Single‐atom catalysts have been proposed as promising electrocatalysts for CO_(2) reduction reactions(CO_(2)RR).Co‐N_(4) active sites have attracted wide attention owing to their excellent CO selectivity and activit...Single‐atom catalysts have been proposed as promising electrocatalysts for CO_(2) reduction reactions(CO_(2)RR).Co‐N_(4) active sites have attracted wide attention owing to their excellent CO selectivity and activity.However,the effect of the local coordination environment of Co sites on CO_(2) reduction reaction pathways is still unclear.In this study,we investigated the CO_(2) reduction reaction pathways on Co‐N_(4) sites supported on conjugated N_(4)‐macrocyclic ligands with 1,10‐phenanthroline subunits(Co‐N_(4)‐CPY)by density functional theory calculations.The local coordination environment of single‐atom Co sites with N substituted by O(Co‐N_(3)O‐CPY)and C(Co‐N_(3)C‐CPY)was studied for comparison.The calculation results revealed that both C and O coordination break the symmetry of the primary CoN_(4) ligand field and induce charge redistribution of the Co atom.For Co‐N_(4)‐CPY,CO was confirmed to be the main product of CO_(2)RR.HCOOH is the primary product of Co‐N_(3)O‐CPY because of the greatly increased energy barrier of CO_(2) to*COOH.Although the energy barrier of CO_(2) to*COOH is reduced on Co‐N_(3)C‐CPY,the desorption process of*CO becomes more difficult.CH3OH(or CH_(4))are obtained by further*CO hydrogenation reduction when using Co‐N_(3)C‐CPY.This work provides new insight into the effect of the local coordination environment of single‐atom sites on CO_(2) reduction reaction pathways.展开更多
Stressed by external forces, it is possible for a cylindric pipeline to change into an elliptic pipeline. To expose the effect of small shape change of the pipeline on the depletion interactions, both the depletion po...Stressed by external forces, it is possible for a cylindric pipeline to change into an elliptic pipeline. To expose the effect of small shape change of the pipeline on the depletion interactions, both the depletion potentials and depletion forces in the hard sphere systems confined by a cylindric pipeline or by an elliptic pipeline are studied by Monte Carlo simulations. The numerical results show that the depletion interactions are strongly affected by the small change of the shape of the pipeline in a way. Furthermore, it is also found that the depletion interactions will be strengthened if the short axis of the elliptic pipeline is decreased.展开更多
In a colloidal system confined by a small cylindric pipeline, the depletion interaction between two large spheres is different to the system confined by two plates, and the influence on depletion interaction from the ...In a colloidal system confined by a small cylindric pipeline, the depletion interaction between two large spheres is different to the system confined by two plates, and the influence on depletion interaction from the pipeline is related to both the size and shape of it. In this paper, the depletion interactions in the systems confined by pipelines of different sizes or different shapes are studied by Monte Carlo simulations. The numerical results show that the influence on depletion force from the cylindric pipeline is stronger than that from two parallel plates, and the depletion force will be strengthened when the diameter of the cylinder is decreased. In addition, we also find that the depletion interaction is rather affected if the shape change of the pipeline is slightly changed, and the influence on depletion force from the shape change is stronger than that from the size change.展开更多
In a three-sphere system, the middle sphere is acted upon by two opposite depletion forces from the other two spheres. It is found that, in this system, the two depletion forces are coupled with each other and result ...In a three-sphere system, the middle sphere is acted upon by two opposite depletion forces from the other two spheres. It is found that, in this system, the two depletion forces are coupled with each other and result in a strengthened depletion force. So the difference of the depletion forces of the three-sphere system and its corresponding two two-sphere systems is introduced to describe the coupling effect of the depletion interactions. The numerical results obtained by Monte- Carlo simulations show that this coupling effect is affected by both the concentration of small spheres and the geometrical confinement. Meanwhile, it is also found that the mechanisms of the coupling effect and the effect on the depletion force from the ~eometry factor are the same.展开更多
In a charged colloidal system, the influence on depletion interaction between two like-charged macro-ions is studied through Monte Carlo simulation in this paper. The numerical results show that this depletion force i...In a charged colloidal system, the influence on depletion interaction between two like-charged macro-ions is studied through Monte Carlo simulation in this paper. The numerical results show that this depletion force is affected by both the electrostatic interactions between charged spheres and charged plates and by the geometrical factor of the two charged plates, and they further indicate that the influence of geometrical confinement on the depletion interaction is larger than that of electrostatic potential.展开更多
