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选择铂为电极电催化乙炔合成草酸,通过紫外-可见分光光度法和红外光谱法对产品进行表征,利用第一性原理计算方法探讨乙炔在催化剂Pt(111)表面的吸附情况,采用循环伏安法(CV)研究铂电极在硫酸钠溶液中氧化乙炔的电极过程,重点测定电极的稳态极化曲线并根据极化曲线推算塔菲尔斜率,结合表观传递系数及反应级数对拟定的乙炔电催化氧化制备草酸的反应机理进行验证. 实验结果表明,乙炔分子在Pt(111)面上呈平行桥键构型时吸附最稳定;铂电极在含体积分数为2%丙酮的0.4 mol·L-1硫酸钠溶液中可将乙炔电催化氧化为草酸;反应的速率控制步骤为. 相似文献
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氮氧自由基电催化氧化盐酸伪麻黄碱的电化学行为及其电化学动力学性质 总被引:1,自引:0,他引:1
运用循环伏安法(CV)、计时电流法(CA)在玻碳电极(GCE)上研究了以氮氧自由基(4-羟基-2,2,6,6-四甲基-哌啶-1-氧自由基,TEMPOL)为均相电子转移媒体电催化氧化盐酸伪麻黄碱(PEH)的电化学行为及其电化学动力学性质.研究结果表明,PEH在GCE上的电化学氧化过程十分迟缓,不易直接发生电化学氧化反应.而在TEMPOL存在时PEH在0.641 V处出现了一个不可逆的氧化峰,且峰电流大幅度增加,表明TEMPOL对PEH的电化学氧化具有良好的电催化作用.在5~1 000 mV/s扫描速度范围内,氧化峰电流(Ipa)与扫描速率平方根(v1/2)呈线性关系,此催化氧化反应是一受扩散控制的电极过程.测定了电催化氧化反应动力学参数:电子转移系数α为0.72,催化反应速率常数k为(2.26±0.05)×103(mol/L)/s.催化体系氧化峰电流与PEH浓度在2.0×10-5~2.0×10-3mol/L范围内呈良好的线性关系,检出限为1.0×10-5mol/L. 相似文献
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新型CNT/nano-TiO_2复合膜电极的制备及其异相电催化性能 总被引:1,自引:1,他引:0
采用溶胶-凝胶法制备了碳纳米管/纳米TiO2(CNT/nano-TiO2)复合溶胶,通过提拉法将复合溶胶涂覆在Ti基体上制得CNT/nano-TiO2复合膜修饰电极(C电极),其电化学性能经循环伏安、计时库仑、交流阻抗谱(EIS)等方法研究.研究结果表明,CNT可阻碍nano-TiO2粒子团聚.在循环伏安图中,C电极的氧化还原峰电流比nano-TiO2膜修饰电极(P 电极)的高出两倍多.通过对草酸溶液的异相电催化反应进一步证明C电极比P电极具有更高的电催化活性,而且对双氧水也有很强的异相电催化还原能力. 相似文献
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以9-氮杂双环[3.3.1]壬烷-N-氧基自由基(ABNO)为电催化媒介, 在NaClO4-MeCN溶液中伯胺通过自氧化偶联反应生成对应的亚胺. 采用循环伏安法研究了ABNO对伯胺的电催化性能. 在相同条件下, 与2,2,6,6-四甲基哌啶氮氧自由基相比, ABNO在伯胺的自氧化偶联反应中表现出更好的电催化反应活性. 采用电化学原位红外光谱技术分析其中间产物为Ph—CH=NH. 在优化的反应条件下, 一系列芳香伯胺可在ABNO电催化作用下自氧化偶联生成对应的亚胺, 产率较高. 相似文献
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应用晶种生长法制得金纳米立方体,Aucore-Pdshell和Aucore-Pdshell-Ptcluster电催化剂,通过改变溶液的H2PdCl4和H2PtCl6的用量以控制Pdshell的厚度和Ptcluster的覆盖度.采用扫描电镜(SEM)、透射电镜(TEM)观察了金纳米立方体的表面结构.利用循环伏安法(CV)研究了不同Pd层厚度的立方体形Aucore-Pdshell纳米粒子和不同Pt岛覆盖度的立方体形Aucore-Pdshell-Ptcluster纳米粒子对甲酸氧化的电催化性能.结果表明,与立方体形Aucore-Pdshell纳米粒子相比,"核-壳-岛"结构的立方体形Aucore-Pdshell-Ptcluster纳米粒子对甲酸的电氧化具有更高活性.当Pd壳层厚度为3层,Pt岛覆盖度为0.5时,电催化活性最高. 相似文献
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金电极表面聚赖氨酸固定微过氧化物酶-11的电化学研究 总被引:1,自引:0,他引:1
通过聚赖氨酸修饰将微过氧化物酶-11(MP-11)固定在金电极表面,制备成MP-11修饰电极.修饰在电极表面上的MP-11的血红素活性中心与电极之间可进行直接的电子传递反应,其氧化还原式电位为-0.39V.该修饰电极对氧的还原具有电催化活性.当MP-11与咪唑发生轴向配位反应时,其氧化还原式电位发生负移,此时对氧的还原不再具有电催化活性. 相似文献
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红外光谱法研究苯胺和环氧丙烷的共聚机理及共聚物的表征 总被引:1,自引:0,他引:1
采用原位红外光谱技术对苯胺和环氧丙烷的电化学共聚机理进行了研究, 研究结果表明, 环氧丙烷能在苯胺及其低聚物阳离子自由基的催化作用下发生α位开环, 与苯胺发生电化学共聚, 生成了含有芳香-脂肪醚结构的共聚物. 采用显微红外成像技术研究苯胺和环氧丙烷共聚物在电极表面的生长特点发现, 该共聚物能在电极表面从中间向两侧有规律地生长. 相似文献
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MeiChaoLI ChunAnMA 《中国化学快报》2005,16(4):551-553
A novel copolymer of polyaniline-poly(propylene oxide) (PAN-PPO) was prepared by cyclic voltammetry (CV) and characterized by FFIR and SEM. It showed good electroactivity for methanol oxidation in H2SO4 solution. 相似文献
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Palladium + tin oxide (Pd + Sn oxide) catalyst was used for methanol electrooxidation, the chemical composition of which was studied by XPS. The XPS st 相似文献
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The electrocatalytic oxidation of nitric oxide(NO) at a glass carbon electrode(GC) modified with functionalized single-walled carbon nanotubes(SWCNTs) was investigated by cyclic voltammetry(CV) and electrochemical impedance spectroscopy(EIS).It was found that the SWCNT modified electrode could speed greatly up the electron transfer rate compared with the bare GC electrode.After the SWCNT was treated with alkali or mixed acids,the reaction rate and activation energy of NO electrooxidation were changed to different extent.Chemical modification of the SWCNT surface is one of the most powerful methods to change the sensitivity of NO electrooxidation reaction.The modified electrode with SWCNT obtained by the firstly alkali treatment and then the mixed acids treatment was the best one for NO electrooxidation,the result of CV was also confirmed by that of EIS.The anodic processes of NO were recognized more clearly by exploring the reaction mechanism of NO electrooxidation at the SWCNT modified electrode. 相似文献
