Using ab initio molecular dynamics(AIMD)simulations,classical molecular dynamics(CMD)simulations,small-angle X-ray scattering(SAXS),and pulsed-field gradient nuclear magnetic resonance(PFG-NMR),the solvation structure...Using ab initio molecular dynamics(AIMD)simulations,classical molecular dynamics(CMD)simulations,small-angle X-ray scattering(SAXS),and pulsed-field gradient nuclear magnetic resonance(PFG-NMR),the solvation structure and ion dynamics of magnesium bis(trifluoromethanesulfonyl)imide(Mg(TFSI)_(2))aqueous electrolyte at 1,2,and 3 m concentrations are investigated.From AIMD and CMD simulations,the first solvation shell of an Mg;ion is found to be composed of six water molecules in an octahedral configuration and the solvation shell is rather rigid.The TFSI^(-)ions prefer to stay in the second solvation shell and beyond.Meanwhile,the comparable diffusion coefficients of positive and negative ions in Mg(TFSI)_(2)aqueous electrolytes have been observed,which is mainly due to the formation of the stable[Mg(H_(2)O_(6))_(2)]^(+)complex,and,as a result,the increased effective Mg ion size.Finally,the calculated correlated transference numbers are lower than the uncorrelated ones even at the low concentration of 2 and 3 m,suggesting the enhanced correlations between ions in the multivalent electrolytes.This work provides a molecular-level understanding of how the solvation structure and multivalency of the ion affect the dynamics and transport properties of the multivalent electrolyte,providing insight for rational designs of electrolytes for improved ion transport properties.展开更多
Ketone coupling via aldol condensation is one of the promising routes to produce cyclic and value-added precursors for renewable hydrocarbon biofuels.A first-principles-based microkinetic modeling is performed to eval...Ketone coupling via aldol condensation is one of the promising routes to produce cyclic and value-added precursors for renewable hydrocarbon biofuels.A first-principles-based microkinetic modeling is performed to evaluate the surface-mediated reaction mechanisms and the role of water molecules in the observed activities for 2-pentanone and 3-pentanone aldol condensation on dehydroxylated MgO(111)surface and hydroxylated terminated surface[OH-MgO(111)].We have identified the enhancement of the surface OH group to MgO(111)surface catalytic activity by destabilizing the binding strength of reaction intermediates and reducing the energy barriers of rate-determining steps(proton transfer and dehydration steps).The 2-pentanone has one elementary step less in the complete reaction mechanism of aldol condensation and preferable energy barrier for proton transfer and dehydration steps,revealing 2-pentanone as terminal ketone is more reactive than 3-pentanone as central ketone.The water molecules dominated the OH-MgO(111)surface after further addition of water,leading to the reduction of turnover frequency of the aldol condensation dimer product as the loss of aldol condensation reaction intermediates in competitive adsorption with water molecules.展开更多
基金supported by the Joint Center for Energy Storage Research(JCESR),a U.S.Department of Energy,Energy Innovation Hub。
文摘Using ab initio molecular dynamics(AIMD)simulations,classical molecular dynamics(CMD)simulations,small-angle X-ray scattering(SAXS),and pulsed-field gradient nuclear magnetic resonance(PFG-NMR),the solvation structure and ion dynamics of magnesium bis(trifluoromethanesulfonyl)imide(Mg(TFSI)_(2))aqueous electrolyte at 1,2,and 3 m concentrations are investigated.From AIMD and CMD simulations,the first solvation shell of an Mg;ion is found to be composed of six water molecules in an octahedral configuration and the solvation shell is rather rigid.The TFSI^(-)ions prefer to stay in the second solvation shell and beyond.Meanwhile,the comparable diffusion coefficients of positive and negative ions in Mg(TFSI)_(2)aqueous electrolytes have been observed,which is mainly due to the formation of the stable[Mg(H_(2)O_(6))_(2)]^(+)complex,and,as a result,the increased effective Mg ion size.Finally,the calculated correlated transference numbers are lower than the uncorrelated ones even at the low concentration of 2 and 3 m,suggesting the enhanced correlations between ions in the multivalent electrolytes.This work provides a molecular-level understanding of how the solvation structure and multivalency of the ion affect the dynamics and transport properties of the multivalent electrolyte,providing insight for rational designs of electrolytes for improved ion transport properties.
基金supported by the Science Foundation of China University of Petroleum,Beijing,China(No.2462022YJRC010).
文摘Ketone coupling via aldol condensation is one of the promising routes to produce cyclic and value-added precursors for renewable hydrocarbon biofuels.A first-principles-based microkinetic modeling is performed to evaluate the surface-mediated reaction mechanisms and the role of water molecules in the observed activities for 2-pentanone and 3-pentanone aldol condensation on dehydroxylated MgO(111)surface and hydroxylated terminated surface[OH-MgO(111)].We have identified the enhancement of the surface OH group to MgO(111)surface catalytic activity by destabilizing the binding strength of reaction intermediates and reducing the energy barriers of rate-determining steps(proton transfer and dehydration steps).The 2-pentanone has one elementary step less in the complete reaction mechanism of aldol condensation and preferable energy barrier for proton transfer and dehydration steps,revealing 2-pentanone as terminal ketone is more reactive than 3-pentanone as central ketone.The water molecules dominated the OH-MgO(111)surface after further addition of water,leading to the reduction of turnover frequency of the aldol condensation dimer product as the loss of aldol condensation reaction intermediates in competitive adsorption with water molecules.
