Covalent organic frameworks(COFs)are considered promising catalysts for photocatalytic CO_(2)reduction reaction(pCO_(2)RR)due to facilitated regulations.However,the instability of COFs with dynamic reversible covalent...Covalent organic frameworks(COFs)are considered promising catalysts for photocatalytic CO_(2)reduction reaction(pCO_(2)RR)due to facilitated regulations.However,the instability of COFs with dynamic reversible covalent bonds and the limited modifiability of COFs with irreversible covalent bonds restricted the enhancement of the pCO_(2)RR performance.Herein,three phthalocyanine-based COFs with ether-linked,CoOP,CoPOP,and CoBOP,were successfully prepared via in situ polycondensation using modifiable bis-phthalonitrile.CoBOP achieved a record of syngas performance in pCO_(2)RR systems with photosensitizers and sacrificial agents(CO 83.7 mmol g^(-1)h^(-1)and H_254.7 mmol g^(-1)h^(-1)),surpassing most COF photocatalysts.Additionally,CoOP,CoPOP,and CoBOP exhibit stabilities in extreme environments owing to their irreversible covalent bonds.Experimental and density functional theory analyses confirm that the optimally matched the lowest unoccupied molecular orbital of the linking unit between the photosensitizer and active unit endowed Co BOP with the highest photoelectron transfer efficiency among the three catalysts,boosting its pCO_(2)RR activity.This work is highly instructive for designing COFs with structure-adjustable and irreversible covalent bonds.展开更多
CO_(2)reduction reaction(CO_(2)RR)electrolyzers based on gas diffusion electrode(GDE)enable the direct mass transfer of CO_(2)to the catalyst surface for participation in the reaction,thereby establishing an efficient...CO_(2)reduction reaction(CO_(2)RR)electrolyzers based on gas diffusion electrode(GDE)enable the direct mass transfer of CO_(2)to the catalyst surface for participation in the reaction,thereby establishing an efficient three-phase reaction interface that significantly enhances current density.However,current hydrophobic modification methods face difficulties in achieving precise and substantial control over wettability,and the hydrophobic modifiers tend to significantly impair the conductivity of the electrode and ion transport capabilities.This study employs Nafion ionomers to hydrophobically modify the threedimensional catalyst layer,revealing the bifunctionality of Nafion.The fluorinated backbone of Nafion ensures the hydrophobicity of the entire catalyst layer,while its sulfonic acid groups promote ion transport,without significantly affecting the conductivity of the electrode.Furthermore,by employing modifiers with distinct wettability characteristics,a highly efficient and large-scale manipulation of the hydrophilic/hydrophobic properties of the catalyst layer was successfully realized.The electrode,constructed with silver nanopowder as a representative catalyst and modified with the hydrophobic ionomer Nafion,exhibits a substantial enhancement in both catalytic activity and durability.The optimized electrode exhibited exceptional electrocatalytic performance in both flow cell and membrane electrode assembly(MEA)configurations.Notably,in the MEA,the electrode achieved a remarkable CO Faradaic efficiency(FE)of 93.3%at a total current density of 200 mA cm^(-2),while maintaining stable operation for over 62 h.展开更多
Electrochemical reduction of CO_(2)(CO_(2)RR)to form high-energy-density and high-value-added multicarbon products has attracted much attention.Selective reduction of CO_(2)to C^(2+)products face the problems of low r...Electrochemical reduction of CO_(2)(CO_(2)RR)to form high-energy-density and high-value-added multicarbon products has attracted much attention.Selective reduction of CO_(2)to C^(2+)products face the problems of low reaction rate,complex mechanism and low selectivity.Currently,except for a few examples,copper-based catalysts are the only option capable of achieving efficient generation of C^(2+)products.However,the continuous dynamic reconstruction of the catalyst causes great difficulty in understanding the structure-performance relationship of CO_(2)RR.In this review,we first discuss the mechanism of C^(2+)product generation.The structural factors promoting C^(2+)product generation are outlined,and the dynamic evolution of these structural factors is discussed.Furthermore,the effects of electrolyte and electrolysis conditions are reviewed in a vision of dynamic surface.Finally,further exploration of the reconstruction mechanism of Cu-based catalysts and the application of emerging robotic AI chemists are discussed.展开更多