文摘Single‐atom catalysts have been proposed as promising electrocatalysts for CO_(2) reduction reactions(CO_(2)RR).Co‐N_(4) active sites have attracted wide attention owing to their excellent CO selectivity and activity.However,the effect of the local coordination environment of Co sites on CO_(2) reduction reaction pathways is still unclear.In this study,we investigated the CO_(2) reduction reaction pathways on Co‐N_(4) sites supported on conjugated N_(4)‐macrocyclic ligands with 1,10‐phenanthroline subunits(Co‐N_(4)‐CPY)by density functional theory calculations.The local coordination environment of single‐atom Co sites with N substituted by O(Co‐N_(3)O‐CPY)and C(Co‐N_(3)C‐CPY)was studied for comparison.The calculation results revealed that both C and O coordination break the symmetry of the primary CoN_(4) ligand field and induce charge redistribution of the Co atom.For Co‐N_(4)‐CPY,CO was confirmed to be the main product of CO_(2)RR.HCOOH is the primary product of Co‐N_(3)O‐CPY because of the greatly increased energy barrier of CO_(2) to*COOH.Although the energy barrier of CO_(2) to*COOH is reduced on Co‐N_(3)C‐CPY,the desorption process of*CO becomes more difficult.CH3OH(or CH_(4))are obtained by further*CO hydrogenation reduction when using Co‐N_(3)C‐CPY.This work provides new insight into the effect of the local coordination environment of single‐atom sites on CO_(2) reduction reaction pathways.
基金Supported by the National Natural Science Foundation of China under Grant No 10375024, and the Scientific Research Fund of Hunan Provincial Education Department.
文摘Stressed by external forces, it is possible for a cylindric pipeline to change into an elliptic pipeline. To expose the effect of small shape change of the pipeline on the depletion interactions, both the depletion potentials and depletion forces in the hard sphere systems confined by a cylindric pipeline or by an elliptic pipeline are studied by Monte Carlo simulations. The numerical results show that the depletion interactions are strongly affected by the small change of the shape of the pipeline in a way. Furthermore, it is also found that the depletion interactions will be strengthened if the short axis of the elliptic pipeline is decreased.
基金supported by the National Natural Science Foundation of China (Grant Nos 10375042 and 10775018)the Scientific Research Fund of Hunan Provincial Education Department and Hunan Provincial Natural Science Foundation of China (GrantNo 08jj6043)the Construct Program of the Key Discipline in Hunan Province,China
文摘In a colloidal system confined by a small cylindric pipeline, the depletion interaction between two large spheres is different to the system confined by two plates, and the influence on depletion interaction from the pipeline is related to both the size and shape of it. In this paper, the depletion interactions in the systems confined by pipelines of different sizes or different shapes are studied by Monte Carlo simulations. The numerical results show that the influence on depletion force from the cylindric pipeline is stronger than that from two parallel plates, and the depletion force will be strengthened when the diameter of the cylinder is decreased. In addition, we also find that the depletion interaction is rather affected if the shape change of the pipeline is slightly changed, and the influence on depletion force from the shape change is stronger than that from the size change.
基金Project supported by the Scientific Research Fund of Hunan Provincial Education Department, China (Grant Nos. 08B028 and 10A075)the Natural Science Foundation of Hunan Province, China (Grant No. 08jj6043)
文摘In a three-sphere system, the middle sphere is acted upon by two opposite depletion forces from the other two spheres. It is found that, in this system, the two depletion forces are coupled with each other and result in a strengthened depletion force. So the difference of the depletion forces of the three-sphere system and its corresponding two two-sphere systems is introduced to describe the coupling effect of the depletion interactions. The numerical results obtained by Monte- Carlo simulations show that this coupling effect is affected by both the concentration of small spheres and the geometrical confinement. Meanwhile, it is also found that the mechanisms of the coupling effect and the effect on the depletion force from the ~eometry factor are the same.
基金supported by the National Natural Science Foundation of China (Grant Nos 10375042 and 10775018)the Scientific Research Fund of Hunan Provincial Education Department and Hunan Provincial Natural Science Foundation of China (GrantNo 08jj6043)the Construct Program of the Key discipline in Hunan Province,China
文摘In a charged colloidal system, the influence on depletion interaction between two like-charged macro-ions is studied through Monte Carlo simulation in this paper. The numerical results show that this depletion force is affected by both the electrostatic interactions between charged spheres and charged plates and by the geometrical factor of the two charged plates, and they further indicate that the influence of geometrical confinement on the depletion interaction is larger than that of electrostatic potential.
