共查询到20条相似文献,搜索用时 0 毫秒
1.
Andjela Abu-Rabi Danijela Jain Slavko Mentus 《Journal of Electroanalytical Chemistry》2007,600(2):364-368
The electrochemical oxidation of the hydroxide ion was studied on a gold rotating disc electrode (RDE), in aqueous NaOH solutions in the presence of lithium perchlorate as a supporting electrolyte. By potentiodynamic polarization within the limits −1.6 V and +1.6 V vs. SCE, it was demonstrated that the overvoltage of the OH− ion oxidation reaction may be significantly reduced with a 5 min long delay at the vertex cathodic potential of −1.6 V. This finding was explained in terms of the type of gold oxide formed on the gold surface under different experimental conditions. 相似文献
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This work reports on the electrocatalytic oxidation of hydroxide using different central metal ion phthalocyanines and porphyrins immobilized on gold electrodes. The apparent electrocatalytic activity of cobalt phthalocyanine or porphyrin modified electrodes was found to be the greatest among the present series of metal ion macrocycles investigated. Copper and unmetallated phthalocyanine or porphyrin modified electrodes show no electrocatalytic behaviour towards hydroxide, such as bare gold. A possible mechanism for the enhanced reactivity of cobalt ion macrocycles towards the oxygen evolution is given. It is also stated that the electrocatalytic activity towards an adsorbate involves several aspects, such as the coordination state of the central metal ion, the nature of the ligand, the stability of the complexes, the number of d electrons, the energy of orbitals and the strength of the bonding between the central metal ion and the axial ligand. 相似文献
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采用纳米二氧化硅模板辅助的共炭化方法,以煤转化副产物煤焦油的蒽油馏分为碳源、三聚氰胺为氮源,制备出高氮元素掺杂、发达介孔结构的氮掺杂介孔炭(NMCs)。结合元素分析、扫描/透射电镜观察、低温氮气吸附-脱附及X射线光电子能谱测试分析,对比考察了不同合成条件对所得样品的组成、结构及其室温催化脱硫性能的影响。结果表明,控制合适的模板剂用量、碳/氮源比例和炭化温度(700℃),所制备的样品具有适宜的氮元素掺杂量及丰富的吡啶/吡咯氮构型、较大比表面积、介孔孔径和孔容,在室温下对H2S的氧化脱除显示出高效催化性能。 相似文献
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乙醇既是一种被广泛使用的溶剂, 也大量存在于乙醇燃料车尾气中. 它是一种挥发性有机化合物(VOCs), 能直接参与光化学反应影响空气质量, 因此去除乙醇很有必要. 催化氧化法消除VOCs 是很有前景的技术, 其关键是催化剂的制备和筛选. 目前, 用于乙醇催化氧化的催化剂主要是贵金属催化剂(Pt, Pd, Rh, Au, Ag)和金属氧化物催化剂(Cu, Mn, Co, Fe),此外, 还有一些钙钛矿型催化剂. MnO2具有多种结构(α, β, γ和δ)和形貌(管状, 棒状, 球状和孔状等). 不同形貌和结构的MnO2具有不同的VOCs 催化氧化性能. 我们已经报道了介孔MnO2, 特别是三维有序介孔MnO2, 具有良好的乙醇催化氧化活性, 有一定的应用前景. 然而, KIT-6老化温度对介孔MnO2孔径的影响, 以及MnO2孔径对催化氧化乙醇活性的影响尚不清楚. 如果通过调整KIT-6老化温度改变介孔MnO2的孔径, 很有可能改善催化剂低温还原性, 氧物种和活性位等, 进而提高其催化性能. 本文以40, 100和150 ℃ 老化合成的KIT-6介孔硅为硬模板, 制备出不同的介孔MnO2催化剂, 分别记作Mn-40, Mn-100和Mn-150, 用于乙醇氧化反应中, 讨论了催化剂孔径对其活性的影响. 采用X 射线粉末衍射(XRD), 氮气吸附-脱附(BET), 扫描电子显微镜(SEM), 氢气程序升温还原(H2-TPR), 氧气程序升温脱附(O2-TPD), X 射线光电子能谱(XPS)等技术对催化剂进行了表征. XRD 广角结果表明, 各催化剂均具有软锰矿型MnO2晶相, 其中Mn-40催化剂存在少量Mn2O3晶相. XRD 小角和SEM结果表明, 各催化剂均为介孔材料, Mn-100催化剂的有序度和对称性最好, KIT-6老化温度的改变使Mn-40和Mn-150的有序度和对称性降低. BET 结果表明, Mn-40, Mn-100和Mn-150分别具有三孔, 双孔和单孔体系. 随着KIT-6老化温度的降低, KIT-6的孔径降低, 而介孔MnO2催化剂的孔径增加. XPS 结果表明, Mn-40因少量Mn2O3晶相的存在而具有较多的Mn3+阳离子和表面晶格氧物种, 能增加催化剂氧空位的数量, 有利于氧物种的吸附, 活化和迁移, 从而增强催化活性. TPR 和TPD表明, Mn-40催化剂具有良好的低温还原性, 它的氧物种容易在低温下脱附并参与氧化反应. 催化剂活性测试结果表明, 随着介孔MnO2催化剂的孔径增加, 其活性增加. 催化剂孔径和活性从大到小的顺序为Mn-40>Mn-100>Mn-150. 以老化温度为40 ℃的KIT-6模板制备的Mn-40催化剂, 具有较高的乙醇转化频率 (TOF), 120 ℃的TOF 为0.11 s-1. Mn-40催化剂具有良好的乙醇氧化催化活性归因于较大孔径, 其孔径呈三孔体系分布, 最大孔径分布在1.9, 3.4和6.6 nm 处, 三孔体系的形成是因为催化剂孔道的对称性和有序度降低. 此外, Mn-40催化剂具有良好的乙醇氧化催化活性也归因于由较多Mn3+阳离子引起的较多表面晶格氧物种和氧空位以及较好的低温还原性. 相似文献
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A. A. Shaikh M. Begum A. H. Khan M. Q. Ehsan 《Russian Journal of Electrochemistry》2006,42(6):620-625
Electrochemical redox behavior of Fe-vit B6 complex is investigated in HEPES buffer in the pH range 5.1–13.1 using cyclic voltammetry. Well-defined anodic and cathodic
peaks are observed in the voltammograms at pH 13.1. At pH 8.0, only one cathodic peak and at pH 5.1, only one anodic peak
are found. At all the pH values, the peak potential separation is much higher than that of a reversible electrochemical reaction.
