Single-entity collisional electrochemistry(SECE)is a branch of single-entity electrochemistry.It can directly characterize entities/particles with single particle resolution through random collisions between particles...Single-entity collisional electrochemistry(SECE)is a branch of single-entity electrochemistry.It can directly characterize entities/particles with single particle resolution through random collisions between particles and electrodes in a solution,and obtain rich physicochemical information,thus becoming one of the frontiers of electroanalytical chemistry in the past two decades.Interestingly,the(micro/nanoscale)sensing electrodes have evolved from a polarizable liquid/liquid(mercury/liquid)interface to a solid/liquid interface and then to a liquid/liquid interface(i.e.,an interface between twoimmiscible electrolyte solutions,ITIES),as if they have completed a cycle(but in fact they have not).ITIES has become the latest sensing electrode in the booming SECE due to its polarizability(up to 1.1 V at the water/a,a,a-trifluorotoluene interface)and high reproducibility.The four measurement modes(direct electrolysis,mediated electrolysis,current blockade,and charge displacement)developed in the realm of SECE at solid/liquid interfaces have also been fully realized at the miniature ITIES.This article will discuss these four modes at the ITIES from the perspectives of basic concepts,operating mechanisms,and latest developments(e.g.,discovery of ionosomes,blockade effect of Faradaic ion transfer,etc.),and look forward to the future development and direction of this emerging field.展开更多
For the diffusion-controlled adsorption, the expression of dynamic surface adsorption P(t) was ob- tained by solving the diffusion equation. Two cases, i.e. the short and long time limits, were mainly discussed in t...For the diffusion-controlled adsorption, the expression of dynamic surface adsorption P(t) was ob- tained by solving the diffusion equation. Two cases, i.e. the short and long time limits, were mainly discussed in this paper. From the measured dynamic surface tension of aqueous surfactant sodium dodecyl sulfate (SDS) solutions at 25 ℃, the adsorption kinetics of SDS at air/solution interface was studied. It was proved that for both of the short and long time limits, the adsorption process of SDS was controlled by diffusion.展开更多
Membrane/solution interface consists of a neutral concentration polai layer(CPL) and a charge layer(CL) under external electrical field, and the neutral CPL can be neglected under high frequency AC electrical field. T...Membrane/solution interface consists of a neutral concentration polai layer(CPL) and a charge layer(CL) under external electrical field, and the neutral CPL can be neglected under high frequency AC electrical field. The relationship of CL thickness e with electrolyte concentration C and fixed ion exchange sites density σ in membrane surface layer can be expressed as e展开更多
In this paper a pH microprobe technique was developed to measure in-situ the pH value at the electrode/solution interface. Iridium oxide was used as a pH sensitive material with good response behavior in the measured ...In this paper a pH microprobe technique was developed to measure in-situ the pH value at the electrode/solution interface. Iridium oxide was used as a pH sensitive material with good response behavior in the measured solutions. The experimental results indicated that the interfacial pH increased with the applied potential, first jumped to a maximum, then slowly decreased at the controlled potential during the electrodeposition process of functional ceramics.展开更多
In situ x-ray diffraction electrochemical method is used to study the activation of silver electrode in KCl solution and UPD lead on silver electrode surface. We found that the activation makes the silver crystal thic...In situ x-ray diffraction electrochemical method is used to study the activation of silver electrode in KCl solution and UPD lead on silver electrode surface. We found that the activation makes the silver crystal thicker in (111), and the arrangement of water molecules on the silver electrode surface with UPD lead is partially ordered.展开更多
In this paper, the eigen function expansions of displacements and stresses of bi-metal laminates with interface cracks are obtained. Furthermore, the stress intensity factors are determined by the variational method t...In this paper, the eigen function expansions of displacements and stresses of bi-metal laminates with interface cracks are obtained. Furthermore, the stress intensity factors are determined by the variational method to satisfy the boundary conditions and there are only line integrals in the variational equations due to the previous satisfaction of all basic equations. The computations show that this method of solution has the advantages of rapid convergency and time-saving. The results obtained by this method for homogeneous material agree with the known ones very well.展开更多