The catalytic activity and selectivity of CO_(2)reduction reaction(CO_(2)RR)towards C1 and C2 products are fundamentally restricted by the inherent linear scaling relationship among the adsorption-free energies of int...The catalytic activity and selectivity of CO_(2)reduction reaction(CO_(2)RR)towards C1 and C2 products are fundamentally restricted by the inherent linear scaling relationship among the adsorption-free energies of intermediates.To face this challenge,we have proposed a novel multifunctional M1M2@BN electrocatalysts to break the linear scaling relationships in CO_(2)RR and efficiently obtain C1 and C2 products.Our results reveal that the optimal limiting potential is increased from−0.58 V for M@BN to−0.39 V for M1M2@BN,which achieves ultrahigh activity of CO_(2)RR.Further mechanism analysis illuminates that M1M2@BN can selectivity modulate the adsorption strength of OCHO*and OCH_(2)O*/OCHOH*,breaking the linear scaling relationship of adsorption-free energies of key intermediates to achieve the enhanced catalytic activity.Notably,the sufficient active sites on M_(1)M_(2)@BN electrocatalysts can promote the sluggish C–C coupling by capturing two CO intermediates simultaneously,further generating high-value multi-carbon(CH_(2)CH_(2)OH)products.Meanwhile,the thermodynamic stability of M1M2@BN has been demonstrated by ab initio molecular dynamics(AIMD)simulations,which shows the feasibility of commercial application in CO_(2)RR.Our findings provide a novel strategy to modulate the binding strength of intermediates and develop the design of efficient multi-active-site CO_(2)RR electrocatalysts.展开更多
夕阳下的山道弯角,一道橘色魅影划破空气,车身以不可思议的角度侧倾入弯,V型双缸的咆哮在峡谷间回荡。这不是一辆温顺的街车,它以近乎反常的姿态流畅掠过弯心。KTM 1290 SUPER DUKE RR,一台以“超级公爵”为名的限量猛兽,正用180kg的轻...夕阳下的山道弯角,一道橘色魅影划破空气,车身以不可思议的角度侧倾入弯,V型双缸的咆哮在峡谷间回荡。这不是一辆温顺的街车,它以近乎反常的姿态流畅掠过弯心。KTM 1290 SUPER DUKE RR,一台以“超级公爵”为名的限量猛兽,正用180kg的轻盈躯体与132k W的狂暴内心,书写着公升级街车操控哲学的新篇章。展开更多
基金financially supported by the Innovation Capability Support Program of Shaanxi—Science and Technology Innovation Team Project(No.2025RS-CXTD-024)the Fundamental Research Foundation of SHCCIG New Materials Technology Research Institute Co.,Ltd(No.D5204230171)+3 种基金the Fundamental Research Funds for the Central Universities(G2025KY05240)the Natural Science Basic Research Program of Shaanxi(Program No.2024JC-YBQN-0073)the Fundamental Research Funds for the Central Universities(No.D5000250204)Young Talent Fund of Association for Science and Technology in Shaanxi(No.20230101)。
文摘Covalent organic frameworks(COFs)are considered promising catalysts for photocatalytic CO_(2)reduction reaction(pCO_(2)RR)due to facilitated regulations.However,the instability of COFs with dynamic reversible covalent bonds and the limited modifiability of COFs with irreversible covalent bonds restricted the enhancement of the pCO_(2)RR performance.Herein,three phthalocyanine-based COFs with ether-linked,CoOP,CoPOP,and CoBOP,were successfully prepared via in situ polycondensation using modifiable bis-phthalonitrile.CoBOP achieved a record of syngas performance in pCO_(2)RR systems with photosensitizers and sacrificial agents(CO 83.7 mmol g^(-1)h^(-1)and H_254.7 mmol g^(-1)h^(-1)),surpassing most COF photocatalysts.Additionally,CoOP,CoPOP,and CoBOP exhibit stabilities in extreme environments owing to their irreversible covalent bonds.Experimental and density functional theory analyses confirm that the optimally matched the lowest unoccupied molecular orbital of the linking unit between the photosensitizer and active unit endowed Co BOP with the highest photoelectron transfer efficiency among the three catalysts,boosting its pCO_(2)RR activity.This work is highly instructive for designing COFs with structure-adjustable and irreversible covalent bonds.