The peak current ratio (i
pa/i
pc) is less than unity and decreases with the scan rate.
Published in Russian in Elektrokhimiya, 2006, Vol. 42, No. 6, pp. 691–697.
The text was submitted by the authors in English. 相似文献
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Ali F. Al-Ghamdi 《Journal of Saudi Chemical Society》2009,13(3):235-241
Square-wave voltammetry was used to explore the adsorption property of ofloxacine complex with iron ion on the hanging mercury drop electrode (HMDE). By employing the adsorptive stripping voltammetric approach, a sensitive electroanalytical method for the quantitative analysis of ofloxacine antibiotic was achieved. A well-developed voltammetric peak was obtained in pH 7.5 Britton–Robinson buffer (B–R buffer) at ?1400 mV. The cyclic voltammetric studies indicated that the reduction process was irreversible and primarily controlled by adsorption. An investigations of the variation of adsorptive voltammetric peak current with supporting electrolyte, pH, accumulation time, accumulation potential, ion concentration, scan rate, pulse amplitude, SW frequency, working electrode area and convection rate has resulted in the recognition of optimal experimental conditions for ofloxacine analysis. The studied electroanalytical signal showed a linear response for ofloxacine in the concentration range 5 × 10?7 to 1.7 × 10?6 mol l?1 (r = 0.999). A limit of detection of 1.1 × 10?8 mol l?1 (3.98 ppb) with relative standard deviation of 1.21 RSD% and mean recovery of 99.6% were obtained. Possible interferences by several substances usually present in pharmaceutical formulation were also evaluated. The analytical quantification of ofloxacine in commercially available pharmaceutical formulation was performed and compared with data from HPLC technique. 相似文献
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Nunes CD Valente AA Pillinger M Rocha J Gonçalves IS 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(18):4380-4390
Mo K-edge XAFS spectra have been measured for ordered mesoporous silica MCM-41 grafted with the complexes [MoO2X2(thf)2] (X=Cl, Br). For grafting reactions in the absence of triethylamine, materials with 1 wt. % Mo are obtained; the Mo K-edge EXAFS results indicate the co-existence of isolated surface-fixed monomeric species [MoO2[(-O)3SiO]2(thf)(n)] and [MoO2[(-O)3SiO]X(thf)(n)]. When Et3N is used in the grafting reactions, materials with 4 wt. % Mo are obtained. The EXAFS data for the material prepared using [MoO2Cl2(thf)2] and Et3N indicate the presence of dinuclear species with two Mo(VI) centres, each with two Mo=O groups and each linked by one or two oxo bridges (Mo...Mo 3.27 A). The molybdenum centres in the material prepared using the dibromo complex comprise mainly isolated four-coordinate dioxomolybdenum(VI) and trioxomolybdenum(VI) monomeric species, with a small contribution from dimeric species. All materials were further characterised in the solid state by powder X-ray diffraction, N2 adsorption analysis, MAS NMR (13C, 29Si) and FTIR spectroscopy. The derivatised MCMs perform differently as catalysts in the liquid-phase oxidation of various olefins and alcohols with tert-butyl hydroperoxide. The highest alkene epoxidation activity was recorded for the catalysts with low metal loading, whereas the material containing oxo-bridged dimers had the highest activity for oxidation of alcohols. The recyclability of all the catalysts was tested: the catalytic activity of the derivatised materials tended to stabilize with ageing. 相似文献
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H. M. Naseem Akhtar A. A. Shaikh M. Q. Ehsan 《Russian Journal of Electrochemistry》2008,44(12):1403-1408
The electrochemical redox behavior of Fe(II)/Fe(III) systems formed during the oxidation of complexes [Fe(C7H4NO3S)2(H2O)4] · 2H2O (Fe-sac) and [Fe(C7H4NO3S)2(C12H8N2] · 2H2O (Fe-sac-phen) have been investigated using cyclic voltammetry in the aqueous medium. In the CVs one pair of well-defined
cathodic and anodic peaks appear for the transfer of single electron in the Fe-sac complex. The peak potentials are much wider
separated as compared with the free (uncoordinated) Fe(II)/Fe(III) system. The ΔE values demonstrate that the electrode process is irreversible. In the presence of secondary ligand, 1,10-phenanthroline (Fe-sac-phen
complex), the redox behavior of iron complexes is quasireversible. The effect of pH on the redox behavior of iron system is
studied in acetate buffer.
