度的关系,用微分法确定反应的级数;在不同温度下对初始浓度为0.033 mol@L-1的Ni2+溶液进行吸附,确定各温度下的反应速率常数,由速率常数与温度的关系,结合Arrhenius方程可得出反应的活化能.研究结果表明,偕胺肟基纤维对水溶液中的Ni2+吸附反应符合一级反应动力学特征;其速率方程c=c0e-kt,速率常数k=0.1716×e-Fa/RT,活化能Ea=13.52 kJ/mol.     

1,3-二苯基-4-丁酰基-5-吡唑酮离解常数的测定

采用电位滴定法 ,在水 -二氧六环混合溶剂体系中 ,测定新β-二酮螯合剂 1,3-二苯基 - 4-丁酰基 - 5 -吡唑酮在不同二氧六环含量时的离解常数 ,通过外推 ,求得其在温度为 2 5± 0 .1℃ ,离子强度为 0 .10时 ,在纯水中的离解常数 p Ka为 4.38。     

硫酸介质中3,5-二(2-吡啶基)-1,2,4-三唑对铜的缓蚀作用的电化学研究

利用动电位扫描、循环极化、循环伏安等电化学方法研究了3,5-二(2-吡啶基)-1,2,4-三唑(HBPT)在0.5 mol/L H2SO4介质中对铜的缓蚀性能.极化曲线研究表明3,5-二(2-吡啶基)-1,2,4-三唑在0.5 mol/L硫酸溶液中对铜的阳极反应起抑制作用,对铜的阴极反应起促进作用,属于阳极型缓蚀剂.循环伏安研究显示3,5-二(2-吡啶基)-1,2,4-三唑可能在电极表面产生吸附或与一价铜发生作用,从而在0.5 mol/L硫酸溶液中对铜起到缓蚀作用.     

超声波下酸化碘酸钾和亚硫酸钠反应的反应速率研究

分别测定在有超声波作用和在无超声波作用条件下 ,酸化碘酸钾 (KIO3 )和亚硫酸钠 (Na2 SO3 )反应的反应速率方程式及活化能 ,从而研究该反应的机理以及超声波在该反应中的作用 ,并确定反应的最佳条件。实验得出 ,超声波对该反应有一定的促进作用 ,但是这种促进作用只提高反应的速率常数和降低反应的活化能 ,并没有改变反应机理。在超声波功率为 30 0W时 ,反应的速率方程表示式为 :v =k·c1 0 9(KIO3 ) ·c1 0 0 (Na2 SO3 )·c1 0 8(H+ ) ,其中 :k =95 0 (mol-1·L) 2 ·s-1,活化能为 17 35kJ·mol-1。实验还得出 ,在温度为2 98K时 ,当KIO3 与Na2 SO3 的初始浓度比为 2∶5 ,H+ 的初始浓度为 0 0 4 2 8mol·L-1,超声功率为 30 0W时 ,反应速率为最快 ,即v =4 31× 10 -4mol·L-1·s-1)。     

Kinetics of C2(a3Πu) radical reactions with NO, N2O, O2, H2 and NH3

Pulsed laser photolysis/laser-induced fluorescence (LP-LIF) is utilized to measure rate constants for C₂(a³Π_u) reactions with NO, N₂O, O₂, H₂ and NH₃. Multiphoton dissociation of C₂Cl₄ at 266 nm is employed for the generation of C₂(a³Π_u) radicals. The C₂(a³Π_u) concentration is monitored by the fluorescence of the (0, 0) band of the (d³Π_g&#8596;a³Π_u) transition at 516.5 nm. C₂(a³Π_u) removal rate constants for the reactions are determined as k_NO = (5.46 ± 0.10) × 10^-11 cm³ molecule^-1 s^-1 , k_N2O = (1.63 ± 0.20) × 10^-13 cm³ molecule^-1 s^-1 , k_N2O = (1.58 ± 0.16) × 10^-11 cm³ molecule^-1 s^-1, k_O2 = (5.92 ± 1.00) × 10^-14 cm³ molecule^-1 s^-1, k_H2< 1.0× 10^-14 cm³ molecule^-1 s^-1. Based on the data analysis and theoretical calculation, we suggest that the C₂(a³Π_u) reactions with H₂ and NH₃ proceed via the hydrogen abstraction mechanism, barriers exist at the entrance channel of the reactions of C₂(a³Π_u) with H₂ and NH₃.     

Binding and endocytosis of monoterbium transferrin by K562 cells

Human serum apotransferrin is the major iron-tran- sport protein in blood. The protein binds iron as Fe3+ at two similar, but not identical, high-affinity binding sites. Although iron bound to human serum apotransferrin is less then 0.1% (~3 mg) of the total body iron, dynamically it is the most important iron pool with the highest rate of turnover. The turnover of transferrin iron is in the order of 30 mg per day and, normally, about 80% of this iron are transported to the bone marrow for hem…     

Walsh spectrum properties of rotation symmetric boolean function

Rotation symmetric function was presented by Pieprzyk. The algebraic configuration of rotation symmetric（RotS） function is special. For a Rots n variables function f（x1, x2, …, xn） we have f（ρn^k （x1, x2, …xn））=f（x1, x2, …, xn） for k=0, 1, …, n-1. In this paper, useing probability method we find that when the parameters of RotS function is under circular translation of indices, its walsh spectrum is invariant. And we prove the result is both sufficient and necessary.     

