The selection of suitable ionic liquids(ILs)is critical for CO_(2)capture and electrocatalytic conversion into valuable chemical products.The screening process can be enhanced with theoretical simulations that reveal ...The selection of suitable ionic liquids(ILs)is critical for CO_(2)capture and electrocatalytic conversion into valuable chemical products.The screening process can be enhanced with theoretical simulations that reveal the property-performance relationship of ILs,accelerating the identification of optimal candidates.However,anhydrous ILs exhibit low dielectric constants and high ion concentrations,challenging traditional first-principles calculations.Additionally,the spatial distribution of CO_(2)in the electric double layer plays a crucial role in determining the electrocatalytic activity.This work proposes a solutioncorrected constant potential model(CPM-sol)to account for the imbalance between the net charge and the number of electrons on the electrode surface through an implicit consideration of ion distributions.By incorporating solution-phase corrections into the conventional CPM model,we reveal the changes in the Fermi level and charge alongside the reaction process.Furthermore,we systematically investigate the impact of various IL properties on electrode surface charging and CO_(2)distribution.The theoretical results highlight the critical role of interactions between solution components,forming chain-like structures,in determining their distribution in confined environments and influencing the electrode surface charge.These findings provide insights for mechanism-guided electrolyte design.展开更多
基金the financial support from the National Science Foundation-Deutsche Forschungsgemeinschaft(NSF-DFG)Lead Agency Activity in Chemistry and Transport in Confined Spaces under grant no.NSF 2234013.
文摘The selection of suitable ionic liquids(ILs)is critical for CO_(2)capture and electrocatalytic conversion into valuable chemical products.The screening process can be enhanced with theoretical simulations that reveal the property-performance relationship of ILs,accelerating the identification of optimal candidates.However,anhydrous ILs exhibit low dielectric constants and high ion concentrations,challenging traditional first-principles calculations.Additionally,the spatial distribution of CO_(2)in the electric double layer plays a crucial role in determining the electrocatalytic activity.This work proposes a solutioncorrected constant potential model(CPM-sol)to account for the imbalance between the net charge and the number of electrons on the electrode surface through an implicit consideration of ion distributions.By incorporating solution-phase corrections into the conventional CPM model,we reveal the changes in the Fermi level and charge alongside the reaction process.Furthermore,we systematically investigate the impact of various IL properties on electrode surface charging and CO_(2)distribution.The theoretical results highlight the critical role of interactions between solution components,forming chain-like structures,in determining their distribution in confined environments and influencing the electrode surface charge.These findings provide insights for mechanism-guided electrolyte design.