Published in Russian in Elektrokhimiya, 2008, Vol. 44, No. 12, pp. 1504–1509.
The text was submitted by author in English 相似文献
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《Electroanalysis》2004,16(16):1359-1365
Electrochemical oxidation of catechols has been studied in the presence of cyanide ion as nucleophile in aqueous solution, by means of cyclic voltammetry and controlled‐potential coulometry. The results indicate that the participation of catechols in the Michael reaction with cyanide ion to form the corresponding o‐dihydroxybenzonitrile. Based on an EC mechanism, the homogeneous rate constants were estimated by comparing the experimental cyclic voltammetric responses with the digital simulated results. 相似文献
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Transfer of lanthanum ion across the adsorption of emulsifier OP at the water-nitrobenzene interface
The transfer of lanthanum ion facilitated by diantipyrylmathane (DAM) across the water/nitrobenzene (w/nb) interface and the adsorption of emulsifier OP at the w/nb interface has been studied by the cyclic voltammetry.The mechanism of the charge transfer reactions is discussed.It has been concluded that the transfer of rare earth metal ion (La3+) facilitated by neutral ionophore (DAM) at the w/nb interface is E mechanism and the nonionic surfactant (emulsifier OP) can participate in the charge transfer process as an ionophore,charge transfer catalyst and inhibitor. 相似文献
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研究了油/水界面电解的示差半微分循环伏安行为。在0.01mol/L LiCl(w)-0.01mol/L TBATCIPB(nb)体系“电位窗”比TBATPB(nb)向正方向扩展约50mV,残余电流基本消除,使“电位窗”内的平台向左右拓宽约50mV。算得界面电容约为16μF/cm~2。考察了琥珀酰胆碱离子在w/nb界面的传递伏安特性,结果与一般半微分循环伏安法相似。但峰形改善,检测限降低一个数量级(1×10~(-6)mol/L),相对标准偏差在5%以内,可用于定量测定琥珀酰胆碱。 相似文献
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The electrode/electrlyte interface is of great signifance to photoelectrochemical (PEC) water oxidation as the reaction mainly occur here. Herein, we focus on the effect of supercapactance of the electrode/electrlyte interface on the performance of PEC. It is discovered that the supercapacitor on the interface is crucial because it links the charge transport and solution ion adsorption on its two sides. In this study, we demonstrate an approach to promote the performance of TiO2 nanowire array (TiO2 NWs) photoanode in photoelectrochemical cells (PECs) by increasing its supercapacitance. A 2−5 nm carbon layer was coated and the interface supercapacitance increases by about 150 times. This enhances the separation rate of electron-hole pairs by collecting more holes. Meanwhile, it also promotes the water oxidation rate by adsorbing more OH− on its surface. As a result, the photocurrent density of C-TiO2 NWs was about 8 times higher than that of its carbon-free counterpart. This approach of increasing the supercapacitance of photoanodes would be attractive for enhancement of the efficiency of PECs and this work demonstrate the importance of supercapacitance of the interface for PECs. 相似文献
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V. S. Arutyunov V. Ya. Basevich V. I. Vedeneev Yu. V. Parfenov O. V. Sokolov 《Russian Chemical Bulletin》1996,45(1):45-48
A decrease of the rate of high pressure oxidation of very rich methane-oxygen mixtures with increasing oxygen concentration was found. The results were confirmed by kinetic simulation of the process. A very distinct temperature dependence of the rate of oxygen conversion can be explained on the basis of a critical change in the reaction mechanism.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 53–56, January, 1996. 相似文献
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Xiubin Ren Xiangyun Guo . College of Chemistry Chemical Engineering Xi’an University of Science Technology Xi’an Shaanxi China . State Key Laboratory of Coal Conversion Institute of Coal Chemistry Chinese Academy of Sciences Taiyuan Shanxi 《天然气化学杂志》2011,20(5):503-506
Monte Carlo method was applied to simulate the oscillatory behavior during partial oxidation of methane under non-isothermal condition. The simulation was performed to examine the influences of heat transfer constant and particle size on the kinetic oscillation. The oscillatory period and amplitude were observed to increase with the increase of heat transfer constant. The increase of catalyst particle size was found to result in short oscillatory period and more or less regular oscillations combined with the formation of oxide down to L=100. 相似文献