The double plate system with a discontinuity in the elastic bonding layer of Winker type is studied in this paper. When the discontinuity is small, it can be taken as an interface crack between the bi-materials or two...The double plate system with a discontinuity in the elastic bonding layer of Winker type is studied in this paper. When the discontinuity is small, it can be taken as an interface crack between the bi-materials or two bodies (plates or beams). By comparison between the number of multifrequencies of analytical solutions of the double plate system free transversal vibrations for the case when the system is with and without disconti- nuity in elastic layer we obtain a theory for experimental vibration method for identification of the presence of an interface crack in the double plate system. The analytical analysis of free transversal vibrations of an elastically connected double plate systems with discontinuity in the elastic layer of Winkler type is presented. The analytical solutions of the coupled partial differential equations for dynamical free and forced vibration processes are obtained by using method of Bernoulli's particular integral and Lagrange's method of variation constants. It is shown that one mode vibration corresponds an infinite or finite multi-frequency regime for free and forced vibrations induced by initial conditions and one- frequency or corresponding number of multi-frequency regime depending on external excitations. It is shown for every shape of vibrations. The analytical solutions show that the discontinuity affects the appearance of multi-frequency regime of time function corresponding to one eigen amplitude function of one mode, and also that time functions of different vibration basic modes are coupled. From final expression we can separate the newgeneralized eigen amplitude functions with correspon- ding time eigen functions of one frequency and multifrequency regime of vibrations.展开更多
Electrocatalytic activity is influenced by the surface charge on the solid catalyst.Conventionally,our attention has been focused on how the surface charge shapes the electric potential and concentration of ionic reac...Electrocatalytic activity is influenced by the surface charge on the solid catalyst.Conventionally,our attention has been focused on how the surface charge shapes the electric potential and concentration of ionic reactant(s)in the local reaction zone.Taking H_(2)O_(2)redox reactions at Pt(111)as a model system,we reveal a peculiar surface charge effect using ab initio molecular dynamics simulations of electrified Pt(111)-water interfaces.In this scenario,the negative surface charge on Pt(111)repels the O-O bond of the reactant(H_(2)O_(2))farther away from the electrode surface.This leads to a higher activation barrier for breaking the O-O bond.Incorporating this microscopic mechanism into a microkinetic-double-layer model,we are able to semi-quantitatively interpret the pH-dependent activity of H_(2)O_(2)redox reactions at Pt(111),especially the anomalously suppressed activity of H_(2)O_(2)reduction with decreasing electrode potential.The relevance of the present surface charge effect is also examined in wider scenarios with different electrolyte cations,solution pHs,crystal facets of the catalyst,and model parameters.In contrast with previous mechanisms focusing on how surface charge influences the local reaction condition at a fixed reaction plane,the present work gives an example in which the location of the reaction plane is adjusted by the surface charge.展开更多
基金supported by the National Natural Science Foundation of China(No.21904143).
文摘Single-entity collisional electrochemistry(SECE)is a branch of single-entity electrochemistry.It can directly characterize entities/particles with single particle resolution through random collisions between particles and electrodes in a solution,and obtain rich physicochemical information,thus becoming one of the frontiers of electroanalytical chemistry in the past two decades.Interestingly,the(micro/nanoscale)sensing electrodes have evolved from a polarizable liquid/liquid(mercury/liquid)interface to a solid/liquid interface and then to a liquid/liquid interface(i.e.,an interface between twoimmiscible electrolyte solutions,ITIES),as if they have completed a cycle(but in fact they have not).ITIES has become the latest sensing electrode in the booming SECE due to its polarizability(up to 1.1 V at the water/a,a,a-trifluorotoluene interface)and high reproducibility.The four measurement modes(direct electrolysis,mediated electrolysis,current blockade,and charge displacement)developed in the realm of SECE at solid/liquid interfaces have also been fully realized at the miniature ITIES.This article will discuss these four modes at the ITIES from the perspectives of basic concepts,operating mechanisms,and latest developments(e.g.,discovery of ionosomes,blockade effect of Faradaic ion transfer,etc.),and look forward to the future development and direction of this emerging field.