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The adsorption and thermal chemistry of 2-butanol and propylene oxide, each individually and when coadsorbed together, were characterized on Pt(111) single-crystal surfaces by using temperature programmed desorption and reflection-adsorption infrared spectroscopies. The formation of chiral superstructures on the surface upon the deposition of submonolayer coverages of enantiopure 2-butoxide species, produced by thermal dehydrogenation of 2-butanol, was highlighted by their difference in behavior toward the adsorption of the two enantiomers of propylene oxide. It was found that a significant enhancement in adsorption is possible on surfaces with the same chirality of the probe molecule, that is, for (R)-propylene oxide adsorption on (R)-2-butoxide layers and for (S)-propylene oxide adsorption on (S)-2-butoxide layers. The propylene oxide probe was found to also adsorb with the ring closer to the surface in those cases. Finally, less butoxide decomposition is seen at higher temperatures from the homochiral pairing, presumably because the coadsorbed propylene oxide forces the alkoxides into a more compact and better packed structure on the surface. 相似文献
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J. L. Hedrick T. P. Russell J. C. Hedrick J. G. Hilborn 《Journal of polymer science. Part A, Polymer chemistry》1996,34(14):2879-2888
A general means of generating nanofoams from thermosetting materials was investigated. Foams were prepared from a thermosetting monomer copolymerized with a thermally labile material, such that the thermally labile coblock is the dispersed phase. Upon thermal treatment, the thermally unstable block undergoes thermolysis, leaving pores where the size and shape are dictated by the initial morphology. For this investigation the thermosetting resin was prepared from a cyanate monomer (4,4′-(hexafluoroisopropylidene) diphenyl-cyanate), with either poly(propylene oxide) or a propylene oxide–urethane copolymer as the thermally labile block. The propylene oxide-based oligomers were molecularly miscible with the cyanate resin over the entire range of compositions, and molecular weights investigated, but developed a two-phase structure upon reaction to form the polycyanurate thermoset. The molecular weight and composition of propylene oxide chemically incorporated into the polycyanurate was varied along with the curing condition, solvents, and catalyst. Dynamic mechanical and small-angle x-ray scattering measurements demonstrated a two-phase morphology in the cured networks wherein the propylene oxide domains are dispersed in the polycyanurate matrix. Upon decomposition of the propylene oxide component, however, the foam was found to collapse. Samples with the larger void size retained, to a large extent, their void composition upon the thermolysis of the propylene oxide component. © 1996 John Wiley & Sons, Inc. 相似文献
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Darensbourg DJ Yarbrough JC Ortiz C Fang CC 《Journal of the American Chemical Society》2003,125(25):7586-7591
