The electrochemical behaviour of the heterobimetallic complex [Pt(C≡C tol)2(dppm)2-Ir(CO)2]+PF-6 was studied via cyclic voltammetry,convolutive voltammetry and chronopotentiometry at glassy carbon electrode in dichlo...The electrochemical behaviour of the heterobimetallic complex [Pt(C≡C tol)2(dppm)2-Ir(CO)2]+PF-6 was studied via cyclic voltammetry,convolutive voltammetry and chronopotentiometry at glassy carbon electrode in dichloromethane solution.The electrochemical parameters calculated from experimental data were tested and confirmed by matching the experimental cyclic voltammograms with the simulated data.It was found that convolutive voltammetry provided higher sensitivity,better resolution and more accurate method for determination of the electrochemical parameters than ordinary cyclic voltammetry.展开更多
The four different schemes of Group Explicit Method (GEM): GER, GEL, SAGE andDAGE have been claimed to be unstable when employed for electrochemical digital simulations withlarge model diffusion coefficient D_M. Howev...The four different schemes of Group Explicit Method (GEM): GER, GEL, SAGE andDAGE have been claimed to be unstable when employed for electrochemical digital simulations withlarge model diffusion coefficient D_M. However, in this investigation, in spite of the conditionalstability of GER and GEL, the SAGE scheme, which is a combination of GEL and GER, was found to beunconditionally stable when used for simulations of electrochemical reaction-diffusions and had aperformance comparable with or even better than the Fast Quasi Explicit Finite Difference Method(FQEFD) in some aspects. Corresponding differential equations of SAGE scheme for digital simulationsof various electrochemical mechanisms with both uniform and exponentially expanded space units wereestablished. The effectiveness of the SAGE method was further demonstrated by the simulations of anEC and a catalytic mechanism with very large homogeneous rate constants.展开更多
用差分法对2个连续不可逆电子转移过程中偶合一个平行化学反应的E_1(C)E_i历程的偏微分扩散方程做了数值解.通过对大量不同参数下得到的解的分析得出了伏安曲线上2个峰电流比i_(p2)/i_(p1)对化学反应动力学参数k-1 t_b或k_2 c b o t_b...用差分法对2个连续不可逆电子转移过程中偶合一个平行化学反应的E_1(C)E_i历程的偏微分扩散方程做了数值解.通过对大量不同参数下得到的解的分析得出了伏安曲线上2个峰电流比i_(p2)/i_(p1)对化学反应动力学参数k-1 t_b或k_2 c b o t_b的工作曲线,利用这些工作曲线可以在不知道电子转移过程参数K_3,α等值的情况下由伏安曲线上的峰电流比求出化学反应速度常数。展开更多
The electrochemical oxidation of 1,4-dihydroxyanthraquinone has been studied in the presence of acetylacetone and benzoylacetone as nucleophiles in a mixture of ethanol/water by means of cyclic voltammetry as a diagno...The electrochemical oxidation of 1,4-dihydroxyanthraquinone has been studied in the presence of acetylacetone and benzoylacetone as nucleophiles in a mixture of ethanol/water by means of cyclic voltammetry as a diagnostic technique.The results indicate the participation of electrochemically produced anthraquinone in the Michael addition reaction with acetylacetone and benzoylacetone to form the corresponding new anthraquinone derivatives.On the basis of the EC mechanism,the observed homogeneous rate constants（kobs）of the reaction of anthraquinone with acetylacetone and benzoylacetone were estimated by comparing the experimental cyclic voltammograms with the digitally simulated results.展开更多
The reaction of electrochemically generated anthradiquinone as a Michael acceptor with 2-mercaptobenzothiazole and 2- mercaptobenzoxazole,as nucleophiles in ethanol/water mixtures has been studied by means of cyclic v...The reaction of electrochemically generated anthradiquinone as a Michael acceptor with 2-mercaptobenzothiazole and 2- mercaptobenzoxazole,as nucleophiles in ethanol/water mixtures has been studied by means of cyclic voltammetry.Our voltammetric data indicate that produced anthradiquinone participates in Michael addition reaction with nucleophiles and via an ECEC mechanism converts to the new anthraquinonethioether derivatives.Based on an EC mechanism,the observed homogeneous rate constant of the Michael reaction of anthradiquinone with nucleophiles were estimated by comparing the experimental cyclic voltammograms with the digital simulated results.展开更多
文摘The electrochemical behaviour of the heterobimetallic complex [Pt(C≡C tol)2(dppm)2-Ir(CO)2]+PF-6 was studied via cyclic voltammetry,convolutive voltammetry and chronopotentiometry at glassy carbon electrode in dichloromethane solution.The electrochemical parameters calculated from experimental data were tested and confirmed by matching the experimental cyclic voltammograms with the simulated data.It was found that convolutive voltammetry provided higher sensitivity,better resolution and more accurate method for determination of the electrochemical parameters than ordinary cyclic voltammetry.
