The authors have investigated the pH and ionic strength response of self-assembled layers formed by adsorption of amphiphilic weak polyelectrolytes. Using the SFA （Surface Forces Apparatus） the authors measured forc...The authors have investigated the pH and ionic strength response of self-assembled layers formed by adsorption of amphiphilic weak polyelectrolytes. Using the SFA （Surface Forces Apparatus） the authors measured force-distance profiles of poly （isoprene）-poly （acrylic acid） block copolymers adsorbed on mica. Also by Atomic Force Microscopy the authors captured single polyelectrolyte molecule adsorbed on a surface. The effect of salt concentration （Cs） and pH upon the height of the brush layers was explored mainly by measuring the forces between two adsorbed polyelectrolyte brushes. At pH = 4 our results are in good agreement with the scaling prediction L0 ∝Cs-1/3 Changing the pH from 4 to 10 causes a remarkable swelling of the polymer layer, but only a weak dependence on salt concentration was detected at the higher pH. This can be attributed to the degree of dissociation, which depends on the local pH value. At low pH the polyelectrolyte chains have a low charge density, while on increasing the pH the degree of dissociation rises, and the increased charge density is followed by swelling of the adsorbed layer. The local concentration of ions in the brush is now greater than that of pH = 4 and approximately equivalent to 0.3 M. So the swelling is only weakly dependent on salt concentration in the range 0.01-1.0 M. The results demonstrate the tunable nature of such self-assembled polyelectroiyte brushes whose height and range of interactions, can be systematically controlled by adjusting the pH and ionic strength of the medium.展开更多
Single-atom catalysts(SACs)have emerged as one of the most competitive catalysts toward a variety of important electrochemical reactions,thanks to their maximum atom economy,unique electronic and geometric structures....Single-atom catalysts(SACs)have emerged as one of the most competitive catalysts toward a variety of important electrochemical reactions,thanks to their maximum atom economy,unique electronic and geometric structures.However,the role of SACs supports on the catalytic performance does not receive enough research attentions.Here,we report an efficient route for synthesis of single atom Zn loading on the N-doped carbon nano-onions(ZnN/CNO).ZnN/CNO catalysts show an excellent high selectivity for CO_(2) electro-reduction to CO with a Faradaic efficiency of CO(FECO)up to 97%at -0.47 V(vs.reversible hydrogen electrode,RHE)and remarkable durability without activity decay.To our knowledge,ZnN/CNO is the best activity for the Zn based catalysts up to now,and superior to single atom Zn loading on the two-dimensional planar and porous structure of graphene substrate,although the graphene with larger surface area.The exact role of such carbon nano-onions(CNO)support is studied systematically by coupling characterizations and electrochemistry with density functional theory(DFT)calculations,which have attributed such good performance to the increased curvature.Such increased curvature modifies the surface charge,which then changes the adsorption energies of key intermediates,and improves the selectivity for CO generation accordingly.展开更多
文摘The authors have investigated the pH and ionic strength response of self-assembled layers formed by adsorption of amphiphilic weak polyelectrolytes. Using the SFA （Surface Forces Apparatus） the authors measured force-distance profiles of poly （isoprene）-poly （acrylic acid） block copolymers adsorbed on mica. Also by Atomic Force Microscopy the authors captured single polyelectrolyte molecule adsorbed on a surface. The effect of salt concentration （Cs） and pH upon the height of the brush layers was explored mainly by measuring the forces between two adsorbed polyelectrolyte brushes. At pH = 4 our results are in good agreement with the scaling prediction L0 ∝Cs-1/3 Changing the pH from 4 to 10 causes a remarkable swelling of the polymer layer, but only a weak dependence on salt concentration was detected at the higher pH. This can be attributed to the degree of dissociation, which depends on the local pH value. At low pH the polyelectrolyte chains have a low charge density, while on increasing the pH the degree of dissociation rises, and the increased charge density is followed by swelling of the adsorbed layer. The local concentration of ions in the brush is now greater than that of pH = 4 and approximately equivalent to 0.3 M. So the swelling is only weakly dependent on salt concentration in the range 0.01-1.0 M. The results demonstrate the tunable nature of such self-assembled polyelectroiyte brushes whose height and range of interactions, can be systematically controlled by adjusting the pH and ionic strength of the medium.
基金This work was supported by the National Key R&D Program of China(2020YFA0710404)the Beijing Natural Science Foundation(2182077)the National Natural Science Foundation of China(21477136,51972281,and 21703250).
文摘Single-atom catalysts(SACs)have emerged as one of the most competitive catalysts toward a variety of important electrochemical reactions,thanks to their maximum atom economy,unique electronic and geometric structures.However,the role of SACs supports on the catalytic performance does not receive enough research attentions.Here,we report an efficient route for synthesis of single atom Zn loading on the N-doped carbon nano-onions(ZnN/CNO).ZnN/CNO catalysts show an excellent high selectivity for CO_(2) electro-reduction to CO with a Faradaic efficiency of CO(FECO)up to 97%at -0.47 V(vs.reversible hydrogen electrode,RHE)and remarkable durability without activity decay.To our knowledge,ZnN/CNO is the best activity for the Zn based catalysts up to now,and superior to single atom Zn loading on the two-dimensional planar and porous structure of graphene substrate,although the graphene with larger surface area.The exact role of such carbon nano-onions(CNO)support is studied systematically by coupling characterizations and electrochemistry with density functional theory(DFT)calculations,which have attributed such good performance to the increased curvature.Such increased curvature modifies the surface charge,which then changes the adsorption energies of key intermediates,and improves the selectivity for CO generation accordingly.
