Phosphoric acid/phosphate solu-tions are commonly used as buffer solutions in the fundamental stud-ies in electrochemistry.Informa-tion on the nature of adsorbed(bi)phosphate as well as the do-main structures is of gr...Phosphoric acid/phosphate solu-tions are commonly used as buffer solutions in the fundamental stud-ies in electrochemistry.Informa-tion on the nature of adsorbed(bi)phosphate as well as the do-main structures is of great impor-tance in unveiling the impact on electrochemical processes occur-ring at electrode electrolyte interface.In this work,the pH effect on the adsorption of phosphate related species on Pd(111)electrode has been investigated by cyclic voltammetry over a broad pH range from 1 to 14.Af-ter carefully analyzing the related onset desorption potential of(bi)phosphate adsorbate to the thermodynamic equilibrium potential of the corresponding electrode reactions,three dif-ferent phosphate related adsorbates have been identified,which are highly pH-dependent.Our analysis reveals that the dominant phosphate anions in bulk solution undergo deprotona-tion upon adsorption.At pH<1.5,the main adsorbate on Pd(111)is;H_(2)PO_(4)^(λ_(1)^(-))in solutions with 1.5<pH<7,the main adsorbate changes into.HPO_(4)^(λ_2^(-))At higher pHs,PO_(4)^(λ_(3)^(-))on electrode surface dominates.The exact charging value ofλ_(i),which represents the true va-lence of the(bi)phosphate adsorbate,could be determined using theoretical calculations.In addition,our results can not rule out the possibility of co-adsorbed H_(3)PO_(4)molecules on Pd(111)at pH<1.5,which needs to be proved by infrared spectroscopy in the future.展开更多
This paper considers nonlinear dynamics of teth- ered three-body formation system with their centre of mass staying on a circular orbit around the Earth, and applies the theory of space manifold dynamics to deal with ...This paper considers nonlinear dynamics of teth- ered three-body formation system with their centre of mass staying on a circular orbit around the Earth, and applies the theory of space manifold dynamics to deal with the nonlinear dynamical behaviors of the equilibrium configurations of the system. Compared with the classical circular restricted three body system, sixteen equilibrium configurations are obtained globally from the geometry of pseudo-potential energy sur- face, four of which were omitted in the previous research. The periodic Lyapunov orbits and their invariant manifolds near the hyperbolic equilibria are presented, and an iteration procedure for identifying Lyapunov orbit is proposed based on the differential correction algorithm. The non-transversal intersections between invariant manifolds are addressed to generate homoclinic and heteroclinic trajectories between the Lyapunov orbits. （3,3）- and （2,1）-heteroclinic trajecto- ries from the neighborhood of one collinear equilibrium to that of another one, and （3,6）- and （2,1）-homoclinic trajecto- ries from and to the neighborhood of the same equilibrium, are obtained based on the Poincar6 mapping technique.展开更多
基金supported by the National Natural Science Foundation of China(No.22172151)。
文摘Phosphoric acid/phosphate solu-tions are commonly used as buffer solutions in the fundamental stud-ies in electrochemistry.Informa-tion on the nature of adsorbed(bi)phosphate as well as the do-main structures is of great impor-tance in unveiling the impact on electrochemical processes occur-ring at electrode electrolyte interface.In this work,the pH effect on the adsorption of phosphate related species on Pd(111)electrode has been investigated by cyclic voltammetry over a broad pH range from 1 to 14.Af-ter carefully analyzing the related onset desorption potential of(bi)phosphate adsorbate to the thermodynamic equilibrium potential of the corresponding electrode reactions,three dif-ferent phosphate related adsorbates have been identified,which are highly pH-dependent.Our analysis reveals that the dominant phosphate anions in bulk solution undergo deprotona-tion upon adsorption.At pH<1.5,the main adsorbate on Pd(111)is;H_(2)PO_(4)^(λ_(1)^(-))in solutions with 1.5<pH<7,the main adsorbate changes into.HPO_(4)^(λ_2^(-))At higher pHs,PO_(4)^(λ_(3)^(-))on electrode surface dominates.The exact charging value ofλ_(i),which represents the true va-lence of the(bi)phosphate adsorbate,could be determined using theoretical calculations.In addition,our results can not rule out the possibility of co-adsorbed H_(3)PO_(4)molecules on Pd(111)at pH<1.5,which needs to be proved by infrared spectroscopy in the future.
基金supported by the National Natural Science Foundation of China(11172020)Talent Foundation supported by the Fundamental Research Funds for the Central Universities+1 种基金Aerospace Science and Technology Innovation Foundation of China Aerospace Science Corporationthe National High Technology Research and Development Program of China(863)(2012AA120601)
文摘This paper considers nonlinear dynamics of teth- ered three-body formation system with their centre of mass staying on a circular orbit around the Earth, and applies the theory of space manifold dynamics to deal with the nonlinear dynamical behaviors of the equilibrium configurations of the system. Compared with the classical circular restricted three body system, sixteen equilibrium configurations are obtained globally from the geometry of pseudo-potential energy sur- face, four of which were omitted in the previous research. The periodic Lyapunov orbits and their invariant manifolds near the hyperbolic equilibria are presented, and an iteration procedure for identifying Lyapunov orbit is proposed based on the differential correction algorithm. The non-transversal intersections between invariant manifolds are addressed to generate homoclinic and heteroclinic trajectories between the Lyapunov orbits. （3,3）- and （2,1）-heteroclinic trajecto- ries from the neighborhood of one collinear equilibrium to that of another one, and （3,6）- and （2,1）-homoclinic trajecto- ries from and to the neighborhood of the same equilibrium, are obtained based on the Poincar6 mapping technique.