文摘The four different schemes of Group Explicit Method (GEM): GER, GEL, SAGE andDAGE have been claimed to be unstable when employed for electrochemical digital simulations withlarge model diffusion coefficient D_M. However, in this investigation, in spite of the conditionalstability of GER and GEL, the SAGE scheme, which is a combination of GEL and GER, was found to beunconditionally stable when used for simulations of electrochemical reaction-diffusions and had aperformance comparable with or even better than the Fast Quasi Explicit Finite Difference Method(FQEFD) in some aspects. Corresponding differential equations of SAGE scheme for digital simulationsof various electrochemical mechanisms with both uniform and exponentially expanded space units wereestablished. The effectiveness of the SAGE method was further demonstrated by the simulations of anEC and a catalytic mechanism with very large homogeneous rate constants.
文摘用差分法对2个连续不可逆电子转移过程中偶合一个平行化学反应的E_1(C)E_i历程的偏微分扩散方程做了数值解.通过对大量不同参数下得到的解的分析得出了伏安曲线上2个峰电流比i_(p2)/i_(p1)对化学反应动力学参数k-1 t_b或k_2 c b o t_b的工作曲线,利用这些工作曲线可以在不知道电子转移过程参数K_3,α等值的情况下由伏安曲线上的峰电流比求出化学反应速度常数。
基金Bu-Ali Sina University Research Council and Center of Excellence in Development of Environmentally Friendly Methods for Chemical Synthesis(CEDEFMCS)for their supportto this work
文摘The electrochemical oxidation of 1,4-dihydroxyanthraquinone has been studied in the presence of acetylacetone and benzoylacetone as nucleophiles in a mixture of ethanol/water by means of cyclic voltammetry as a diagnostic technique.The results indicate the participation of electrochemically produced anthraquinone in the Michael addition reaction with acetylacetone and benzoylacetone to form the corresponding new anthraquinone derivatives.On the basis of the EC mechanism,the observed homogeneous rate constants（kobs）of the reaction of anthraquinone with acetylacetone and benzoylacetone were estimated by comparing the experimental cyclic voltammograms with the digitally simulated results.
基金the Bu-Ali Sina University Research Council and Center of Excellence in Development of Chemical Methods(CEDCM)for their support of this work
文摘The reaction of electrochemically generated anthradiquinone as a Michael acceptor with 2-mercaptobenzothiazole and 2- mercaptobenzoxazole,as nucleophiles in ethanol/water mixtures has been studied by means of cyclic voltammetry.Our voltammetric data indicate that produced anthradiquinone participates in Michael addition reaction with nucleophiles and via an ECEC mechanism converts to the new anthraquinonethioether derivatives.Based on an EC mechanism,the observed homogeneous rate constant of the Michael reaction of anthradiquinone with nucleophiles were estimated by comparing the experimental cyclic voltammograms with the digital simulated results.
