The rate-limited activation of N≡N triple bonds with high bond energies has been a bottleneck in photoctalytic nitrogen fixation.Here,polymeric carbon nitride with frustrated Lewis pairs(FLPs) was constructed by inse...The rate-limited activation of N≡N triple bonds with high bond energies has been a bottleneck in photoctalytic nitrogen fixation.Here,polymeric carbon nitride with frustrated Lewis pairs(FLPs) was constructed by inserting electron-deficient magnesium into g-C_(3)N_(4)(CN).The synergistic interactions between Mg and amino groups in CN led to a 7.2 fold increase in the photoreactivity of nitrogen(N_(2)) fixation by carbon nitride.展开更多
Photocatalytic CO_(2)reduction is a promising route toward carbon neutrality,yet its practical application is hindered by the high activation energy barrier of v,rapid recombination of photo-generated electrons,and po...Photocatalytic CO_(2)reduction is a promising route toward carbon neutrality,yet its practical application is hindered by the high activation energy barrier of v,rapid recombination of photo-generated electrons,and poor product selectivity of traditional catalysts.Frustrated Lewis pairs(FLPs),which feature spatially separated Lewis acid and base sites,have recently emerged as a novel strategy to overcome these limitations.This review systematically examines the progress in FLPs-based photocatalytic systems.We focus on the construction stra-tegies for FLPs active sites,the optimization of charge carrier dynamics,and the synergistic electron transfer mechanisms with photoactive components.Central theme is the elucidation of microscopic mechanisms gov-erning CO_(2)activation,key intermediate conversion,and the efficient utilization of photogenerated electrons.By synthesizing current knowledge and outlining future prospects,this review aims to provide a theoretical framework that guides the rational design of highly active and selective catalysts for solar-driven CO_(2)reduction.展开更多
Heterogeneous solid frustrated-Lewis-pair(FLP)catalyst is of great promise in practical hydrogenation applications.It has been found that all-solid FLPs can be created on ceria via surface oxygen vacancy regulation.Co...Heterogeneous solid frustrated-Lewis-pair(FLP)catalyst is of great promise in practical hydrogenation applications.It has been found that all-solid FLPs can be created on ceria via surface oxygen vacancy regulation.Consequently,it is desired to investigate the mechanisms of the FLP-catalyzed hydrogenation of C=C and C=O and provide insight into the modification of CeO_(2)catalysts for the selective hydrogenation.In this work,the reaction mechanism of the hydrogenation of CH_(2)=CH_(2)and CH_(3)CH=O at the FLP sites constructed on CeO_(2)(110)surface was investigated by density functional theory(DFT),with the classical Lewis acid-base pairs(CLP)site as the reference.The results illustrate that at the CLP site,the dissociated hydride(H^(δ−))forms a stable H−O bond with the surface O atom,while at the FLP site,H^(δ−)is stabilized by Ce,displaying higher activity on the one hand.On the other hand,the electron cloud density of the Ce atom at the FLP site is higher,which can transfer more electrons to the adsorbed C_(C=C)and O_(C=O)atoms,leading to a higher degree of activation for C=C and C=O bonds,as indicated by the Bader charge analysis.Therefore,compared to the CLP site,the FLP site exhibits higher hydrogenation activity for CH_(2)=CH_(2)and CH_(3)CH=O.Furthermore,at the FLP sites,it demonstrates high efficiency in catalyzing the hydrogenation of CH_(2)=CH_(2)with the rate-determining barrier of 1.04 eV,but it shows limited activity for the hydrogenation of CH_(3)CH=O with the rate-determining barrier of 1.94 eV.It means that the selective hydrogenation of C=C can be effectively achieved at the FLP sites concerning selective hydrogenation catalysis.The insights shown in this work help to clarify the reaction mechanism of the hydrogenation of C=C and C=O at FLP site on CeO_(2)(110)and reveal the relationship between the catalytic performance and the nature of the active site,which is of great benefit to development of rational design of heterogeneous FLP catalysts.展开更多
基金supported by the National Natural Science Foundation of China (No.42377227)Beijing Natural Science Foundation (No.2232061)。
文摘The rate-limited activation of N≡N triple bonds with high bond energies has been a bottleneck in photoctalytic nitrogen fixation.Here,polymeric carbon nitride with frustrated Lewis pairs(FLPs) was constructed by inserting electron-deficient magnesium into g-C_(3)N_(4)(CN).The synergistic interactions between Mg and amino groups in CN led to a 7.2 fold increase in the photoreactivity of nitrogen(N_(2)) fixation by carbon nitride.