基金National Key R&D Program of China(2023YFA1507902,2021YFA1500804)the National Natural Science Foundation of China(22121004,22038009,22250008)+2 种基金the Haihe Laboratory of Sustainable Chemical Transformations(CYZC202107)the Program of Introducing Talents of Discipline to Universities,China(No.BP0618007)the Xplorer Prize,China,for their financial support。
文摘CO_(2)reduction reaction(CO_(2)RR)electrolyzers based on gas diffusion electrode(GDE)enable the direct mass transfer of CO_(2)to the catalyst surface for participation in the reaction,thereby establishing an efficient three-phase reaction interface that significantly enhances current density.However,current hydrophobic modification methods face difficulties in achieving precise and substantial control over wettability,and the hydrophobic modifiers tend to significantly impair the conductivity of the electrode and ion transport capabilities.This study employs Nafion ionomers to hydrophobically modify the threedimensional catalyst layer,revealing the bifunctionality of Nafion.The fluorinated backbone of Nafion ensures the hydrophobicity of the entire catalyst layer,while its sulfonic acid groups promote ion transport,without significantly affecting the conductivity of the electrode.Furthermore,by employing modifiers with distinct wettability characteristics,a highly efficient and large-scale manipulation of the hydrophilic/hydrophobic properties of the catalyst layer was successfully realized.The electrode,constructed with silver nanopowder as a representative catalyst and modified with the hydrophobic ionomer Nafion,exhibits a substantial enhancement in both catalytic activity and durability.The optimized electrode exhibited exceptional electrocatalytic performance in both flow cell and membrane electrode assembly(MEA)configurations.Notably,in the MEA,the electrode achieved a remarkable CO Faradaic efficiency(FE)of 93.3%at a total current density of 200 mA cm^(-2),while maintaining stable operation for over 62 h.
文摘Electrochemical reduction of CO_(2)(CO_(2)RR)to form high-energy-density and high-value-added multicarbon products has attracted much attention.Selective reduction of CO_(2)to C^(2+)products face the problems of low reaction rate,complex mechanism and low selectivity.Currently,except for a few examples,copper-based catalysts are the only option capable of achieving efficient generation of C^(2+)products.However,the continuous dynamic reconstruction of the catalyst causes great difficulty in understanding the structure-performance relationship of CO_(2)RR.In this review,we first discuss the mechanism of C^(2+)product generation.The structural factors promoting C^(2+)product generation are outlined,and the dynamic evolution of these structural factors is discussed.Furthermore,the effects of electrolyte and electrolysis conditions are reviewed in a vision of dynamic surface.Finally,further exploration of the reconstruction mechanism of Cu-based catalysts and the application of emerging robotic AI chemists are discussed.
基金financially supported by the National Natural Science Foundation of China(Nos.52403306 and 51902084)the Natural Science Foundation of Hebei Province(Nos.B2024202047 and B2020202089)+1 种基金the Hebei Province Higher Education Science and Technology Research Foundation(No.QN2019030)the Program for Changjiang Scholars and Innovative Research Team in University(No.PCSIRT:IRT17R33).
文摘The catalytic activity and selectivity of CO_(2)reduction reaction(CO_(2)RR)towards C1 and C2 products are fundamentally restricted by the inherent linear scaling relationship among the adsorption-free energies of intermediates.To face this challenge,we have proposed a novel multifunctional M1M2@BN electrocatalysts to break the linear scaling relationships in CO_(2)RR and efficiently obtain C1 and C2 products.Our results reveal that the optimal limiting potential is increased from−0.58 V for M@BN to−0.39 V for M1M2@BN,which achieves ultrahigh activity of CO_(2)RR.Further mechanism analysis illuminates that M1M2@BN can selectivity modulate the adsorption strength of OCHO*and OCH_(2)O*/OCHOH*,breaking the linear scaling relationship of adsorption-free energies of key intermediates to achieve the enhanced catalytic activity.Notably,the sufficient active sites on M_(1)M_(2)@BN electrocatalysts can promote the sluggish C–C coupling by capturing two CO intermediates simultaneously,further generating high-value multi-carbon(CH_(2)CH_(2)OH)products.Meanwhile,the thermodynamic stability of M1M2@BN has been demonstrated by ab initio molecular dynamics(AIMD)simulations,which shows the feasibility of commercial application in CO_(2)RR.Our findings provide a novel strategy to modulate the binding strength of intermediates and develop the design of efficient multi-active-site CO_(2)RR electrocatalysts.
文摘夕阳下的山道弯角,一道橘色魅影划破空气,车身以不可思议的角度侧倾入弯,V型双缸的咆哮在峡谷间回荡。这不是一辆温顺的街车,它以近乎反常的姿态流畅掠过弯心。KTM 1290 SUPER DUKE RR,一台以“超级公爵”为名的限量猛兽,正用180kg的轻盈躯体与132k W的狂暴内心,书写着公升级街车操控哲学的新篇章。