Microcalorimetric study on the antibiotic activity of clarithromycin and erythromycin

By using LKB-2277 Bioactivity Monitoring System, the heat effect changes in the process of inhibitory action of clarithromycin and erythromycin onEscherichia coli at 37°C were determined. Quantitative analysis showed that relationship between antibiotic concentrationc and rate contantk ofEscherichia coli growth, and half inhibitory ratio concentration IC₅₀: clarithromycin:k=0. 030 03–1. 1736×10⁻³ c, 8. 45 mg ·L⁻¹; erythromycin:k=0.031 08–8.4657×10⁻⁴ c, 14. 45 mg·L⁻¹. As a result of the microcalorimetry experiments, it not only indicated that antibacterial activity of clarithromycin was stronger than that of erythromycin, but also reported the changeable features of thermodynamics of the bacterial cell in biological, biochemical and metabolic process under different drug action. Foundation item: Supported by Natinal Natural Science Fundation of China (29973030), Natural Science Fundation of Hubei Province (98J052) and Post-doctoral Science Fundation of China Biography, SHEN Xue-song (1956-), Associate professor Research direction: biothermochemistry.     

Rate constants for the reaction of ozone with <Emphasis Type="Italic">n</Emphasis>-butyl, <Emphasis Type="Italic">s</Emphasis>-butyl and <Emphasis Type="Italic">t</Emphasis>-butyl methyl sulfides

The rate constants for the ozone reactions with n-butyl methyl sulfide （n-BMS, CHaCH2CH2CH2SCH3）, sec-butyl methyl sulfide （s-BMS, CH3CH2（CH3）CHSCHa） and tert-butyl methyl sulfide （t-BMS, （CH3）3CSCH3） were measured using our smog chamber under supposedly pseudo-first-order conditions at 30002 K and 760 Torr. The experimental determined rate constants for n-butyl, s-butyl and t-butyl methyl sulfide are （1.23 ± 0.06）×10-19, （5.08 ± 0.19）×10-20 and （2.26 ± 0.14）×10-20 cm3 molecule-1· s-1, respectively. The reactivity-structure relationship of the reactions was discussed and used to illustrate the mechanism of the ozone reaction with thioethers. The results enrich the kinetics data of atmospheric chemistry.     

Restricted allowable generalized quantum gates

An allowable generalized quantum gate (introduced by Long, Liu and Wang) has the form of U = Σ _k=0 ^d−1 c _k U _k , where U _k’s are unitary operators on a Hilbert space H and |Σ _k=0 ^d−1 c _k |⩽1 and |c _k |⩽1 (0⩽k⩽d−1). In this work we consider a kind of AGQGs, called restricted allowable generalized quantum gates (RAGQGs), satisfying 0 < Σ _k=0 ^d−1|c _k |⩽1. Some properties of the set RAGQG(H) of all RAGQGs on H are established. Especially, we prove that the extreme points of RAGQG(H) are exactly unitary operators on H and that B(H)=R ⁺ RAGQG(H).     

An explanation to the high efficiency ofm-THPC (temporfin) used in photodynamic therapy

Meso-tetrahydroxylphenyl chlorin (m-THPC) is one of the most efficient prospective sensitizers used in photodynamic therapy (PDT). ESR spectroscopy, fluorescence quenching experiments and cyclic voltammogram measurement were used to study its redox properties. The results showed that the ability of m-THPC generating superoxide radical anions was very strong, and the rate constant of m-THPC fluorescence quenching by oxygen k_q (O₂)=1.46×10¹⁰ mol^-1·s^-1. The values of fluorescence quen- ching rate constant of m-THPC by some other electron acceptors, such as methyl viologen (MV²⁺) and anthraquinone (An), were also measured. And they were k_q (MV²⁺)=5.51×10⁹ mol^-1·s^-1, k_q (An)=7.81×10⁹ mol^-1·s^-1. The oxidation potential of m-THPC was examined to be +0.62 V (vs. NHE) in acetonitrile. All these suggested that m-THPC should be a much stronger electron donor than photofrin, the currently used in clinical photodrug, and may react easily through electron transfer with biological matter to yield various radicals. So it seemed reasonable that the type Ⅰ reaction may play an important role in the high activity of m-THPC-PDT.     

氮化碳自组装包裹对SnO2TiO2复合锂离子电池负极材料电化学性能的影响

通过简单的石墨相氮化碳(g-C₃N₄)纳米片自组装沉积法,制备了g-C₃N₄包裹的SnO₂-TiO₂纳米复合材料.扫描电子显微镜观察显示,g-C₃N₄均匀地包裹在SnO₂-TiO₂纳米颗粒上.SnO₂-TiO₂-C₃N₄纳米复合材料被用作锂离子电池的负极材料,在0.2C的倍率下循环20次后,比容量达到380.2 mA·h·g^-1,明显高于未经g-C₃N₄包裹的纯的SnO₂(51.6 mA·h·g^-1)和SnO₂-TiO₂纳米复合材料.在0.1~0.5C的倍率充放电测试中,SnO₂-TiO₂-C₃N₄纳米复合材料的比容量仅从490 mA·h·g^-1衰减到330 mA·h·g^-1,高倍率下抗衰减性能优于同类材料.材料优异的电化学性能归功于g-C₃N₄的包裹处理,这不仅增强了固体电解质界面(SEI)的稳定性,也抑制了锂离子嵌入-脱出时SnO₂和TiO₂纳米颗粒的体积变化.