基金the National Natural Science Foundation of China(22278190)Qing Lan Project of Jiangsu Province(2023)+1 种基金Open Project of State Key Laboratory of Structural Chemistry(20230022)Jiangsu Collaborative Innovation Center of Technology and Material of Water Treatment.
文摘Photocatalytic CO_(2)reduction is a promising route toward carbon neutrality,yet its practical application is hindered by the high activation energy barrier of v,rapid recombination of photo-generated electrons,and poor product selectivity of traditional catalysts.Frustrated Lewis pairs(FLPs),which feature spatially separated Lewis acid and base sites,have recently emerged as a novel strategy to overcome these limitations.This review systematically examines the progress in FLPs-based photocatalytic systems.We focus on the construction stra-tegies for FLPs active sites,the optimization of charge carrier dynamics,and the synergistic electron transfer mechanisms with photoactive components.Central theme is the elucidation of microscopic mechanisms gov-erning CO_(2)activation,key intermediate conversion,and the efficient utilization of photogenerated electrons.By synthesizing current knowledge and outlining future prospects,this review aims to provide a theoretical framework that guides the rational design of highly active and selective catalysts for solar-driven CO_(2)reduction.
基金supported by the National Natural Science Foundation of China(22302115,22072079)the Fundamental Research Program of Shanxi Province(202303021221056).
文摘Heterogeneous solid frustrated-Lewis-pair(FLP)catalyst is of great promise in practical hydrogenation applications.It has been found that all-solid FLPs can be created on ceria via surface oxygen vacancy regulation.Consequently,it is desired to investigate the mechanisms of the FLP-catalyzed hydrogenation of C=C and C=O and provide insight into the modification of CeO_(2)catalysts for the selective hydrogenation.In this work,the reaction mechanism of the hydrogenation of CH_(2)=CH_(2)and CH_(3)CH=O at the FLP sites constructed on CeO_(2)(110)surface was investigated by density functional theory(DFT),with the classical Lewis acid-base pairs(CLP)site as the reference.The results illustrate that at the CLP site,the dissociated hydride(H^(δ−))forms a stable H−O bond with the surface O atom,while at the FLP site,H^(δ−)is stabilized by Ce,displaying higher activity on the one hand.On the other hand,the electron cloud density of the Ce atom at the FLP site is higher,which can transfer more electrons to the adsorbed C_(C=C)and O_(C=O)atoms,leading to a higher degree of activation for C=C and C=O bonds,as indicated by the Bader charge analysis.Therefore,compared to the CLP site,the FLP site exhibits higher hydrogenation activity for CH_(2)=CH_(2)and CH_(3)CH=O.Furthermore,at the FLP sites,it demonstrates high efficiency in catalyzing the hydrogenation of CH_(2)=CH_(2)with the rate-determining barrier of 1.04 eV,but it shows limited activity for the hydrogenation of CH_(3)CH=O with the rate-determining barrier of 1.94 eV.It means that the selective hydrogenation of C=C can be effectively achieved at the FLP sites concerning selective hydrogenation catalysis.The insights shown in this work help to clarify the reaction mechanism of the hydrogenation of C=C and C=O at FLP site on CeO_(2)(110)and reveal the relationship between the catalytic performance and the nature of the active site,which is of great benefit to development of rational design of heterogeneous FLP catalysts.