The catalysis of the reaction of carbon dioxide with epoxides (cyclohexene oxide or propylene oxide) using the (salen)Cr(III)Cl complex as catalyst, where H(2)salen = N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexenediimine (1), to provide copolymer and cyclic carbonate has been investigated by in situ infrared spectroscopy. As previously demonstrated for the cyclohexene oxide/CO(2) reaction in the presence of complex 1, coupling of propylene oxide and carbon dioxide was found to occur by way of a pathway first-order in catalyst concentration. Unlike the cyclohexene oxide/carbon dioxide reaction catalyzed by complex 1, which affords completely alternating copolymer and only small quantities of trans-cyclic cyclohexyl carbonate, under similar conditions propylene oxide/carbon dioxide produces mostly cyclic propylene carbonate. Comparative kinetic measurements were performed as a function of reaction temperature to assess the activation barrier for production of cyclic carbonates and polycarbonates for the two different classes of epoxides, i.e., alicyclic (cyclohexene oxide) and aliphatic (propylene oxide). As anticipated in both instances the unimolecular pathway for cyclic carbonate formation has a larger energy of activation than the bimolecular enchainment pathway. That is, the energies of activation determined for cyclic propylene carbonate and poly(propylene carbonate) formation were 100.5 and 67.6 kJ.mol(-1), respectively, compared to the corresponding values for cyclic cyclohexyl carbonate and poly(cyclohexylene carbonate) production of 133 and 46.9 kJ.mol(-1). The small energy difference in the two concurrent reactions for the propylene oxide/CO(2) process (33 kJ.mol(-1)) accounts for the large quantity of cyclic carbonate produced at elevated temperatures in this instance. 相似文献
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丙烯环氧化制环氧丙烷是催化领域的最关键的挑战之一. 本文对作者等近年来开展的以一氧化二氮为氧化剂的铁催化体系和以氧气为氧化剂的铜催化体系的研究进展进行了综述. 在这两类催化体系中,碱金属离子(特别是K )的修饰作用均是获得较高环氧丙烷选择性的关键. 碱金属离子通过调变催化剂中铁或铜物种的分散度、配位环境和酸碱性等,实现了对反应途径的调控,使反应朝着有利于环氧丙烷生成的方向进行. 活性金属组分(铁或铜)与氧化剂(一氧化二氮或氧气)间的特定的组合对丙烯环氧化反应的发生也起着重要作用. 推测在两类催化体系中,氧化剂均在具有特定结构和价态的铁或铜活性位上活化,产生导致丙烯环氧化反应发生的亲电性活性氧物种. 相似文献
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Lehenmeier MW Bruckmeier C Klaus S Dengler JE Deglmann P Ott AK Rieger B 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(32):8858-8869
The homogeneous dinuclear zinc catalyst going back to the work of Williams et al. is to date the most active catalyst for the copolymerisation of cyclohexene oxide and CO2 at one atmosphere of carbon dioxide. However, this catalyst shows no copolymer formation in the copolymerisation reaction of propylene oxide and carbon dioxide, instead only cyclic carbonate is found. This behaviour is known for many zinc‐based catalysts, although the reasons are still unidentified. Within our studies, we focus on the parameters that are responsible for this typical behaviour. A deactivation of the catalyst due to a reaction with propylene oxide turns out to be negligible. Furthermore, the catalyst still shows poly(cyclohexene carbonate) formation in the presence of cyclic propylene carbonate, but the catalyst activity is dramatically reduced. In terpolymerisation reactions of CO2 with different ratios of cyclohexene oxide to propylene oxide, no incorporation of propylene oxide can be detected, which can only be explained by a very fast back‐biting reaction. Kinetic investigations indicate a complex reaction network, which can be manifested by theoretical investigations. DFT calculations show that the ring strains of both epoxides are comparable and the kinetic barriers for the chain propagation even favour the poly(propylene carbonate) over the poly(cyclohexene carbonate) formation. Therefore, the crucial step in the copolymerisation of propylene oxide and carbon dioxide is the back‐biting reaction in the case of the studied zinc catalyst. The depolymerisation is several orders of magnitude faster for poly(propylene carbonate) than for poly(cyclohexene carbonate). 相似文献