文摘For the diffusion-controlled adsorption, the expression of dynamic surface adsorption P(t) was ob- tained by solving the diffusion equation. Two cases, i.e. the short and long time limits, were mainly discussed in this paper. From the measured dynamic surface tension of aqueous surfactant sodium dodecyl sulfate (SDS) solutions at 25 ℃, the adsorption kinetics of SDS at air/solution interface was studied. It was proved that for both of the short and long time limits, the adsorption process of SDS was controlled by diffusion.
基金Project(02-09-01) supported by Panzhihua Iron and Steel Corporation,China
文摘Membrane/solution interface consists of a neutral concentration polai layer(CPL) and a charge layer(CL) under external electrical field, and the neutral CPL can be neglected under high frequency AC electrical field. The relationship of CL thickness e with electrolyte concentration C and fixed ion exchange sites density σ in membrane surface layer can be expressed as e
文摘In this paper a pH microprobe technique was developed to measure in-situ the pH value at the electrode/solution interface. Iridium oxide was used as a pH sensitive material with good response behavior in the measured solutions. The experimental results indicated that the interfacial pH increased with the applied potential, first jumped to a maximum, then slowly decreased at the controlled potential during the electrodeposition process of functional ceramics.
基金This paper was suported by the National Natural Science Foundation of China.
文摘In situ x-ray diffraction electrochemical method is used to study the activation of silver electrode in KCl solution and UPD lead on silver electrode surface. We found that the activation makes the silver crystal thicker in (111), and the arrangement of water molecules on the silver electrode surface with UPD lead is partially ordered.
文摘In this paper, the eigen function expansions of displacements and stresses of bi-metal laminates with interface cracks are obtained. Furthermore, the stress intensity factors are determined by the variational method to satisfy the boundary conditions and there are only line integrals in the variational equations due to the previous satisfaction of all basic equations. The computations show that this method of solution has the advantages of rapid convergency and time-saving. The results obtained by this method for homogeneous material agree with the known ones very well.
文摘The double plate system with a discontinuity in the elastic bonding layer of Winker type is studied in this paper. When the discontinuity is small, it can be taken as an interface crack between the bi-materials or two bodies (plates or beams). By comparison between the number of multifrequencies of analytical solutions of the double plate system free transversal vibrations for the case when the system is with and without disconti- nuity in elastic layer we obtain a theory for experimental vibration method for identification of the presence of an interface crack in the double plate system. The analytical analysis of free transversal vibrations of an elastically connected double plate systems with discontinuity in the elastic layer of Winkler type is presented. The analytical solutions of the coupled partial differential equations for dynamical free and forced vibration processes are obtained by using method of Bernoulli's particular integral and Lagrange's method of variation constants. It is shown that one mode vibration corresponds an infinite or finite multi-frequency regime for free and forced vibrations induced by initial conditions and one- frequency or corresponding number of multi-frequency regime depending on external excitations. It is shown for every shape of vibrations. The analytical solutions show that the discontinuity affects the appearance of multi-frequency regime of time function corresponding to one eigen amplitude function of one mode, and also that time functions of different vibration basic modes are coupled. From final expression we can separate the newgeneralized eigen amplitude functions with correspon- ding time eigen functions of one frequency and multifrequency regime of vibrations.
文摘Electrocatalytic activity is influenced by the surface charge on the solid catalyst.Conventionally,our attention has been focused on how the surface charge shapes the electric potential and concentration of ionic reactant(s)in the local reaction zone.Taking H_(2)O_(2)redox reactions at Pt(111)as a model system,we reveal a peculiar surface charge effect using ab initio molecular dynamics simulations of electrified Pt(111)-water interfaces.In this scenario,the negative surface charge on Pt(111)repels the O-O bond of the reactant(H_(2)O_(2))farther away from the electrode surface.This leads to a higher activation barrier for breaking the O-O bond.Incorporating this microscopic mechanism into a microkinetic-double-layer model,we are able to semi-quantitatively interpret the pH-dependent activity of H_(2)O_(2)redox reactions at Pt(111),especially the anomalously suppressed activity of H_(2)O_(2)reduction with decreasing electrode potential.The relevance of the present surface charge effect is also examined in wider scenarios with different electrolyte cations,solution pHs,crystal facets of the catalyst,and model parameters.In contrast with previous mechanisms focusing on how surface charge influences the local reaction condition at a fixed reaction plane,the present work gives an example in which the location of the reaction plane is adjusted by the surface charge.